Craqueo cataltico de polmeros; estudio

de diferentes sistemas polmero/catalizador

Deseada Berenguer Muoz

UNIVERSIDAD DE ALICANTE
DEPARTAMENTO DE INGENIERA QUMICA

CRAQUEO CATALTICO DE POLMEROS;

ESTUDIO DE DIFERENTES SISTEMAS
POLMERO/CATALIZADOR

Memoria para optar al Grado

de Doctor presentada por

Deseada Berenguer Muoz

Alicante, 2008

D. ANTONIO MARCILLA GOMIS, Catedrtico del Departamento de Ingeniera

Qumica de la Facultad de Ciencias de la Universidad de Alicante, y

Da. AMPARO GMEZ SIURANA, Profesora Titular del Departamento de

Ingeniera Qumica de la Facultad de Ciencias de la Universidad de Alicante,

CERTIFICAMOS:
Que Da. DESEADA BERENGUER MUOZ, Licenciada en Qumicas,
ha realizado bajo nuestra direccin, en el Departamento de Ingeniera
Qumica de la Facultad de Ciencias de la Universidad de Alicante, el
trabajo que con el ttulo CRAQUEO CATALTICO DE POLMEROS;
ESTUDIO

DE

DIFERENTES

SISTEMAS

POLMERO/CATALIZADOR constituye su memoria para aspirar al

Grado de Doctor, reuniendo a nuestro juicio, las condiciones necesarias
para ser presentada y defendida ante el Tribunal correspondiente.

Y para que conste a los efectos oportunos, en cumplimiento de la

legislacin vigente, firmamos el presente certificado en Alicante, a 24 de
Noviembre de 2008.

Fdo. Antonio Marcilla Gomis

Fdo. Amparo Gmez Siurana

VB

Vicente Gomis Yages

Director de Departamento
i

Este trabajo no hubiera sido posible sin la colaboracin de muchas

personas, a las que me gustara agradecrselo con estas palabras.

En primer lugar, me gustara dar las gracias a mis directores de Tesis

Antonio Marcilla Gmis y Amparo Gmez Siurana, por darme la oportunidad de
realizar esta Tesis bajo su tutela, adems de por su apoyo incondicional y su
dedicacin a lo largo de la misma.

Quisiera tambin agradecer a mis compaeros del departamento, por las

largas charlas en el stano que me animaron e hicieron ms llevaderos esos das
complicados, especialmente a Rosa Navarro, Isabel Martnez, Reme Hernndez y
Fran Valds que tras estos aos se han convertido para mi en unos buenos
amigos. Tambin destacar la inestimable ayuda del grupo de polmeros, del
departamento de Ingeniera Qumica, ya que sin su ayuda y consejos la totalidad
de este trabajo no hubiera sido posible: Maribel Beltrn, ngela Garca, Juan
Carlos Garca, Sergio Menargues, sin olvidar a Manolo Asensio y Manuel
Rodrguez, sin cuya sabidura no sabramos como hacer funcionar ms de un
equipo.

Finalmente quisiera agradecer el apoyo que me brind mi familia para

embarcarme en esta aventura, a mi madre Antonia, mi padre Daniel, y a mi
hermana Vanesa, gracias por todo. Y un agradecimiento muy especial a Rafa,
que me ha acompaado en este viaje, gracias por estar siempre ah, gracias por
escucharme y gracias por apoyarme incondicionalmente y por no dejar que me
rinda nunca, t si que vales

iii

Lista de Publicaciones

La tesis expuesta a continuacin consta de las siguientes publicaciones, las cuales

aparecen referidas en el texto, mediante su correspondiente numeracin romana.
I. A. Marcilla, A. Gmez-Siurana and D. Berenguer, Study of the influence of the
characteristics of different acid solids in the catalytic pyrolysis of different
polymers, Applied Catalysis A: General, Volume 301, Issue 2, February 2006,
Pages 222-231.
II. A. Marcilla, A. Gmez-Siurana and D. Berenguer, Study of the early deactivation
in pyrolysis of polymers in the presence of catalysts, Journal of Analytical and
Applied Pyrolysis, Volume 79, Issues 1-2, May 2007, Pages 443-449.
III. A. Marcilla, A. Gmez-Siurana, J.C. Garca Quesada and D. Berenguer,
Characterization of high-impact polystyrene by catalytic pyrolysis over Al-MCM41: Study of the influence of the contact between polymer and catalyst, Polymer
Degradation and Stability, Volume 92, Issue 10, October 2007, Pages 1867-1872.
IV. A. Marcilla, A. Gmez-Siurana, J.C. Garca Quesada, and D. Berenguer,
Characterization of Styrene-Butadiene copolymers by catalytic pyrolysis over AlMCM-41, Journal of Analytical and Applied Pyrolysis, Available online 4
September 2008.
V. A. Marcilla, A. Gmez-Siurana, A.O. Odjo, R. Navarro and D. Berenguer,
Characterization of vacuum gas oillow density polyethylene blends by
thermogravimetric analysis, Polymer Degradation and Stability, Volume 93, Issue
3, March 2008, Pages 723-730.
VI. A. Marcilla, A. Gmez-Siurana, D. Berenguer, Study of the decomposition of
Vacuum Gas Oils-Low Density Polyethylene blends: evolution of the gases,
Polymer Degradation and Stability, Available online 24 July 2008.

Otras publicaciones del autor relacionadas con la Tesis.

1 - A. Marcilla, A. Gmez-Siurana and D. Berenguer, Study of the influence of the

characteristics of different acid solids in the catalytic pyrolysis of different polymers,
(Mediterranean Congress of Chemical Engineering), Noviembre 2005, Poster.

2 - A. Marcilla, A. Gmez-Siurana, J.C. Garca Quesada and D. Berenguer, Influence of

the polymer/catalyst mixing degree in the different decomposition stages in the MCM41 catalytic pyrolysis of HIPS, (Mediterranean Congress of Chemical Engineering),
Noviembre 2005, Poster.

3 - A. Marcilla, A. Gmez-Siurana and D. Berenguer, Study of the Early Deactivation

in the catalytic Pyrolysis of Polymers, (International Symposium on Analytical and
Applied Pyrolysis), Junio 2006, Poster.

4 - Marcilla A., Odjo A. O., Garcia-Qeusada J. C., Gmez-Siurana A., Martinez R. N.,
Berenguer D. M., Design and Construction of a Fluid Catalytic Cracking Pilot Plant for
Vacuum Gas Oil-Plastic Wastes Blends Co-Processing, (Chemical Reactor Engineering
Conference), Agosto 2007, Poster.

5 - Marcilla A., Odjo A. O., Garcia-Quesada J. C., Gomez-Siurana A., Berenguer D.,
Martinez R. N., Flow Behaviour of Blends of Vacuum Gas Oil and Low Density
Polyethylene Blends, (Chemical Reactor Engineering Conference), Agosto 2007,
Poster.

6 - Marcilla A., Odjo A.O., Garca-Quesada J.C., Gmez A., Martnez R.N., Berenguer
D., Flow Properties of Vacuum Gas OilLow Density Polyethylene Blends, Fuel
Processing Technology, (2007), pp. 0378-3820.

7 - A. Marcilla, A. Gmez-Siurana, J.C. Garca Quesada and D. Berenguer,

Characterization of Styrene-Butadiene copolymers by catalytic pyrolysis over AlMCM-41, (International Symposium on Analytical and Applied Pyrolysis), Mayo 2008,
Poster.

vi

8 - Odjo A.O., Marcilla-Gomis A., Martinez R.N., Gmez-Siurana A., Garca-Quesada

J.C., Berenguer Muoz D., Garca-Corts A.N., Prediction of the Viscosity of Vacuum
Gas Oil-Low Density Polyethylene Blends under Varying Shear Rates, Concentrations
and Temperaturas, International Journal of Chemical Reactor Engineering: Vol. 6
(2008) pp.1542-6580.

9 - A. Marcilla, A. Gmez-Siurana, and D. Berenguer, Study of the decomposition of

Vacuum Gas Oils-Low Density Polyethylene Blends by GC/MS; Evolution of the
gases, (11th Mediterranean Congress of Chemical Engineering), Octubre 2008, Poster.

10 - A. Marcilla, A. Gmez-Siurana, and D. Berenguer, Study of the decomposition of

Vacuum Gas Oils-Low Density Polyethylene Blends by GC/MS; Evolution of the
liquids, (11th Mediterranean Congress of Chemical Engineering), Octubre 2008, Poster.

11 - A. Marcilla, M. I. Beltrn, D. Berenguer, A.N, Garca, J.C. Garca-Quesada, A.

Gmez-Siurana, M. R. Hernndez, I. Martinez, R. Navarro, F. Valdes, Catalytic
pyrolysis of polymers. Study of the activity of catalysts and deactivation and
regeneration processes Current Topics in Catalysis (2008), en Prensa.

vii

ndice

NDICE
Agradecimientos.iii
Lista de publicaciones.v
Otras comunicacionesvi
ndice.......ix
ndice de tablas..xii
ndice de figuras...xiii

1. RESUMEN...1

2. INTRODUCCIN...7
2.1. Reciclado de residuos plsticos11
2.1.1. Reciclado mecnico...12
2.1.2. Reciclado qumico.15
2.1.2.1. Degradacin trmica...16
2.1.2.2. Pirlisis cataltica18
2.1.2.3. Gasificacin.21
2.1.2.4. Hidrogenacin.22
2.1.3. Recuperacin de energa23
2.1.4. Problemas y perspectivas actuales del reciclado25
2.2. Estructura y propiedades de los catalizadores utilizados en el reciclado
qumico de los plsticos...28
2.2.1. Estructura de las zeolitas29
2.2.2. Caractersticas de las zeolitas.31
2.2.2.1. Propiedades fsicas..31
2.2.2.2. Propiedades qumicas..32
2.2.2.3. Propiedades catalticas33
2.2.2.4. Desactivacin de los materiales zeolticos..35
2.3. Principales materiales de SiO2-Al2O3 utilizados como catalizadores...37
2.3.1. Zeolita HZSM-5.37
2.3.2. Material MCM-41..39
2.3.3. Zeolita USY...40
ix

ndice

2.3.4. Zeolita Beta41

2.3.5. Catalizador de equilibrio FCC.......42
2.4. Materiales Plsticos..43
2.4.1. Clasificacin...47
2.4.1.1. Segn su origen...47
2.4.1.2. Segn su mecanismo de polimerizacin.47
2.4.1.3. Segn su composicin qumica...48
2.4.1.4. Segn sus aplicaciones48
2.4.1.5. Segn su comportamiento al elevar su temperatura49
2.5. Mecanismos de degradacin.50
2.5.1. Craqueo trmico.50
2.5.2. Craqueo cataltico..52
2.5.2.1. Reacciones de los carbocationes sobre los centros activos
del catalizador..52
2.5.2.2. Reacciones Mecanismos de craqueo cataltico en
polmeros.55

3. OBJETIVOS..59

4. MATERIALES Y MTODOS.63
4.1. Catalizadores seleccionados.63
4.1.1. Catalizadores sintetizados en este trabajo..63
4.1.1.1. Preparacin de la zeolita HZSM-5.63
4.1.1.2. Preparacin del material MCM-41..64
4.1.1.3. Zeolitas comerciales67
4.2.

Tcnicas

de

caracterizacin

de

los

materiales

slidos

cidos. 67
4.2.1. Difraccin de Rayos X (DRX)..68
4.2.2. Microscopia electrnica de transmisin (TEM)69
4.2.3. Microscopia electrnica de barrido (SEM)...70
4.2.4. Isotermas de adsorcin de nitrgeno.72
4.2.5. Fluorescencia de Rayos X (FRX)..77
4.2.6. Desercin trmica programada (DTP) de amoniaco.78

ndice

4.2.7. Resonancia magntica nuclear de 27Al y 29 Si...81

4.3. Caractersticas de los materiales empleados.82
4.3.1. Polmeros...82
4.3.2. Catalizadores..84
4.4. Tcnicas, condiciones experimentales y equipos empleados...85
4.4.1. Tcnicas experimentales empleadas en el desarrollo de la tesis....85
4.4.1.1. Anlisis termogavimtrico (TGA)..85
4.4.1.2. Espectrometra FTIR conectada en lnea con un
analizador termogavimtrico (TGA/FTIR).86
4.4.1.3. Anlisis en un Reactor de lecho fijo ...87
4.4.2.

Condiciones

experimentales

empleadas

en

los

distintos

trabajos.91
4.4.2.1. Publicacin I; Study of the influence of the characteristics
of different acid solids in the catalytic pyrolysis of different polymers..91
4.4.2.2. Publicacin II; Study of the early deactivation in
pyrolysis of polymers in the presence of catalysts..91
4.4.2.3.

Publicacin

III;

Characterization

of

high-impact

polystyrene by catalytic pyrolysis over Al-MCM-41: Study of the influence of the

contact between polymer and catalyst.92
4.4.2.4. Publicacin IV; Characterization of Styrene-Butadiene
copolymers by catalytic pyrolysis over Al-MCM-41......94
4.4.2.5. Publicacin V; Characterization of vacuum gas oillow
density polyethylene blends by thermogravimetric analysis ..95
4.4.2.6. Publicacin VI; Study of the decomposition of Vacuum
Gas

Oils-Low

Density

Polyethylene

blends:

evolution

of

the

gases

.....96

5. CONCLUSIONES.99

6. BIBLIOGRAFA.107

xi

ndice

NDICE DE TABLAS

Tabla 2.1. Plsticos ms comunes en los residuos de origen domstico....10

Tabla 2.2. Poder calorfico de diferentes materiales.......................................................23
Tabla 2.3. Ventajas e inconvenientes de las diferentes vas de reciclado...26
Tabla 2.4. Tratamiento de residuos plsticos en Europa................................................27
Tabla 2.5. Ejemplos de cdigos de zeolitas....................................................................37
Tabla 4.1. Reactivos empleados para la sntesis de la zeolita HZSM-5.........................64
Tabla 4.2. Reactivos empleados para la sntesis de los materiales MCM-41.................65
Tabla 4.3. Propiedades fisicoqumicas de los materiales plsticos seleccionados.83
Tabla 4.4. Propiedades fisicoqumicas de los catalizadores...84
Tabla 4.5. Asignacin de los picos obtenidos en cromatografa de gases......................90

xii

ndice

NDICE DE FIGURAS
Figura 2.1. Consumo de plsticos en Espaa en 2005.........................................8
Figura 2.2. Posibles vas de reciclado..............................................................................9
Figura 2.3. Esquema del reciclado mecnico.14
Figura 2.4. Esquema del reciclado qumico...15
Figura 2.5. Esquema del proceso de recuperacin energtica23
Figura 2.6. Estructura de las zeolitas..............................................................................30
Figura 2.7. Estructura y dimensiones de los poros de la zeolita HZSM5.......................................................................................................................................38
Figura 2.8. Poro hexagonal del material MCM-41.........................................................39
Figura 2.9. Crecimiento del material MCM-41..............................................................40
Figura 2.10. Estructura y dimensiones de los poros de la zeolita USY..41
Figura 2.11. Estructura y politipos de la zeolita Beta.42
Figura 2.12. Polimerizacin del estireno para dar poliestireno; n indica el grado de
polimerizacin.45
Figura 2.13. Diferencia entre polmero lineal y polmero ramificado...45
Figura 2.14. a) Homopolmero b) Copolmero alternante c) Copolmero en bloque d)
Copolmero aleatorio e) Copolmero de injerto...46
Figura 2.15. Fuerza relativa cualitativa de los centros cidos necesarios en las
reacciones de iones carbenio...52
Figura 4.1. DRX de una Zeolita A.................................................................................69
Figura 4.2. Microfotografa obtenida por TEM de la zeolita HZSM-5.........................70
Figura 4.3. Imagen obtenida por SEM de una zeolita USY comercial..........................71
Figura. 4.4. Representacin esquemtica de los seis tipos de isotermas de
adsorcin..73
Figura 4.5. Isoterma de N2 a 77K tpica de una zeolita HZSM-5..................................74
Figura 4.6. Curva DTG obtenida a partir de la DTP de NH3 para un material
MCM-41.........................................................................................................................80
Figura 4.7. RMN

27

Al de HZSM-5...............................................................................82

Figura 4.8. Esquema del montaje TGA/FTIR................................................................87

Figura 4.9. Diagrama del reactor de lecho fijo...88

xiii

ndice

Figura 4.10. Cromatograma de gases obtenido en la descomposicin del polietileno

mediante pirolisis trmica y cataltica.90

xiv

RESUMEN

Resumen

En la ltima dcada se ha impuesto la opinin de que la pirlisis de los plsticos

es la tecnologa ms interesante para el desarrollo de un proceso a gran escala en el que
se traten plsticos de diferente naturaleza para su reciclado qumico. Sin embargo, la
pirlisis trmica es un proceso que requiere un elevado gasto energtico, debido a la
baja capacidad calorfica de los plsticos. La adicin de un catalizador en el proceso
permite reducir la temperatura de descomposicin y aumenta la selectividad a ciertos
productos. En el presente trabajo se han puesto a punto mtodos de sntesis y
caracterizacin de diferentes catalizadores slidos cidos que sean de utilidad en el
proceso de pirlisis de polmeros. Los materiales sintetizados se han caracterizado y se
ha estudiado la influencia de las principales caractersticas fisicoqumicas y texturales
sobre su actividad para catalizar el proceso de pirlisis de diferentes polmeros. Con esta
finalidad, se han sintetizado y caracterizado tres slidos cidos diferentes.

HZSM-5

MCM-41(47)

MCM-41(7)

y las tcnicas de caracterizacin empleadas han sido:

Microscopa electrnica de transmisin (TEM)

Microscopa electrnica de barrido (SEM)

Resonancia magntica nuclear (RMN)

Adsorcin de nitrgeno a 77 K

Fluorescencia de rayos X (FRX)

Desorcin trmica programada (DTP) de amoniaco

Difraccin de rayos X (DRX)

La actividad cataltica de dichos slidos en la pirlisis de polmeros se ha

evaluado a la vista de su comportamiento en la pirlisis de cuatro polmeros con
diferentes caractersticas estructurales:

Polietileno de baja densidad (LDPE)

Polipropileno (PP)
1

Resumen

Poliestireno de alto impacto (HIPS)

Copolmero de etileno y acetato de vinilo con un 27.5% de acetato de

vinilo (EVA)

El comportamiento de los diferentes sistemas polmero-catalizador se estudi

mediante ensayos de pirlisis trmica y de pirlisis cataltica en una termobalanza y en
una termobalanza conectada en lnea con un espectrmetro FTIR. Los resultados
obtenidos en este estudio han sido recogidos en la publicacin I que lleva por ttulo
Study of the influence of the characteristics of different acid solids in the catalytic
pyrolysis of different polymers.

A raz del estudio mediante termogravimetra de la actividad cataltica de los

distintos slidos cidos, se observ que los materiales que presentan una elevada rea
superficial as como una elevada acidez, como es el caso del material MCM-41(7),
presentaban un comportamiento no observado anteriormente por otros autores. En
primer lugar se observ que las curvas de prdida de peso obtenidas en la
descomposicin de los diferentes polmeros presentaban un hombro a bajas
temperaturas, siendo ste ms importante conforme aumentaban los impedimentos
estricos asociados a los sustituyentes laterales del polmero. Para estudiar este efecto se
seleccion el catalizador MCM-41(7) y se realizaron experimentos en termobalanza
donde se realizaron sucesivos ciclos de calentamiento/enfriamiento. En dichos ensayos
se calent hasta la temperatura donde se observaba dicho hombro, siendo est siempre
inferior a la temperatura de la principal etapa de descomposicin e inferior a la
temperatura en la que se produce la pirlisis trmica, garantizando as que el efecto
estudiado se deba exclusivamente a la presencia del catalizador. Tras cuatro ciclos de
calentamiento/enfriamiento, se realiz un experimento completo de pirolisis hasta 550
C, tanto del material resultante de los ciclos sucesivos, como de una mezcla de dicho
material y polmero fresco, observndose que la importancia relativa de este hombro
disminua sensiblemente y que la temperatura de mxima velocidad de descomposicin
para la etapa principal de degradacin aumentaba.

Los resultados de este estudio se muestran en la publicacin II Study of the

early deactivation in pyrolysis of polymers in the presence of catalysts.

Resumen

Por otro lado, el estudio de la descomposicin cataltica del poliestireno de alto

impacto (HIPS) en presencia de los catalizadores con elevado tamao de poro, como los
MCM-41, mostr la existencia de tres etapas diferentes de descomposicin, que no
aparecan en presencia del resto de slidos cidos, con menor tamao de poro, como la
zeolita ZSM-5, y que podra estar relacionada con la descomposicin, en etapas
diferentes, de dos tipos de dominios en el polmero, de poliestireno y de polibutadieno.
Adems, la importancia relativa de dichas etapas pareca depender en gran medida del
grado de contacto entre las partculas del polmero y las partculas del catalizador.

Para estudiar este efecto en mayor profundidad se moli y tamiz una muestra
de HIPS, con la finalidad de obtener fracciones con diferente tamao de partcula, y se
estudio el comportamiento de dichas fracciones en presencia del catalizador MCM41(7) mediante termogravimetria. Como resultado de este estudio se presenta la
publicacin III donde se comprueba la influencia del grado de contacto entre el
polmero y el catalizador Characterization of high-impact polystyrene by catalytic
pyrolysis over Al-MCM-41: Study of the influence of the contact between polymer and
catalyst.

Los resultados obtenidos sugieren la posibilidad de utilizar tcnicas de pirlisis

cataltica similares a las aplicadas hasta el momento para llevar acabo el estudio de la
descomposicion de otros copolmeros de poliestireno-polibutadieno, como es el caso de
los SBS. Para ello se desarroll y aplic un modelo pseudocintico que permite evaluar
la cantidad relativa del polmero que evoluciona a travs de cada etapa de
descomposicin, y se estudio la importancia del contacto existente entre el copolmero y
el catalizador empleado. Los resultados de este estudio se muestran en la publicacin IV
Characterization of Styrene-Butadiene copolymers by catalytic pyrolysis over AlMCM-41.

Los trabajos descritos en los prrafos precedentes surgen como consecuencia del
estudio sistemtico realizado para cubrir el objetivo general planteado inicialmente de
estudiar el reciclado de residuos plsticos mediante el proceso de pirlisis cataltica.
Con este mismo objetivo, se consider la posibilidad de llevar a cabo el proceso
utilizando unidades similares a las de craqueo cataltico en lecho fluidizado (FCC) de
las refineras, y disolviendo el material plstico en un gasleo de vaco similar al que se
3

Resumen

suele usar como alimento para obtener productos dentro del rango de las gasolinas. Con
el fin de evaluar esta posibilidad, se prepararon muestras con diferentes relaciones
VGO/Polietileno, y se realizaron diferentes estudios. En primer lugar, se analiz en
termobalanza el comportamiento de las mezclas frente a diferentes catalizadores,
utilizando tanto los sintetizados en el laboratorio como con otros slidos cidos
comerciales, as como tambin un catalizador de FCC de equilibrio. Se trabajo con
diferentes

relaciones

muestra:catalizador.

Tambin

se

determin

mediante

termogravimetria en atmsfera oxidante, la cantidad de coque depositado sobre cada

catalizador. Los resultados de este estudio aparecen reflejados en la publicacin V que
lleva por ttulo Characterization of vacuum gas oillow density polyethylene blends by
thermogravimetric analisis

Finalmente se estudi en un reactor de lecho fijo la evolucin con la temperatura

(o el tiempo) de la composicin de los productos obtenidos en la descomposicin de
VGO, PE y la mezcla VGO/PE al 10% en presencia del catalizador de FCC de
equilibrio con una relacin catalizador:polmero de 7:1. Por un lado se recogen en gases
generados en bolsas tedlar. Las muestras recogidas fueron posteriormente analizadas
mediante CG/MS, lo que permiti identificar los diferentes compuestos generados y
analizar la evolucin de stos con la temperatura. Los resultados correspondientes a la
evolucin de la composicin de los gases generados en el proceso de descomposicin
trmica y cataltica del PE, VGO, y la mezcla VGO-PE se recogen en la publicacin VI
Study of the decomposition of Vacuum Gas Oils-Low Density Polyethylene blends:
evolution of the gases.

INTRODUCCIN
2.1. Reciclado de residuos plsticos
2.1.1. Reciclado mecnico
2.1.2. Reciclado qumico
2.1.3. Recuperacin de energa
2.1.4. Problemas y perspectivas actuales del reciclado
2.2. Estructura y propiedades de los catalizadores utilizados en el
reciclado qumico de los plsticos
2.2.1. Estructura de las zeolitas
2.2.2. Caractersticas de las zeolitas
2.3. Principales materiales de SiO2-Al2O3 utilizados como
catalizadores
2.3.1. Zeolita HZSM-5
2.3.2. Material MCM-41
2.3.3. Zeolita USY
2.3.4. Zeolita Beta
2.3.5. Catalizador de equilibrio FCC
2.4. Materiales plsticos
2.4.1. Clasificacin
2.5. Mecanismos de degradacin durante los procesos de pirolisis
2.5.1. Craqueo trmico
2.5.2. Craqueo cataltico

Introduccin
Desde 1970, la produccin de plsticos en el mundo ha crecido drsticamente;
as, entre 1989 y 2004, la produccin de plstico en el oeste de Europa aument de 100
a 225 millones de toneladas al ao, con un crecimiento aproximado del 3-5% por ao
(APME, 2006). Este crecimiento es debido a que los plsticos juegan un papel crucial
en cada uno de los aspectos de la vida cotidiana, incorporando avances tecnolgicos y
mejorando la calidad de vida.

Los avances en investigacin y desarrollo tecnolgico han convertido a los

plsticos en uno de los materiales ms verstiles, ligeros y eficientes en el
aprovechamiento de los recursos. Por lo tanto, al analizar el uso de los recursos
disponibles, para poder mantener y desarrollar el ritmo de vida de la sociedad actual, es
fundamental considerar todas las etapas de la vida de los plsticos, desde la extraccin
de las materias primas y la fabricacin de los materiales, hasta el fin de su vida til,
pasando por la fase de utilizacin.

La inmensa mayora de los plsticos se obtiene a partir de materias primas

derivadas de productos petroqumicos, coproductos del petrleo o del gas natural.
Gracias a las continuas innovaciones en los materiales y en los procesos de ingeniera,
la amplia familia de plsticos disponibles hoy en da permite un ahorro de recursos
durante su fabricacin y uso. Por ejemplo en Europa el sector del automvil emplea
cerca de 2 millones de toneladas de plsticos al ao, cerca del 7% de la produccin
mundial, lo cual requiere el equivalente de 3,5 millones de toneladas de petrleo para su
fabricacin (APME, 2006). Sin embargo, gracias a la ligereza de los plsticos
empleados en la fabricacin de componentes de automviles, se obtiene un ahorro de 12
millones de toneladas de petrleo cada ao al hacer ms eficaz el uso del combustible;
eso deriva tambin en la consiguiente reduccin de las emisiones de CO2 en una cuanta
de 30 millones de toneladas al ao (APME, 2006).

Otro campo donde es particularmente til en empleo de plsticos es el sector del

envasado, donde su uso conlleva una reduccin considerable en el peso de los
productos. Por ejemplo, el 50% de las mercancas de Europa se envasan en plstico y
estos mismos plsticos representan tan solo el 20% del total de los envases producidos.
En los ltimos diez aos se ha producido una disminucin de cerca del 28% en el peso
promedio de los plsticos usados en los artculos envasados, lo cual representa una
7

Introduccin

reduccin de 1,8 millones de toneladas. Adems se ha calculado que, sin el uso de los
plsticos, el peso promedio de los envases aumentara en un 291% (APME, 2006).

Otro ejemplo de aplicacin donde se producen mejoras ambientales por el uso de

los plsticos es en la edificacin. El equivalente energtico que se utiliza para fabricar
aislamientos de espumas de plstico (EPS o PUR), se recupera tras un ao de uso de
estos aislamientos.

Como ya se ha dicho, los materiales plsticos estn presentes en la vida diaria en

multitud de aplicaciones. Segn las cifras del el Centro Espaol de Plsticos (CEP,
2005), los datos correspondientes al ao 2005 en Espaa muestran que el sector de
envase y embalaje contina siendo el principal mercado respecto a la demanda de
materias plsticas, con una participacin del 46,8% respecto al total de los plsticos
consumidos, tal y como se puede observar en el siguiente grfico (figura 2.1).

Juguetes
1,7%

Otros 4,3%

Agricultura
5,9%

Electrodomesticos
2,3%
Automovil
9,4%

Pinturas
2,7%

Piezas
industriales
2,1%
Mobiliario
5,9%

Envasado
46,8%

Electrnica
3,8%

Construccin
15,1%

Figura 2.1. Consumo de plsticos en Espaa en 2005 (CEP, 2005)

El Centro Espaol de Plsticos http://www.cepinform.es/esp/publicaciones/estudiosector.asp

Sin embargo, los productos plsticos derivados de cada una de estas aplicaciones
no tienen el mismo tiempo de vida media, es decir, no se convierten en residuos al
mismo tiempo. Unas aplicaciones generan los residuos al ao de su uso (envases, por
ejemplo) y otras al cabo de cincuenta aos o ms (construccin, por ejemplo). El resto
de aplicaciones presentan valores intermedios. Este es, por ejemplo, el caso de un
ordenador, un electrodomstico, un coche, muebles o los plsticos agrcolas utilizados
8

Introduccin
para varias campaas. As en la figura 2.2 se han representado de una forma
esquemtica las diferentes etapas que integran el ciclo de vida para los plsticos, que
van desde su fabricacin y uso, hasta las posibles vas de reciclado, sobre las que se
incidir con mayor detalle ms adelante.
Hidrlisis
Reciclado
Directo
Materias
Primas

Produccin

Material de
Desecho

Envasado

Reciclado
Qumico

Incineracin

Gliclisis

Monomeros

Despolmeracin
Trmica

Gas de Sntesis

Gasificacin

Pirlisis

Va Trmica

Termlisis

Corriente
Hidrocarburos

Uso

Distribucin

Despolimeracin
Qumica

Otros

Craqueo
Craqueo

Energa

Va Cataltica

Hidrocraqueo
Hidrogenacin

Vertedero

RECICLADO
RECICLADO

CICLO DE VIDA
Reciclado

Producto

Proceso

Figura 2.2. Posibles vas de reciclado [1]

Si se analizara el contenido de una bolsa de basura de origen domestico, lo que

se observara es que alrededor del 14% de su peso se debe a plsticos, y en su mayora
provienen de envases de un solo uso y de todo tipo de envoltorios y embalajes (bolsas
de polietileno, bandejas de espuma...). La clasificacin ms comn de los residuos
plsticos habituales en el mbito domstico y su proporcin se muestra en la Tabla 2.1.

Est claro que todo consumo genera un residuo. Los plsticos representan un
recurso muy valioso y apreciado como para convertirse en productos de desecho y ser
tirados a la basura directamente. Sin embargo, actualmente muchos de estos residuos
acaban en vertederos, cuando realmente se podran aprovechar como materias primas de
nuevos materiales (reciclado) o como fuente de energa (valorizacin energtica).

Introduccin

Tabla 2.1. Tipos de plsticos ms comunes y composicin

en los residuos de origen domstico
Siglas
PET
HDPE
PVC
LDPE
PP

PS

OTROS

Cdigo
reciclaje

Nombre y principales usos

Tereftalato de polietileno. Botellas de bebidas
y bandejas para microondas.
Polietileno de alta densidad. Botellas para
leche y de lquidos de limpieza.
Cloruro de polivinilo. Bandejas de comida, film
transparente, botellas para agua mineral y
champs.
Polietileno de baja densidad. Bolsas de plstico
y basura.
Polipropileno. Envases margarinas y bandejas
para microondas.
Poliestireno. Botes de yogur, bandejas de
espuma para carnes y pescados, cajas de
hamburguesas, envases de huevos, cubertera de
plstico, envases protectores de equipos
electrnicos y juguetes.
Termoplsticos.
Termoestables.

Composicin
de los residuos
plsticos
5%
13%
14%

19%
15%
6%

12%
16%

La otra cara de este proceso est relacionada con las cuestiones ambientales,
econmicas y sociales que plantea el crecimiento de los residuos slidos en general y
que incluyen:

Saturacin de los depsitos tradicionales de basura, saturacin de vertederos, e

incremento de la incineracin. Se ha tenido que crear nuevos vertederos, con la
problemtica adicional de la bsqueda de ubicaciones que planteen los mnimos
conflictos. La creacin de nuevas incineradoras plantea los mismos problemas
sociales que los vertederos y, aunque la incineracin de plsticos proporciona
una energa similar a la gasolina, no pueden incinerarse directamente con la
basura, ya que producen contaminantes atmosfricos muy peligrosos para la
salud y el medio ambiente.

Demanda pblica de servicios de recogida selectiva de basuras. La recogida

selectiva de basuras tiene muchas ventajas, entre ellas la disminucin de los
costes de reciclaje, y a veces tiene una buena acogida social.

10

Introduccin
-

Polucin ambiental visible y efecto negativo en el turismo.

Establecimiento de obligaciones legales para cumplir la legislacin (recogida,

reciclado...)

2.1. RECICLADO DE RESIDUOS PLSTICOS

Cuando se habla del tratamiento de los residuos plsticos, las opciones que
existen son las mismas que para el resto de residuos, y estn basadas en la aplicacin de
las tres "erres": reducir, reutilizar y recuperar, aunque con algunas particularidades
debidas a las caractersticas propias de estos materiales.

La reduccin en origen es el primer paso hacia una gestin de residuos

satisfactoria. Supone la utilizacin de menos cantidad de plsticos para cubrir las
necesidades con la misma eficacia. Tambin supone disear el producto de forma que se
reduzca el consumo de material y se simplifique el nmero de plsticos diferentes
utilizados en cada objeto.

Por otra parte, hay que tener en cuenta que los plsticos presentan una serie de
caractersticas que los hace materiales idneos para ser reutilizados, ya que son
duraderos, lavables, resistentes, esterilizables, etc. Con el desarrollo de envases ligeros
de recambio, este concepto est cada vez ms vigente, tanto en el sector de la
distribucin (cajas, pallets, bidones industriales y otros) como en el hogar.

Una vez que han sido agotadas las vas anteriores, los plsticos pasan a
convertirse en residuos. En este momento se propone su recuperacin, que se puede
realizar esencialmente de tres maneras alternativas: el reciclado mecnico, el reciclado
qumico y la recuperacin energtica.

11

Introduccin

2.1.1. Reciclado mecnico

Hoy en da, en la mayor parte de las zonas donde se utilizan plsticos se estn
desarrollando infraestructuras para el reciclado mecnico, para poder utilizar los
residuos como material para la fabricacin de los nuevos productos plsticos.

El reciclado mecnico consiste en el tratamiento de los residuos plsticos por

medio de la presin y el calor para volver a darles forma y conseguir otros objetos
iguales o distintos de los iniciales. El primer paso para su realizacin es la recogida de
los residuos, que bien puede ser en realizada por los propios consumidores, o bien en
una planta de separacin a la que lleguen mezclados entre s o con otros residuos. Se
trata, en resumen, de obtener residuos de termoplsticos identificados, separados por
tipos, fciles de recoger y que se puedan obtener en grandes cantidades.

Por ello, los residuos plsticos ideales para el reciclado mecnico son aquellos
objetos de mayor tamao, por ejemplo botellas, parachoques y depsitos de gasolina de
los automviles fuera de uso, o residuos recogidos en grandes cantidades como es el
caso del film procedente de invernaderos.

Como ya se ha mencionado, el proceso de reciclado mecnico en s mismo

comienza con la clasificacin de los residuos u objetos de plstico usados. Los
productos constituidos por un solo material, una vez separados y clasificados, pueden
pasar a la etapa siguiente, en la que se aplicar el tratamiento a los distintos plsticos
considerndolos como producto nico. En casos especficos y con la tecnologa
adecuada, una corriente determinada de productos (por ejemplo, residuos termoplsticos
mezclados procedentes de recogida selectiva de envases) puede ser tratada sin
separacin. En todo caso los materiales plsticos ms complejos o no termoplsticos
deben ser rechazados en la etapa de clasificacin.

El paso siguiente en el proceso de reciclado es la trituracin o molienda, que se

realiza en dos etapas, con una etapa previa de eliminacin de contaminantes (papeles,
etiquetas, etc). A continuacin, el producto se almacena en un silo intermedio donde el
material espera hasta la siguiente etapa del proceso.

12

Introduccin
Antes de pasar a la etapa final en necesario un nuevo proceso de lavado de los
plsticos y una posterior separacin de otras sustancias contaminantes, etapa que se
puede repetir si fuera necesario, para pasar despus a una etapa de centrifugado y
secado del material, tras la cual pasa a ser almacenado en nuevos silos intermedios en
los que, adems, se realiza una homogenizacin que garantice una calidad constante y
adecuada.

Finalmente, el producto triturado, limpio, seco y homogneo se alimenta a una

extrusora y tras el proceso de aditivado y granceado, se obtiene la granza lista para ser
procesada por diferentes tcnicas. Fundamentalmente, se pueden considerar tres tipos de
procesados diferentes:

a) Procesado del producto reciclado directamente. En este caso, las piezas

obtenidas tienen en general propiedades inferiores a las fabricadas con polmero
virgen.
b) Mezcla de la granza reciclada con polmero virgen para alcanzar las prestaciones
requeridas. El ejemplo tpico es la adicin de polmero virgen a la mezcla de
termoplsticos para la fabricacin, por ejemplo, de perfiles.
c) Coextrusin del producto reciclado. Un ejemplo de esta tcnica es la fabricacin
de botellas para bebidas, en la que la capa intermedia puede ser de polmero
reciclado y la interior (en contacto con el producto) y la exterior son de polmero
virgen.

El resultado de estos tratamientos es la obtencin de nuevos objetos de plstico

reciclado: bolsas, maceteros, tuberas de drenaje, pallets para el transporte, seales de
trfico, bancos para parques, etc. Algunos de estos objetos son habituales en nuestra
vida cotidiana desde hace aos, como por ejemplo las bolsas de basura o las tuberas de
desages, mientras que otros son ms novedosos y estn en estos momentos iniciando
su entrada en los mercados. El proceso de reciclado mecnico se muestra en modo
esquemtico en la Figura 2.3.

13

Introduccin

Figura 2.3. Esquema del reciclado mecnico

El reciclado mecnico a nivel industrial se realiza en Espaa prcticamente

desde la aparicin del plstico como material y de la instalacin de las primeras
industrias transformadoras. La antigedad media del sector de reciclado es de unos 30
aos y, en estos momentos, hay cerca de cien empresas dedicadas a la recuperacin y el
reciclado de los plsticos. Las dos terceras partes de estas empresas se encuentran en
Catalua y Levante, debido a la concentracin existente en estas zonas de industrias
transformadoras. Desde que surgieron en Espaa las primeras experiencias de recogida
selectiva de plsticos, muchas de las industrias recicladoras han empezado a tratar
tambin los residuos procedentes de las mismas.

Como es fcil deducir, el futuro de la recuperacin de los envases plsticos por

esta va est directamente influenciado por la extensin de la red de recicladores a las
zonas donde actualmente no existen o su nmero es muy escaso, debido a los altos
costes de transporte de un residuo tan ligero, que hara inviable la recuperacin si las
distancias a las plantas de reciclado fueran grandes.

Segn el 8 Informe Anual de Cicloplast titulado "Estadsticas sobre Consumo,

Generacin y Gestin de Plsticos en Espaa, ao 2003", el reciclado total de plsticos
en Espaa en el ao 2003 fue de unas 329.000 toneladas, frente a las 181.000 toneladas
recicladas en 1997. El sector de procedencia de los mismos es fundamentalmente el
sector industrial (69% de la capacidad), siendo estos residuos principalmente recortes de
materias primas (52%), de envases y embalajes industriales postconsumo (17%). En
menor medida los residuos provienen de otros sectores como el agrcola, el comercial,
el domstico o el de la automocin.

14

Introduccin
El plstico de mayor consumo en Espaa, que es el polietileno, sigue siendo
lder en trminos de reciclado. El polietileno (de alta y de baja densidad) representa el
71,4% del total de los plsticos que se reciclaron en nuestro pas, seguido por el PVC.
En menor medida se reciclan polipropileno y poliestireno; el reciclado de PET en
Espaa sigue siendo mnimo.

2.1.2. Reciclado qumico

Durante el reciclado qumico, los residuos y las piezas de plstico usadas se
descomponen a travs de un proceso qumico para dar lugar a componentes ms
sencillos, pudiendo llegar a la obtencin de los monmeros, que pueden ser utilizados
nuevamente como materias e incluso pueden servir para producir nuevamente polmeros
que dan lugar a nuevos productos (Figura 2.4).

Figura 2.4. Esquema del reciclado qumico

A diferencia de lo que ocurre en el reciclado mecnico, este procedimiento se

puede aplicar tanto a mezclas de distintos polmeros, con lo que se evita la necesidad de
separacin por tipos, como a polmeros termoestables. El reciclado qumico puede
realizarse mediante diferentes procesos, como la pirlisis (trmica y cataltica), la
hidrogenacin y la gasificacin. Estos procesos representan alternativas de
recuperacin de los residuos plsticos que se encuentran actualmente en fase de
desarrollo. Las instalaciones de reciclado qumico europeas que estn operativas a nivel
comercial se encuentran sobre todo en Alemania (Kaminsky y col., 1995).

15

Introduccin

Algunas opciones para llevar a cabo la descomposicin de plsticos tienen la

ventaja de que se pueden realizar utilizando parcialmente la infraestructura existente en
las refineras con tecnologa ya contrastada. Los inconvenientes que presenta esta
alternativa se centran en:

1) El coste de la necesaria separacin y clasificacin de plsticos.

2) Las dificultades asociadas a la alimentacin del equipo de tratamiento,
preferiblemente en una corriente fluida.
3) La necesidad de eliminacin de contaminantes como el cloro y el nitrgeno.

Una vez resueltos los mayores problemas tecnolgicos de estos mtodos, el reto
es hacer interesante la economa de estos tratamientos, cuya competitividad depender
siempre del precio del barril de petrleo, ya que suponen la mezcla del residuo plstico
con el crudo que se alimenta a la refinera.

2.1.2.1. Degradacin trmica

En la ltima dcada se esta imponiendo la opinin de que la termlisis o pirlisis
de los plsticos es la tecnologa ms interesante para el desarrollo de un proceso a gran
escala, en el que se traten conjuntamente plsticos de diferente naturaleza, sin necesidad
de invertir un elevado esfuerzo en la separacin selectiva de los residuos plsticos.
Adems, un proceso de craqueo, trmico o cataltico, puede integrarse en la operacin
de una refinera con el consiguiente ahorro.

La compaa qumica alemana BASF ha construido una planta de

transformacin de desechos plsticos en Ludwigshaffen: en el proceso, los plsticos
mezclados y aglomerados son fundidos; el cloruro de hidrgeno generado se absorbe y
se extrae y la materia que resta es despolimerizada en un reactor de lecho fluidizado a
400 C y transformada en un producto lquido en un porcentaje del 60 % y un 20 % en
gas (Arandes y col., 2004). Esta unidad es rentable gracias a la subvencin del
organismo encargado de la gestin de las actividades de transformacin de desechos de
los embalajes de la zona del Rin. Duales System Deutchsland (DSD) ofrece una prima
de 144 euros por cada tonelada de desechos de plsticos tratados en la nueva planta.

16

Introduccin
En USA y en Europa se han desarrollado procesos de pirlisis trmica en
reactores rotatorios y de lecho fluidizado. Los reactores de lecho fluidizado ofrecen
condiciones muy adecuadas para este proceso, ya que presentan:

1) Elevada capacidad de transporte de calor y de materia entre fases, lo que reduce

la energa requerida en un proceso que es fuertemente endotrmico.
2) Rgimen isotermo y, como consecuencia, uniformidad de temperatura.
3) Reducido tiempo de contacto de los productos primarios de pirlisis (entre
varios segundos y 1,5 min frente a los 20 min de los reactores rotatorios), lo que
minimiza las reacciones secundarias de los productos primarios de la pirlisis,
ofreciendo como consecuencia una mayor uniformidad del producto.

Tambin puede destacarse la versatilidad de los equipos de lecho fluidizado para

el tratamiento del conjunto de los materiales plsticos. Esta es una propiedad interesante
si se tiene en cuenta la heterogeneidad de estos materiales. As por ejemplo, la
separacin de los plsticos procedentes de uso domstico ofrece un 57% de poliolefinas,
14% de policloruro de vinilo, 1% de poliestireno, 5% de otros plsticos o papel, junto
con un 5% de materiales inorgnicos tales como arena y sales (Arandes y col., 2004).

El proceso de pirlisis puede combinarse con la valorizacin energtica del

producto. Se ha descrito un proceso, que se esta llevando a cabo en Suiza, en el que se
trata los residuos slidos urbanos compactndolos, desgasificndolos y pirolizndolos
en una etapa a 600 C, de donde los gases producidos son alimentados a un horno de
incineracin a 2000 C (Arandes y col., 2004). Siemens KWU dispone de otro proceso
en el que los residuos son pirolizados en un horno rotatorio a 450 C. Cada tonelada de
residuos genera 655 kg de gas y 345 kg de slidos y el gas se alimenta en un incinerador
a 1300 C. El coste es de 208 $/t, un 30% menos que los costes de incineracin en
Alemania (Fouhy y col., 1993).

La estrategia perseguida en la pirlisis trmica es la optimizacin del proceso

para conseguir los productos ms rentables, recuperando los monmeros tales como
etileno, propileno, estireno, y obteniendo un elevado rendimiento de aromticos:
benceno, tolueno, xilenos (Kaminsky y Rssler, 1992). Los elevados requerimientos
energticos de la pirlisis pueden compensarse mediante la combustin parcial de los
17

Introduccin

plsticos, de forma que la pirlisis se pueda mantener autotrmicamente en el intervalo

600-800 C.

2.1.2.2. Pirlisis cataltica

Varios autores han estudiado la influencia de diferentes catalizadores en los
mecanismos de descomposicin trmica de distintos materiales (Munteanu y col., 1981,
Varhegyi y col., 1998, Carrasco, 1993, Marcilla y col., 2001a, 2001b, 2002, Hagelberg
y col., 2002). La adicin de un catalizador mejora la calidad de los productos obtenidos
en la pirlisis de residuos plsticos y adems permite reducir la temperatura de
descomposicin y aumenta la selectividad a ciertos productos (Ohkita y col., 1993,
Pinto y col., 1999). Por tanto, mediante la eleccin del catalizador adecuado, se puede
optimizar la distribucin de productos obtenidos, para, por ejemplo, obtener
combustibles de una mayor calidad que los que proporciona la pirlisis trmica.

De acuerdo con Aguado y Serrano (1999), el craqueo cataltico presenta las

siguientes ventajas:

La

rotura

de

las

cadenas

de

polmero

comienza

temperaturas

considerablemente menores que en la descomposicin trmica.

Cuando se comparan el craqueo cataltico y el craqueo trmico llevados a la

misma temperatura, el craqueo cataltico transcurre a mayor rapidez, es decir,
con menor energa de activacin.

Los productos obtenidos en el craqueo cataltico son de mayor calidad que los
obtenidos en la descomposicin trmica. As, la presencia de una elevada
proporcin de estructuras ramificadas, cclicas y aromticas en los lquidos
producidos, les confiere propiedades muy similares a las de las gasolinas
comerciales. Adems, la distribucin de productos puede modificarse mediante
la seleccin del catalizador.

Los catalizadores slidos cidos, tales como las zeolitas, favorecen las
reacciones de transferencia de hidrgeno en dichos centros cidos. Adems, el acceso de
las molculas a los centros reactivos del catalizador, as como el desarrollo de los
productos finales en el interior de los poros est limitado por su tamao. Por tanto, la
18

Introduccin
preferencia por el uso de las zeolitas en este tipo de procesos se debe a su gran acidez y
al efecto estrico que presentan, factores que controlan la calidad de los productos
aportando selectividad en la forma y el tamao (Pinto y col., 1999, Onu y col., 1999).
En la actualidad, la relacin entre la calidad y la fuerza de los centros cidos del
catalizador y la composicin de los productos de la pirlisis constituye un tema de
investigacin que est recibiendo mucha atencin dentro de la literatura cientfica. Los
slidos cidos ms utilizados como catalizadores son: zeolitas sintticas, slice-almina,
zeolitas naturales y otros aluminosilicatos con estructura porosa adecuada.

Parte de los trabajos que se estn llevando a cabo en este campo se centran en el
estudio de la formacin de coque durante el proceso de craqueo (Benito y col., 1996,
Lin y col., 1997, Guisnet y col., 1996, 2001, Arandes y col., 1999, Pater y col., 1999),
que se deposita en la superficie del catalizador haciendo que ste se desactive
gradualmente y que requiera procesos de regeneracin en los que se elimina total o
parcialmente el coque formado. En general, los problemas que se presentan son
similares a los que se plantean en las operaciones de refino cataltico de la industria del
refino de petrleo.

Dado que el principal componente plstico de los residuos slidos urbanos es el

PE, ste es el polmero cuya pirlisis, tanto trmica como cataltica, ha sido ms
estudiada (Kaminsky y col., 1989, 1992, 1995, Conesa y col., 1997, Scott y col., 1990),
siguindole en importancia el PP, (Kim y col., 2002, Marcilla y col., 2003a, 2003b). La
posibilidad de modificar en la direccin deseada la composicin de los productos de
pirlisis, por ejemplo aumentando la cantidad de alquenos o de aromticos, se ha
abordado mediante el estudio de la pirlisis trmica de mezclas de plsticos (Pinto y
col., 1999). Este objetivo se consigue, por ejemplo, aumentando la proporcin de PP y
PS de la mezcla de partida, sin embargo, ni tcnica ni econmicamente es factible
obtener una composicin inicial determinada de los residuos plsticos. Por tanto, el uso
de catalizadores adecuados para optimizar la formacin de determinados productos se
plantea tambin como una buena alternativa que permitira evitar la separacin previa
de los componentes de los residuos plsticos.

Los estudios sobre la pirlisis cataltica de polmeros pueden plantearse

utilizando diferentes tcnicas y equipos, dependiendo de cual sea el objetivo principal
19

Introduccin

de la investigacin que se este realizando. En general, existen varios mtodos para la

realizacin del craqueo cataltico de polmeros:

Craqueo cataltico de polmeros mediante contacto directo de ste con el

catalizador. Puede realizarse en distintos tipos de reactores, en equipos
especficos de pirlisis flash (pyroprobe), termobalanza, etc. (Sharratt y col.,
1997, Park y col., 1999, Serrano y col., 2001).

Craqueo trmico del polmero y posterior craqueo cataltico de los compuestos

de pirlisis (Okhita y col., 1993, Sakata y col., 1996, 1999, Onu y col., 1999).

Como se mencion anteriormente, un enfoque alternativo, que cobra cada vez

ms importancia para el reciclado terciario, se basa en el hecho de que es posible
disolver algunos polmeros en las alimentaciones usuales del proceso de craqueo
cataltico en lecho fluidizado (FCC) de las refineras y convertirlos en productos del
rango de la gasolina (Ng y col, 1995). Este enfoque se presenta como factible en las
unidades actuales de FCC sin cambios importantes en la tecnologa de las mismas dada
su versatilidad (King y col., 1992), que permite procesar alimentaciones ampliamente
variables.

Los polmeros de base olefnica (polietileno, polipropileno) y de base estirnica

(poliestireno, poliestireno-polibutadieno), que tienen consumo masivo, podran
ciertamente reciclarse mediante el proceso antes mencionado, ya que se disuelven sin
inconvenientes en las alimentaciones tpicas de las unidades de FCC, que son los
gasoleos de vaco (VGO). Ng (1995) estudi la conversin de polietileno segn este
proceso, disolvindolo en un VGO comercial y observ que para una determinada
relacin de catalizador/alimentacin era posible aumentar la produccin de gasolina
significativamente; sin embargo, estos estudios fueron realizados utilizando un reactor
de lecho fijo, por lo que cualquier extensin de estos resultados a la operacin comercial
debe hacerse con una cierta cautela.

En general, el proceso consiste en una operacin cclica, donde las partculas del
catalizador, de un tamao promedio de 70 m, circulan en un reactor de lecho
fluidizado, donde se desactiva por deposicin carbonosa en el reducido tiempo de
contacto con los hidrocarburos reactivos (tpicamente menor a 10 segundos), y pasan
20

Introduccin
posteriormente a un regenerador donde el coque es quemado. El catalizador regenerado
regresa al reactor y reiniciar as el ciclo (King, 1992). Debido a esto, el catalizador sufre
fuertes cambios desde su estado original hasta alcanzar el que se denomina estado de
equilibrio, que es con el que el catalizador regenerado entra de nuevo al reactor de
FCC.

Normalmente, el catalizador empleado en los procesos de craqueo cataltico es

un catalizador compuesto, donde su principal componente es una zeolita (habitualmente
la zeolita Y), que est dispersada sobre una matriz que puede poseer caractersticas muy
variadas, que van desde matrices activas (alminas) a matrices inactivas (slice,
caolines), ms diversos aditivos de funcin especfica.

El proceso de FCC implica un conjunto muy complejo de reacciones catalizadas

por los centros cidos de la zeolita; entre otras, craqueo, isomerizacin, transferencia de
hidrgeno y oligomerizacin. Las reacciones de transferencia de hidrgeno tienen una
fuerte incidencia sobre la calidad de los productos del FCC, dado que al consumir
olefinas y naftnicos para generar parafinas y aromticos, hacen que se pierda octanaje
de las gasolinas (Sedran y col., 1994). As, es deseable minimizarlas, pero sin prdida
excesiva de actividad en los catalizadores. En este sentido, debe tenerse presente que la
densidad de sitios cidos interconectados parece ser un parmetro clave incidente en
este tipo de reacciones, y est directamente relacionado con el tamao de celda unitaria
(de la Puente y Sedran, 2000; Galiano y Sedran, 1997). Las reacciones de
oligomerizacin por su parte, generadoras de hidrocarburos de alto peso molecular, han
sido muy poco estudiadas sobre catalizadores de FCC. stas dependen de la densidad de
sitios cidos, aparentemente en mayor medida que las reacciones de transferencia de
hidrgeno (Olah y col., 1985). Consecuentemente, el efecto de la desaluminizacin sera
tambin un factor muy importante sobre este tipo de reacciones, ya que si la
desaluminizacin es excesiva podra llegar a inhibirlas de manera significativa.

2.1.2.3. Gasificacin
En un proceso de gasificacin tiene lugar la oxidacin parcial de los
hidrocarburos para producir gas de sntesis (mezcla de monxido de carbono e
hidrgeno), que puede utilizarse como combustible para la generacin de electricidad,
21

Introduccin

como materia prima para la fabricacin de metano o amonaco o incluso como agente
reductor para la produccin de acero en altos hornos. Esta tcnica presenta la ventaja,
frente a otros procedimientos de reciclado qumico, de poder admitir como alimentacin
toda la corriente de residuos municipales, sin necesidad de separar previamente los
plsticos.

Son muchas las compaas que estn investigando esta opcin de reciclado,
entre ellas Shell Oil (Reinink, A. y col., 1993), pero es Thermoselec, S.A. (Locarno,
Suiza) quien lidera esta tecnologa. En su planta piloto instalada en Verbania (Italia) se
tratan 4,2 t/h de residuos slidos municipales, que producen 500 kg de gas de sntesis,
220 kg de escoria, 23 kg de metales y 18 kg de sales por cada tonelada de residuo
tratado. En el proceso, los residuos, previamente compactados y desgasificados, se
pirolizan a 600 C y alimentan al gasificador a 2.000 C. El gas de sntesis obtenido, una
vez limpio, se quema en una turbina de gas para producir 300 kw de electricidad. Est
prevista la puesta en marcha en Alemania de una planta de 20 t/h.

2.1.2.4. Hidrogenacin
Para el aprovechamiento de los residuos plsticos tambin se pueden utilizar
procesos catalticos de refino tales como la hidrogenacin cataltica. La hidrogenacin
es, por el momento, el proceso ms desarrollado, as por ejemplo, Veba Oel modific
en 1992 una unidad de tratamiento de residuos de crudo en Bottrop (Alemania) para
coalimentarla con plsticos molidos, pudiendo reciclar hasta 40.000 t/ao de residuos
plsticos con contenidos en PVC de hasta un 10% ( Fouhy, K. y col., 1993). La unidad
opera a 150-300 kg/cm2 y 470 C, en atmsfera de hidrgeno, y produce un crudo
sinttico (syncrude) que contiene un 60% de parafinas, 30% de nafta, 9% de aromticos
y un 1% de olefinas. La conversin es del 80%, con una eficiencia energtica del 88%,
va neutralizacin del HCl generado. Este crudo sinttico se utiliza para alimentar una
refinera y complejos petroqumicos cercanos.

En los procesos de hidrogenacin cataltica, la transformacin de los residuos

tiene lugar en presencia de zeolitas, aluminosilicatos o catalizadores supercidos,
originando como productos fracciones de hidrocarburos de diferente composicin y uso:
C4-C7 para gasolina y C8-C16 para lubricantes sintticos u oligmeros que se que se
22

Introduccin
pueden emplear como depresores del punto de congelacin o para mejorar el ndice de
viscosidad de aceites lubricantes. As, el proceso Kurata (Dawans, F. 1994),
desarrollado a escala piloto, y basado en el craqueo cataltico en presencia de un
catalizador polimetlico, permite tratar mezclas de polmeros con contenidos en PVC de
hasta un 20%, originado como producto principal un aceite hidrocarbonado con menos
de 100 ppm de cloro. La reaccin tiene lugar a baja temperatura (200 - 250 C), presin
atmosfrica y en ausencia de oxgeno para evitar la formacin de dioxinas.

2.1.3. Recuperacin de Energa

Los plsticos usados pueden ser aprovechados como combustible por su elevado
poder calorfico; por ejemplo, un kilogramo de polietileno produce la misma energa
que un kilogramo de fuel o de gas natural y mucha ms que el carbn (tabla 2.2). Por
ello se hace til, en los casos en los que no sea viable el reciclado mecnico o qumico,
aprovechar este potencial de los residuos plsticos como fuente de electricidad o calor.
Esta alternativa est especialmente indicada para aquellos residuos que presentan
deterioro o suciedad, como es el caso de una parte de los plsticos que proceden de la
agricultura o en determinados casos de residuos slidos urbanos. En la Figura 2.5 se
muestra de forma esquemtica el proceso de recuperacin energtica.

Figura 2.5. Esquema del proceso de recuperacin energtica

Tabla 2.2. Poder calorfico de diferentes materiales

Material

Plsticos

Carbn

Gas Natural

Fuel

Papel

Poder Calorfico (MJ/kg)

46

29

48

44

17

23

Introduccin

Se ha determinado que los residuos plsticos generados por una familia y que
acaban en los vertederos en Europa en un ao contienen energa suficiente para calentar
agua para 500 baos o para que un televisor funcione durante 5.000 horas. Un ejemplo
ms: un envase de yogur de 0,3 litros contiene la energa necesaria para mantener una
bombilla encendida durante una hora.

La recuperacin de energa a partir de los residuos plsticos puede llevarse a

cabo de varias maneras tal y como se muestra en los ejemplos que se describen a
continuacin:

Recuperacin de energa de los residuos plsticos mezclados con el resto de los

residuos slidos urbanos (RSU). Los plsticos suponen en Espaa casi un 11%
de los RSU y aumentan considerablemente el poder energtico de los RSU.
Alrededor del 60% de las plantas de incineracin de RSU en Europa realizan
recuperacin de energa. La mayor parte de ellas usa un intercambiador de calor
y una caldera para producir energa para la poblacin. Otro gran nmero usa
tambin la primera salida de vapor para mover una turbina y producir
electricidad.

Recuperacin de residuos plsticos separados del resto de RSU mediante

combustin. En este caso se tratan exclusivamente los residuos plsticos que no
sean aptos para el reciclado mecnico. Un claro ejemplo de la recuperacin de
energa de los residuos plsticos es en el caso de los residuos agrcolas. Cuando
los plsticos han sido degradados por el aire y el sol durante varias temporadas,
se aconseja la valorizacin energtica, ya que su recuperacin por va mecnica
implica un impacto medioambiental mayor que el beneficio que se va a obtener.

Uso de los residuos plsticos como combustibles alternativos en plantas

cementeras. En la actualidad, muchas centrales trmicas y cementeras utilizan
como combustible el carbn. La utilizacin de residuos plsticos como sustituto
parcial del carbn incrementa el poder calorfico a la vez que disminuye
substancialmente la emisin de dixido de carbono, produce menos metales
pesados, no genera dixido de azufre, al no ser el azufre un componente de los
plsticos y produce menos cenizas, lo que implica un menor impacto ambiental.
Diferentes residuos plsticos son adecuados como combustibles en cementeras,

24

Introduccin
como por ejemplo, el film agrcola y ciertos residuos plsticos del comercio e
industria y recortes industriales.

En definitiva, la obtencin de energa a partir de residuos y, en particular, de los

residuos plsticos, puede ser una solucin a la dependencia actual que se tiene en
Europa de las importaciones de combustibles fsiles, que se estima ser un 70% en el
ao 2010 si el escenario contina como en la actualidad. Solo el 10% de los residuos
municipales de Europa podran cubrir el 5% de sus propias necesidades energticas y
ahorraran 14 millones de toneladas de petrleo al ao.

2.1.4. Problemas y perspectivas actuales del reciclado

En el campo del reciclado de plsticos hay dos tipos de problemas: los
problemas tcnicos y los problemas logsticos. Entre los problemas tcnicos se
encuentran:

La heterogeneidad de los materiales constitutivos de los envases.

Falta de identificacin de los materiales en algunos envases.

El volumen que ocupan, que dificulta no slo el proceso de recoleccin, sino

tambin el proceso de reciclado.

Existe una estacionalidad para el reciclado. Este es un problema de carcter

tcnico-econmico, pues existen temporadas que favorecen y otras que
perjudican el reciclado. Por ejemplo cuando baja el precio de los plsticos, los
recicladores se ven en el problema de no poder comercializar el producto.

Dentro de los problemas logsticos figuran:

Falta de educacin del consumidor final. Los ciudadanos comnmente no saben

bien que hacer con los residuos plsticos, de forma que todos van a desembocar
al basurero, mezclados con los dems desechos.

Inexistencia de un marco jurdico para el manejo de los residuos slidos

urbanos. Aunque puede ser que todo est bien definido legalmente, lo cierto es
que hay un cierto desconocimiento.

25

Introduccin

Carencia de un organismo responsable del manejo integral de los residuos

slidos urbanos.

Falta de compromiso y toma de conciencia real de los sectores involucrados

A modo de resumen en la Tabla 2.3 se muestra una comparacin entre las tres
principales vas de reciclado y se analizan las principales ventajas e inconvenientes que
presenta cada mtodo. En general, el reciclado mecnico es el ms extendido debido, a
que en es un proceso sencillo, aunque presenta una serie de inconvenientes como la
necesidad de separacin, ya que solo se puede aplicar a un tipo de plsticos a la vez, y
solo a plsticos que no sean termoestables. Adems el material resultante es de menor
calidad (deficiencias en color y en propiedades plsticas) lo cual limita la demanda en el
mercado.

Tabla 2.3. Ventajas e inconvenientes de las diferentes vas de reciclado

Reciclado

Ventajas

Mecnico

Recuperacin Energtica

Necesidad de separacin

Solo se puede aplicar a plsticos

termoestables

sencillas

Es posible obtener energa

Posibilidad de ubicacin
cerca de ciudades

Qumico

Proceso e instalaciones

Inconvenientes

Bajo coste de tratamientos

El material resultante es de menor calidad

Poca demanda en el mercado

Gran inversin inicial

Necesidad de depuracin de gases

Coste de mantenimiento elevado si no

existe recuperacin energtica

Se generan cenizas

Necesita temperaturas elevadas (proceso

No es necesaria la
separacin de los distintos

muy endotrmico).

plsticos.

A estas temperaturas se pueden formar

dioxinas y furanos.

Se obtiene un amplio abanico de

productos.

La recuperacin energtica permite obtener energa, adems de que existe la

posibilidad de ubicar las incineradoras prximas a las ciudades, con lo que se abaratan
los costes de transporte. Sin embargo requieren una gran inversin inicial, adems de la
26

Introduccin
necesidad de depurar los gases que como ya se ha dicho presentan sustancias muy
toxicas a bajas concentraciones, y se generan cenizas.

La gran ventaja del reciclado qumico (pirlisis trmica) es que no es necesario

la separacin de los plsticos, sin embargo presenta una serie de desventajas que en
muchos casos se pueden solucionar con el uso de catalizadores como las zeolitas, es
decir, mediante la pirlisis cataltica. Entre estos inconvenientes hay que destacar que
este proceso es muy endotrmico con lo que es necesario trabajar a temperaturas
elevadas que pueden dar lugar a la formacin de dioxinas y furanos. El empleo de
catalizadores permite reducir sensiblemente la temperatura de trabajo, con lo se evita la
formacin de dichas sustancias. Adems, debido a la propiedad de tamiz molecular que
presentan las zeolitas, se pueden obtener fracciones de hidrocarburos ms selectivas,
como combustibles tipo gasolinas, lubricantes, etc.

Por ltimo, si se analiza la evolucin del proceso de eliminacin de plsticos en

los ltimos aos en Europa, se puede observar una mayor tendencia hacia el reciclado y
a la recuperacin de energa, pero que segn los datos obtenidos en el 2006, estn muy
lejos de la previsiones que se manejaban en el ao 2000, y solo se consigui reducir en
un 39 % la cantidad de plstico que termina su vida en el vertedero (tabla 2.4).

Tabla 2.4. Tratamiento de residuos plsticos en Europa (APME)

Destino

1992

Previsto Datos
2000

2006

77%

10%

50%

Reciclado mecnico

8%

20%

19%

Reciclado qumico

0%

20%

1%

15%

50%

30%

Vertedero

Recuperacin energtica

27

Introduccin

2.2.

ESTRUCTURA

PROPIEDADES

DE

LOS

CATALIZADORES UTILIZADOS EN EL RECICLADO QUMICO

DE LOS PLSTICOS
Como se ha puesto de manifiesto en el apartado anterior, diversos autores han
estudiado la influencia de diferentes catalizadores en los mecanismos de
descomposicin trmica de distintos materiales plsticos (Munteanu y col., 1981,
Varhegyi y col., 1998, Carrasco, 1993, Marcilla y col., 2001a, 2001b, 2002),
observndose que la adicin de un catalizador mejora la calidad de los productos
obtenidos en la pirlisis y adems permite reducir la temperatura de descomposicin y
aumenta la selectividad a ciertos productos (Ohkita y col., 1993, Pinto y col., 1999).

Los catalizadores slidos cidos, tales como las zeolitas, favorecen las
reacciones de transferencia de hidrgeno debido a la presencia de numerosos centros
cidos que, junto a la limitaciones que presentan sus tamaos de poro, permite controlar
la calidad de los productos, aportando selectividad en la forma y el tamao (Pinto y col.,
1999, Onu y col., 1999).

Las zeolitas fueron descritas por primera vez por el minerlogo sueco Cronstedt
(1756), al descubrir un mineral (Estilbita) que perda agua cuando se calentaba, un
proceso ahora conocido como intumescencia. l denomin a este mineral zeolite, del
griego zeo (hervir) y lithos (piedra), piedra que hierve. A partir de entonces, las zeolitas
se han considerado como un grupo de minerales especifico compuesto por unas 50
especies (Fleischer y Mandarino, 1991).

El estudio y las aplicaciones de las zeolitas han aumentado considerablemente en

las ltimas dcadas. Centenares de miles de toneladas de zeolitas se usan cada ao para
eliminar la dureza del agua, en detergentes, como catalizadores, como absorbentes, para
controlar el pH de los suelos, la humedad y como aditivos de abonos (Bekkum y col.,
1991). Actualmente, la investigacin en zeolitas se centra en estudios relacionados con
la sntesis, las propiedades de intercambio catinico y sus aplicaciones como
catalizadores.

28

Introduccin

2.2.1. Estructura de las zeolitas

Las zeolitas son aluminosilicatos hidratados altamente cristalinos de los
elementos de los grupos I y II, en particular, Na, K, Mg, Ca, Sr, y Ba, que al
deshidratarse desarrollan, en el cristal ideal, una estructura porosa con dimetros de
poro mnimos de 3 a 10 .

Una zeolita puede definirse como un mineral aluminosilicato cuya estructura

forma cavidades ocupadas por iones grandes y molculas de agua con gran libertad de
movimiento, que permiten el cambio inico y la deshidratacin reversible. La formula
emprica general de las zeolitas es la siguiente (Breck, 1974):

xMe 2 / n .xAl 2 O3 . ySiO 2 .wH 2 O

donde Me es el catin intercambiable y n su estado de oxidacin, y vale 2 o ms, y w
representa el agua contenida en los huecos de la zeolita.

La unidad bsica de la estructura cristalina de una zeolita son los tetraedros de

[Si O4]4- y [AlO4]5- que se unen entre si compartiendo sus oxgenos. La unin de estos
tetraedros conduce a una unidad bsica. As por ejemplo la unidad de 6 anillos (6R)
estara formada por seis tetraedros. El octaedro truncado est formado por 24 cationes y
se conoce como caja beta o unidad sodalita. A partir de la caja base de la sodalita se
pueden construir diferentes estructuras de zeolitas. En el caso ms sencillo del
empaquetamiento cbico, se forma la estructura de la hidoxi-sodalita, con dimetro de
poro reducido (2.3 ). Si estas estructuras bsicas se unen formando cubos, la estructura
se ensancha dando lugar a la zeolita A (4.2 ). Por el contrario, si se unen formando
formas hexagonales, la estructura es ms compleja y menos densa, obtenindose la
zeolita X (faujasita) (7.3), tal como se muestra en la Figura 2.6 (McGaughey y col.,
2004).

Los sistemas de canales presentes en las zeolitas se clasifican segn su

orientacin espacial en unidimensionales (mordenita), bidimensionales (heulandita), y
tridimensionales (zeolitas A, X, Y). Los canales se encuentran limitados por ventanas de

29

Introduccin

8, 10 o un mximo de 12 tomos de oxgeno, lo que en definitiva determina el tamao

de los poros.

La presencia de aluminio en el interior de la estructura de la zeolita le confiere

una carga neta negativa por cada tomo de aluminio incorporado, que se neutraliza con
iones de carga opuesta, siendo los ms tpicos cationes alcalinos (Na+, K+,...),
alcalinoterreos (Ca+2, Ba+2,..), lantnidos (La+3), o protones (Davis, 1991).

Figura 2.6. Estructura de las zeolitas

Las propiedades fsicas de las zeolitas las proveen de aspectos nicos para una
variedad amplia de aplicaciones prcticas. Segn Breck (1974) las zeolitas se
caracterizan por las siguientes propiedades:

30

Alto grado de hidratacin.

Baja densidad y un gran volumen hueco cuando se deshidratan.

Alta estabilidad de la estructura cristalina cuando se deshidratan.

Introduccin

Propiedades de intercambio de cationes.

Presencia de canales moleculares uniformes.

Capacidad de adsorber gases y vapores.

Propiedades catalticas, debidas a su elevada superficie especfica.

2.2.2. Caractersticas de las zeolitas

2.2.2.1. Propiedades fsicas
La caracterizacin de cualquier zeolita siempre incluye la descripcin bsica de
sus caractersticas fisicoqumicas y estructurales. Una de las propiedades de mayor
importancia es la evaluacin de la superficie fsica del catalizador. Existen diversos
mtodos para caracterizar esta propiedad, uno de los ms extendidos es el Brunauer,
Emmett y Teller (BET), que permite obtener el rea superficial de un slido basndose
en la adsorcin de un gas inerte, generalmente N2, a baja temperatura. Otra propiedad
relevante es el tamao de poro. La idea central del mtodo BET consiste en que
conocida la cantidad gas adsorbido necesario para formar una monocapa y el rea que
ocupa una de estas molculas adsorbidas, es posible estimar el rea del slido.

En la mayora de los slidos la superficie no es totalmente plana. Es ms, en el

caso de los slidos porosos y muy especialmente en el caso de las zeolitas, la adsorcin
y las reacciones ocurren fundamentalmente en los poros. Se reconocen tres tipos de
poros atendiendo a su tamao; si son mayores de 50 nm se conocen como macroporos,
si su dimetro est comprendido entre 2 y 50 nm se trata de mesoporos y si son menores
de 2 nm, como es el caso de los poros de las zeolitas, son microporos. La distribucin
de tamao de poro se determina igualmente a partir de la adsorcin de un gas, pero con
la aplicacin de otro mtodo, como el mtodo BJH, que considera la condensacin
capilar en los poros usando la ecuacin clsica de Kelvin. En cuanto al rea externa de
un catalizador, se la puede definir como el rea de la superficie del material excluyendo
al rea del propio microporo.

Otra propiedad importante es la relacin Si/Al. Esta relacin vara mucho de

unos materiales a otros, e incluso el mismo material puede presentar distintas
relaciones.
31

Introduccin

2.2.2.2. Propiedades qumicas

Las aplicaciones de las zeolitas naturales se basan en una o ms de sus
propiedades qumicas, que generalmente, incluyen el intercambio de iones, adsorcin o
deshidratacin y rehidratacin. Estas propiedades estn en funcin de la estructura
cristalina de cada especie y de su composicin catinica.

Propiedades de adsorcin. Los grandes canales centrales de entrada y las

cavidades de las zeolitas se llenan de molculas de agua que forman las esferas de
hidratacin alrededor de los cationes cambiables. Si el agua es eliminada, otras
molculas con dimetros lo suficientemente pequeos para que puedan pasar a travs de
los canales de entrada pueden ser fcilmente adsorbidas en las cavidades centrales. Las
molculas demasiado grandes no pueden entrar en los poros y quedan excluidas, dando
origen a las propiedades de tamices moleculares que presentan las zeolitas.

Propiedad de intercambio de cationes. Las propiedades de intercambio catinico

de una zeolita se pueden describir como la sustitucin de los iones sodio de las zeolitas
por cationes de otros tamaos y cargas. sta es una de las caractersticas esenciales de
las zeolitas ya que permite modificar considerablemente las propiedades y adaptar el
uso de la zeolita a las aplicaciones ms diversas, siendo ampliamente utilizadas en
cuatro reas: detergentes, extraccin de amoniaco de efluentes de agua, extraccin y
almacenamiento de istopos radiactivos y en la agricultura.

Deshidratacin Rehidratacin. Las zeolitas pueden ser clasificadas en dos

grandes grupos:

a) Las que muestran cambios estructurales mnimos durante la deshidratacin y exhiben

una continua prdida de peso en funcin de la temperatura.
b) Las que sufren cambios estructurales significativos durante la deshidratacin,
incluyendo colapsos (derrumbes).

Un ejemplo tpico del primer tipo son las zeolitas naturales como la mordenita,
la erionita y las zeolitas sintticas como lo son la A y la X, las cuales son trmicamente
estables hasta 700-800C. Durante la deshidratacin, las zeolitas del segundo grupo,
32

Introduccin
sufren una prdida reversible de agua a bajas temperaturas, pero si se sigue elevando la
temperatura sufren un mayor cambio estructural que les hace perder su carcter
zeoltico.

2.2.2.3. Propiedades Catalticas

La existencia de centros cidos en la red y la posibilidad de inducir nuevos
centros cidos (Beck, 1974, 1992, Gates, 1992) convierten a las zeolitas en excelentes
catalizadores, tanto en la industria petroqumica, catalizando reacciones de craqueo
entre otras, como en la industria farmacutica.

En una zeolita se pueden encontrar dos tipos de centros cidos: de Lewis y de

Brnsted. La acidez de las zeolitas procede de la carga neta asociada a cada tomo de
aluminio incorporado a la estructura. Cuando las cargas negativas generadas en la
zeolita son neutralizadas por un protn enlazado a un oxgeno, el enlace producido es
mucho ms dbil que el que se produce entre dos tomos de silicio, lo que lo convierte
en un centro cido de Brnsted. Este tipo de centros suele estar ubicados en el interior
de las zeolitas, dentro de los poros. Los centros de Lewis, por su parte, se generan por
prdida de una molcula de agua a partir de dos centros de Brnsted, y estn
relacionados con tomos de aluminio localizados en zonas exteriores de la estructura.

De acuerdo con lo expuesto anteriormente, la cantidad de centros de Brnsted

producidos depender del contenido de aluminio existente en el interior de la zeolita.
Adems existe una relacin entre la cantidad de centros de Brnsted y de Lewis en el
material, que viene controlada por la temperatura de calcinacin de la muestra de forma
que se mantiene prcticamente constante segn la expresin:
B+2L = Constante
donde B representa el nmero de centros de Brnsted y L el nmero de centros de
Lewis (Lnyi and col., 2001).

Por su parte, la fuerza de dichos centros cidos est asociada a diferentes

factores, como la relacin Si/Al. As, al ir disminuyendo la relacin Si/Al dentro de un
mismo material, aumenta la acidez, ya que aumenta el numero de centros cidos. Esto
33

Introduccin

hace que sea posible obtener una gran variedad de propiedades cidas dentro de una
misma zeolita.

La localizacin de los sitios cidos en la estructura, sin embargo, sigue siendo un

tema controvertido. Generalmente se acepta que parte de los centros cidos de Brnsted
estn situados en la zona de la boca del poro de las zeolitas y que son stos los
responsables del comportamiento no selectivo de las zeolitas, ya que las reacciones en
los centros cidos situados en esta zona son ms frecuentes que las reacciones
producidas en el interior de los poros, que se ven dificultadas por la difusin de los
reactivos o los productos en el interior de los poros de las zeolitas. La localizacin de
los sitios cidos de Brnsted influye de forma determinante en la actividad y en la
selectividad de zeolitas. Por tanto, la influencia de los sitios cidos situados en la regin
externa de la boca de los poros de las zeolitas no puede ignorarse, ya que se estima que
engloba al 3-5% de la cantidad total de sitios cidos (Zheng, 2002), aunque se sigue
considerando que la mayora de los sitios cidos de Brnsted estn situados en las
intersecciones de los poros de las zeolitas (Zheng, 2002).

A pesar de todo, los slidos cidos no se suelen sintetizar en su forma cida, sino
que, generalmente, es necesario un tratamiento de intercambio inico con una sal
amoniacal, seguido de una calcinacin que permite eliminar el amoniaco intercambiado,
generndose as los centros cidos:
500 C
NH 4 X + MZ NH 4 Z + MX
NH 3 + HZ + MX

donde Z es la zeolita, X el anin de la sal amoniacal (cloruro, bromuro, nitrato) y M es

el metal que intercambia la zeolita.

Las propiedades cidas de las zeolitas, junto a su comportamiento como tamices

moleculares, es lo que hace que estas sustancias sean muy apreciadas en catlisis
selectiva. Existen cuatro tipos de selectividad (Wardd, 1984):

34

Introduccin
-

Selectividad en los reactivos: los centros cidos internos solo son accesible a
unas molculas de reactivo determinadas, generalmente debido a que el resto de
los reactivos no caben en los poros.

Selectividad en los productos: se origina por las diferencias en las velocidades

de difusin de las distintas molculas formadas en el interior de la zeolita.
Aquellas que permanezcan ms tiempo en el interior de la zeolita podrn sufrir
reacciones secundarias

Selectividad en el estado de transicin: la obtencin de determinados productos

se encuentra obstaculizada porque sus estados de transicin no se pueden formar
en el interior de la zeolita por impedimentos estricos.

Control del trfico molecular: El tamao y la forma de los canales ejerce una
gran influencia en la difusin tanto de los reactivos como de los productos, as
por ejemplo la difusin en la zeolita ZSM-5 es cinco veces ms rpida en los
canales rectos que en los sinuosidales.

2.2.2.4. Desactivacin de los materiales zeolticos

La estabilidad de un catalizador es un factor especialmente importante en su
aplicacin industrial y se relaciona directamente con la vida til del catalizador. La vida
de operacin de un catalizador debe ser evaluada en funcin de la cantidad de productos
formados, de manera que en el mnimo de tiempo debe permitir amortizar el costo del
catalizador y la operacin del proceso.
El fenmeno de la desactivacin de un catalizador est ntimamente ligado a la
estabilidad. Segn varios autores (Moulijin y col., 2001, Bartholomew y col., 2001), las
principales causas de desactivacin son:
1) Envenenamiento de la superficie cataltica por una molcula que se adsorbe
fuertemente. El envenenamiento de la superficie est relacionado con la
adsorcin fuerte en la superficie del catalizador, tanto de reactivos como de
productos. De esta forma, los adsorbatos dbiles presentes en el medio de
reaccin no tienen acceso a los centros activos, con lo que se pierde la actividad
del catalizador.

35

Introduccin

2) Coquizacin (formacin de coque) de la superficie por deshidrogenacin de

algunos hidrocarburos cclicos. Durante la transformacin de compuestos
orgnicos sobre los materiales zeolticos se genera un residuo carbonoso, que
queda retenido en el interior de los poros, en la superficie o en ambas zonas. En
general los depsitos carbonosos que se acumulan en el interior de las zeolitas
pueden clasificarse en dos tipos; coque duro, que est formado por estructuras
con un elevado nmero de anillos aromticos condensados y suele formarse a
elevadas temperaturas, y coque blando, que tiende a formarse a bajas
temperaturas y presenta menor aromaticidad y peso molecular. Cuando el
tamao del poro de las zeolitas es pequeo, las reacciones de los compuestos
aromticos voluminosos esta impedida estricamente, por lo que, en general, la
formacin de coque es muy baja (zeolita ZSM-5). Cuando el tamao de poro es
intermedio, se pueden dar las reacciones de ciclacin y deshidrogenacin para
dar compuestos aromticos sencillos y cicloparafinas, con lo que se favorece la
formacin de coque blando (zeolita Beta). En las zeolitas de tamao de poro
grande, los compuestos aromticos pueden combinarse y dar compuestos ms
complejos que favorecen la formacin de coque duro (zeolita USY). En las
zeolitas la desactivacin por coque es muy importante, y a medida que aumenta
la cantidad de coque en la superficie y en los poros, el nmero de centros cidos
disponibles y la difusin local se reduce, reduciendose por tanto la actividad del
catalizador.
3) Reconstruccin trmica de la superficie con disminucin del rea activa
(sinterizacin). Es un proceso fsico causado por un calentamiento local, que
puede darse durante la preparacin del catalizador (calcinacin), durante la
reaccin (distribucin heterognea, puntos calientes) o la regeneracin
(combustin del coque), que modifica y altera la superficie del catalizador
disminuyendo el rea activa del mismo.
4) Prdida de la fase activa por desgaste del catalizador. Cuando algunos
catalizadores se desactivan pueden ser regenerados para recuperar sus
propiedades (totalmente o en parte). El proceso de regeneracin est ligado al
proceso de desactivacin. Algunos catalizadores durante los procesos catalticos
se desactivan muy rpido por la formacin de carbn en su superficie y deben
36

Introduccin
ser continuamente regenerados. La desactivacin por coque es reversible, ya que
se puede eliminar mediante tratamientos oxidativos a altas temperaturas.
Desgraciadamente, la regeneracin puede alterar la estructura fsica del material,
ya que se trabaja bajo condiciones muy severas.

2.3.

PRINCIPALES

MATERIALES

DE

SiO2-Al2O3

UTILIZADOS COMO CATALIZADORES

Las zeolitas no son una familia de slidos cristalinos fcilmente definible. Hoy
en da se conocen cerca de 140 estructuras de zeolitas de las cuales, cerca de 40 son
zeolitas naturales. La nomenclatura de zeolitas es algo confusa puesto que cada
fabricante ha utilizando sus propios nombres y abreviaturas. Para superar este problema
se cre un sistema de cdigo formado por tres letras. Estos cdigos se han asignado a
cada tipo de estructura independientemente de su composicin qumica real. As por
ejemplo, en la Tabla 2.5 se muestra el cdigo de seis familias de zeolitas, junto con la
abreviatura de la que procede el cdigo y el nombre completo que lo origin. A
continuacin se describen las principales caractersticas de los materiales estudiados en
este trabajo.
Tabla 2.5. Ejemplos de cdigos de zeolitas [2]
Codigo
LTA
LTL
FAU
MFI
CLO
BEA

Abreviatura
Linde Type A
Linde Type L
FAUjasita
ZSM-5 (FIve)
CLOverite
Zeolita BEtA

Nombre Completo
Zeolita A (Linde Division, Union Carbide)
Zeolita L (Linde Division, Union Carbide)
Zeolite Socony Movil- Five
Four-leafed clover shaped pore opening

2.3.1. Zeolita HZSM-5

La zeolita HZSM-5 es uno de los catalizadores ms verstiles. Pertenece al
grupo MFI (Tabla 2.5) y fue sintetizada por primera vez por la empresa Socony Movil
(Argauer y Landolt, 1972). El nmero 5 que aparece en la denominacin del material
representa la abertura de los poros de la zeolita, en .
37

Introduccin

La HZSM-5 es una zeolita con una alta relacin Si/Al, donde la sustitucin de un
ion silicio (carga 4+) por un ion de aluminio (carga 3+) requiere la presencia adicional
de un protn. Este protn es el que proporciona a la zeolita su alto nivel de acidez. La
zeolita HZSM-5 es un material altamente poroso y presenta dos tipos de poros, ambos
formados por anillos de oxgeno de 10 miembros. El primer tipo de poro es recto y con
la seccin transversal elptica, en el segundo tipo los poros rectos se intersecan
perpendicularmente, dando lugar un patrn en zigzag. Las dimensiones de las aberturas
de los poros para esta zeolita son 5.3 x 5.6 en el plano [010] y 5.1 x 5.5 en el plano
[100] (vase la Figura 2.7)

Como ya se ha dicho, la zeolita ZSM-5 se puede sintetizar con relaciones Si/Al

bastante elevadas (10-). Es ampliamente utilizada en diferentes procesos dada su alta
acidez y selectividad, derivada de su reducido tamao de poro, siendo una de sus
aplicaciones ms importantes la obtencin de gasolinas sintticas a partir de metanol.

Figura 2.7. Estructura y dimensiones de los poros de la zeolita ZSM-5 (IZA)

38

Introduccin

2.3.2. Material MCM-41

En 1992, investigadores de la empresa Mobil sintetizaron una familia de tamices
moleculares mesoporosos, conocidos como M41S, en el cual la mesofase hexagonal
(MCM-41) posee canales altamente regulares y cuyo tamao de poro puede variar
dentro de un intervalo que se extiende desde 1.2 hasta 10 nm y que, adems, presenta
una rea superficial grande y una buena estabilidad trmica (Kresge y col., 1992).

As pues, el material MCM-41 es un aluminosilicato de muy baja cristalinidad,

formado por una estructura uniforme de canales hexagonales, cuyo dimetro se puede
variar entre 12-100 mediante una adecuada seleccin de las condiciones de sntesis
(temperatura, relacin Si/Al, etc.). Presenta una estructura porosa unidimensional, sin
interconexin entre los poros. En la figura 2.8 se muestra la forma tpica de un poro del
MCM-41.

Figura 2.8. Poro hexagonal del material MCM-41 [3]

La primera vez que se sintetiz este material se utiliz un medio bsico,

temperaturas superiores a 100C, presiones autogeneradas y tiempos de sntesis
superiores a 24h. Sin embargo, hoy en da se ha conseguido sintetizar en condiciones
mucho ms suaves: temperatura ambiente, sin presin y en unas pocas horas (Aguado y
col., 2000). Segn Beck (1992), la fuerza impulsora de la sntesis del MCM-41 es la
interaccin electroesttica entre las micelas cargadas del surfactante promotor de la
estructura y las especies aninicas de silicio y aluminio. Este mecanismo de sntesis es
marcadamente diferente al de las zeolitas, donde la construccin ocurre a partir de iones

39

Introduccin

individuales, que se combinan para dar una estructura cristalina. En la figura 2.9 se
presenta un esquema del proceso de obtencin del MCM-41.

TUBO Micelar

MICELA
Surfactante

Silicato

Calcinacin

AGRUPACIN PSEUDOHEXAGONAL

MCM-41

Figura 2.9. Crecimiento del material MCM-41 [3]

La posibilidad de incorporar aluminio en la estructura del MCM-41 provoc un

inters considerable, ya que permita obtener un material con mayores propiedades
cidas que las zeolitas, que unido a su carcter mesoporoso, el cual permita una mejor
accesibilidad a la totalidad de sus centros cidos, lo converta en un catalizador
sumamente interesante para reacciones que implicasen molculas voluminosas.

2.3.3. Zeolita HUSY

Entre 1949 y 1954 Milton y Breck descubrienron diversas zeolitas sintticas de
elevado valor comercial, entre ellas las zeolitas A, X e Y. Estas zeolitas posean una
composicin rica en Al y fueron las primeras que se introdujeron comercialmente como
adsorbentes y catalizadores.

En 1969, investigadores de la compaa Grace (EEUU) realizaron las primeras

modificaciones qumicas sobre zeolitas con la finalidad de aumentar su estabilidad
trmica e hidrotrmica. Dichas pruebas consistieron en un tratamiento de la zeolita Y
con vapor de agua a altas temperaturas. El material resultante posea una mayor
estabilidad trmica e hidrotrmica, por lo que se denomin zeolita Y ultra-estable,
conocida tambin por las siglas USY (Ultrastable Steaming zeolite Y). Adems, se
40

Introduccin
observ que su estructura era ms rica en Si que la HY y que se haba aumentado la
acidez del material.

Figura 2.10. Estructura y dimensiones de los poros de la zeolita USY (IZA)

La zeolita ultraestable Y (USY) es un tipo de zeolita que presenta una relacin
de Si/Al ms baja y un mayor tamao de poro mayor que la zeolita ZSM-5. La
estructura de la zeolita USY se caracteriza por presentar grandes cavidades
(supercages), esencialmente esfricas, constituidas por anillos de 12 tomos de oxgeno,
formando un sistema de poros tridimensionales, con un tamao de poro de 7.4 en el
plano [111], y una supercage de 13 (Figura 2.10).

2.3.4. Zeolita Beta

La zeolita Beta es un material rico en silicio, con un tamao de poro grande que
fue sintetizada por primera vez por Wadlinger y col. en 1967. La estructura de la zeolita
Beta fue descrita por primera vez por Treacy y col. (1988) como un hbrido entre dos
estructuras distintas pero similares, que presentan simetra tetragonal y monoclnica.

Ambos sistemas estn constituidos por anillos de 12 tomos de oxgeno, que dan
lugar a canales tridimensionales interconectados, y presentan tres direcciones
cristalogrficas; dos morfolgicamente idnticas de canales lineales perpendiculares al
plano [00l] que corren en dos direcciones diferentes, a y b, y una tercera direccin
paralela al eje de c, de forma sinusoidal. Los canales sinusoidales presentan aberturas
circulares (5.6 5.6 ), y los canales rectos tienen aberturas elpticas. La nica
diferencia entre los dos organismos polimorfos est en la dimensin del poro de los
41

Introduccin

canales rectos. En el sistema tetragonal, los canales rectos tienen aberturas de 6.0 x 7.3
(politipo A), mientras que en el sistema monoclnico tiene una abertura de 6.8 x 7.3
(politipo B) (Corma y col., 1996). En la Figura 2.11 se puede ver la estructura
tridimensional de la zeolita Beta, as como un ejemplo de los poros en el plano [100] y
en el plano [001], y la disposicin de los dos politipos A y B.

Figura 2.11. Estructura y politipos de la zeolita Beta (IZA)

2.3.5. Catalizador de FCC

El catalizador de FCC (craqueo cataltico en lecho fluidizado o Fluid Catalytic
Cracking) es un polvo fino y poroso compuesto de xidos de silicio y aluminio. Cuando
este catalizador se airea con un gas, el polvo adquiere la propiedad de parecer un fluido,
lo que le permite comportarse como un lquido. Esta propiedad es lo que le permite
tomar el nombre de catalizador de craqueo fluidizado.

Los catalizadores de FCC son materiales complejos conformados por varios

componentes, cada uno de los cuales est diseado para mejorar el comportamiento
total del catalizador. Los componentes contenidos en la mayora de los catalizadores de
FCC son: zeolita, arcilla, una matriz que puede ser activa o inerte, y aglutinantes.
42

Introduccin
La fuente principal de la actividad del catalizador es la zeolita. Especficamente,
la zeolita empleada en el catalizador de craqueo es la faujasita, un aluminosilicato
tridimensional con una abertura de poro de 8-9 , aunque a veces el catalizador
presenta otras zeolitas como aditivos, como puede ser el caso de la zeolita ZSM-5. La
faujasita se encuentra en la naturaleza, pero debido a su escasez, es sintetizada
comercialmente, y segn el mtodo manufactura y tratamiento hay dos zeolitas bsicas
usadas como catalizadores que tienen comportamientos distintos:

Estndar: HY

Ultraestable: HUSY

La zeolita HUSY descrita en la seccin 2.3.3 de esta memoria, es sin duda la

zeolita ms usada en los catalizadores de FCC. Como ya se ha dicho es un
aluminosilicato cristalino y microporoso constituido por tetraedros de [SiO4]4- y
[AlO4]5- coordinados a travs de puentes de oxgeno no lineales que posee un sistema de
poro grande conectado a travs de ventanas de dimetro mximo de 7.4 , constituida
por anillos de 12 tomos de oxgeno dando lugar a canales tridimensionales y con una
relacin Si/Al entre 3 y 5 (Figura 2.10).

Normalmente la zeolita se encuentra dispersa en una matriz activa constituida

por diversos aditivos que hacen difcil el proceso de caracterizacin, de evaluacin, de
seleccin, de escalamiento y de prediccin de su comportamiento cataltico en las
condiciones reales del proceso. La matriz amorfa suele estar constituida por slice,
almina, caoln, arcilla y diferentes aditivos como promotores de combustin,
reductores de emisiones de SOx, mejoradores de octano y pasivadores de Ni y V.

2.4. MATERIALES PLSTICOS

Los polmeros naturales, por ejemplo la lana, la seda, la celulosa, etc., se han
empleado profundamente y han tenido mucha importancia a lo largo de la historia. Sin
embargo, hasta finales del siglo XIX no aparecieron los primeros polmeros sintticos,
como por ejemplo el celuloide.

43

Introduccin

Los primeros polmeros que se sintetizaron se obtenan a travs de

transformaciones de polmeros naturales. En 1839 Charles Goodyear realiz el
vulcanizado del caucho. El nitrato de celulosa se sintetiz accidentalmente en el ao
1846 por el qumico Christian Friedrich Schnbein y en 1868, John W. Hyatt sintetiz
el celuloide a partir de nitrato de celulosa.

El primer polmero totalmente sinttico se obtuvo en 1909, cuando el qumico

belga Leo Hendrik Baekeland fabric la baquelita a partir de formaldehdo y fenol.
Otros polmeros importantes se sinterizaron en aos siguientes, por ejemplo el
poliestireno (PS) en 1911 o el policloruro de vinilo (PVC) en 1912.

En 1922, el qumico alemn Hermann Staudinger comienza a estudiar los

polmeros y en 1926 expone su hiptesis de que se trata de largas cadenas de unidades
pequeas unidas por enlaces covalentes. Propuso las frmulas estructurales del
poliestireno y del polioximetileno, tal como las conocemos actualmente, como cadenas
moleculares gigantes, formadas por la asociacin mediante enlace covalente de ciertos
grupos atmicos llamados "unidades estructurales". Este concepto se convirti en el
"fundamento" de la qumica macromolecular slo a partir de 1930, cuando fue aceptado
ampliamente. En 1953 recibi el Premio Nobel de Qumica por su trabajo.

Por lo tanto, los polmeros se pueden describir como macromolculas

(generalmente orgnicas) formadas por la unin de molculas ms pequeas llamadas
monmeros. Por ejemplo, el poliestireno es un polmero formado a partir de la unidad
repetitiva estireno.

La reaccin por la cual se sintetiza un polmero a partir de sus monmeros se

denomina polimerizacin (Figura 2.12). En el caso del PS, que se muestra en la Figura
2.12, el mecanismo por el cual se produce la reaccin de polimerizacin es
polimerizacin por pasos o polimerizacin en cadena. En cualquier caso, el tamao de
la cadena depender de parmetros como la temperatura o el tiempo de reaccin,
teniendo cada cadena un tamao distinto y, por tanto, una masa molecular distinta, por
lo que se habla de masa promedio para el polmero. La polimerizacin en etapas
(condensacin) necesita monmeros bifuncionales.

44

Introduccin

n
Figura 2.12. Polimerizacin del estireno para dar poliestireno; n indica el grado de
polimerizacin

Por otra parte, los polmeros pueden ser lineales, formados por una nica cadena
de monmeros, como el polietileno de alta densidad (HDPE) o bien esta cadena puede
presentar ramificaciones de mayor o menor tamao, como el polietileno de baja
densidad LDPE (Figura 2.13). Tambin se pueden formar entrecruzamientos
provocados por el enlace entre tomos de distintas cadenas.

Figura 2.13. Diferencia entre polmero lineal y polmero ramificado

La naturaleza qumica de los monmeros, su masa molecular y otras propiedades

fsicas, as como la estructura que presentan, determinan diferentes caractersticas para
cada polmero. Por ejemplo, si un polmero presenta entrecruzamiento, el material ser
ms difcil de fundir que si no lo presentara. Adems, los enlaces entre carbonos en los
polmeros no son equivalentes entre s; por eso dependiendo de la estereoqumica de los
enlaces, un polmero puede ser: atctico (sin orden), isotctico (mismo orden), o
sindiotctico (orden alternante). Las propiedades de un polmero pueden verse
modificadas severamente dependiendo de su estereoqumica.

45

Introduccin

En el caso de que el polmero provenga de un nico tipo de monmero se

denomina homopolmero y si proviene de varios monmeros diferentes se llama
copolmero o heteropolmero. Por ejemplo, el poliestireno es un homopolmero, pues
proviene de un nico tipo de monmero, el estireno, mientras que si se parte de estireno
y butadieno se puede obtener un copolmero de estos dos monmeros, como es el caso
del polibutadieno/estireno (SBS).

En los copolmeros, los monmeros pueden distribuirse de diferentes maneras,

particularmente para polmeros naturales. As, los monmeros pueden repetirse de
forma aleatoria, ordenada como en los polipptidos de las protenas o en los
polinucletidos de los cidos nucleicos o peridica, como en el peptidoglucano o en
algunos polisacridos.

Los monmeros que conforman la cadena de un copolmero se pueden ubicar en

la cadena principal alternndose segn diversos patrones, dando lugar a copolmeros
alternantes, copolmeros en bloque, copolmeros aleatorios o copolmeros de injerto
(Figura 2.14). Para lograr estos diseos, la reaccin de polimerizacin y los
catalizadores empleados deben ser los adecuados para cada caso en particular.

Figura 2.14. a) Homopolmero b) Copolmero alternante c) Copolmero en bloque d)

Copolmero aleatorio e) Copolmero de injerto

46

Introduccin

2.4.1. Clasificacin
Existen varias formas posibles de clasificar los polmeros, sin que stas sean
excluyentes entre s:

2.4.1.1. Segn su origen

Polmeros naturales. Existen en la naturaleza muchos polmeros y las

biomolculas que forman los seres vivos son macromolculas polimricas. Por
ejemplo, las protenas, los cidos nucleicos, los polisacridos (como la celulosa
y la quitina), el hule o caucho natural, la lignina, etc.

Polmeros semisintticos. Se obtienen por transformacin de polmeros

naturales. Por ejemplo, la nitrocelulosa, el caucho vulcanizado, etc.

Polmeros sintticos. Muchos polmeros se obtienen industrialmente a partir de

los monmeros. Por ejemplo, el nylon, el poliestireno, el cloruro de polivinilo, el
polietileno, etc.

2.4.1.2. Segn su mecanismo de polimerizacin

Polmeros de condensacin. La reaccin de polimerizacin implica en cada paso

la formacin de una molcula de baja masa molecular, por ejemplo agua.

Polmeros de adicin. La polimerizacin no implica la liberacin de ningn

compuesto de baja masa molecular. Esta polimerizacin se genera cuando un
"catalizador" inicia la reaccin. Este catalizador favorece la rotura de un doble
enlace carbono-carbono en los monmeros, que se van uniendo uno tras otro
hasta que la reaccin termina.

Otra clasificacin puede ser la que diferencia entre:

Polmeros formados por etapas. La cadena de polmero va creciendo

gradualmente mientras haya monmeros disponibles, aadiendo un monmero
cada vez. Esta categora incluye todos los polmeros de condensacin de
Carothers y adems algunos otros que no liberan molculas pequeas pero s se
forman gradualmente, como por ejemplo los poliuretanos.

47

Introduccin

Polmeros formados por reaccin en cadena. Cada cadena individual de

polmero se forma a gran velocidad, mediante un mecanismo de reccin en
cadena y luego queda inactiva, a pesar de estar rodeada de monmero.
Coincidente con los polmeros de adicin.

2.4.1.3. Segn su composicin qumica

Poliolefinas, formados mediante la polimerizacin de olefinas, como por

ejemplo el polietileno y el polipropileno

Polmeros estirnicos, que incluyen al estireno entre sus monmeros, como el

poliestireno, copolmeros butadieno-estireno-butadieno (SBS), HIPS.

Polmeros vinlicos halogenados, que incluyen tomos de halgenos (fluor,

cloro...) en su composicin, como PVC y politetrafluoroetileno (PTFE).

Polmeros acrlicos. Formados a partir de monmeros acrlicos, como el

polimetacrilato de metilo (PMMA).

Polmeros orgnicos no vinlicos. Son polmeros de condensacin o formados

por etapas y, adems de carbono, tienen tomos de oxgeno o nitrgeno en su
cadena principal.

2.4.1.4. Segn sus aplicaciones

Atendiendo a sus propiedades y usos finales, pueden clasificarse en:

Elastmeros. Son materiales con muy bajo mdulo de elasticidad y alta

extensibilidad; es decir, se deforman mucho al someterlos a un esfuerzo pero
recuperan su forma inicial al eliminar el esfuerzo. En cada ciclo de extensin y
contraccin los elastmeros absorben energa, una propiedad denominada
resiliencia.

Plsticos. Son aquellos polmeros que, ante un esfuerzo suficientemente intenso,

se deforman irreversiblemente, no pudiendo volver a su forma original. Hay que
resaltar que el trmino plstico se aplica a veces incorrectamente para referirse a
la totalidad de los polmeros.

48

Introduccin

Fibras. Presentan alto mdulo de elasticidad y baja extensibilidad, lo que

permite confeccionar tejidos cuyas dimensiones permanecen estables.

Recubrimientos. Son polmeros, normalmente lquidos, que se adhieren a la

superficie de otros materiales para otorgarles alguna propiedad, por ejemplo
resistencia a la abrasin.

Adhesivos. Son polmeros que combinan una alta adhesin y una alta cohesin,
lo que les permite unir dos o ms cuerpos por contacto superficial.

2.4.1.5. Segn su comportamiento al elevar su temperatura

Dependiendo de si el material funde y fluye o por el contrario no lo hace al ser
calentado por encima de determinada temperatura se diferencian dos tipos de polmeros:

Termoplsticos, que fluyen (pasan al estado fundido) al calentarlos y se

vuelven a endurecer (vuelven al estado slido) al enfriarlos. Su estructura
molecular presenta pocos (o ningn) entrecruzamientos. Ejemplos: PE, PP,
PVC.

Termoestables, que no fluyen, y lo nico que se consigue al calentarlos es

que se descompongan qumicamente. Este comportamiento se debe a una
estructura con entrecruzamientos que impiden los desplazamientos relativos
de las molculas.

La clasificacin de los polmeros termoplsticos o termoestables es

independiente de la clasificacin de elastmeros, plsticos o fibras. Existen plsticos
que presentan un comportamiento termoplstico y otros que se comportan como
termoestables. Esto constituye de hecho la principal subdivisin del grupo de los
plsticos y hace que a menudo cuando se habla de "los termoestables" en realidad se
haga referencia slo a "los plsticos termoestables". Pero ello no debe hacer olvidar que
los elastmeros tambin se dividen en termoestables (la gran mayora) y termoplsticos
(una minora, pero con aplicaciones muy interesantes).

49

Introduccin

2.5.

MECANISMOS

DE

DEGRADACIN

DURANTE

LOS

PROCESOS DE PIROLISIS
2.5.1. Craqueo trmico
La pirlisis trmica de polmeros ha sido ampliamente estudiada desde hace aos
por diferentes autores. En el caso concreto del polietileno, Oakes y colaboradores
(Oakes y col., 1949) encontraron que este polmero era estable hasta una temperatura de
290C, degradndose a un polietileno de menor peso molecular a mayores temperaturas.
El proceso de descomposicin trmica de este polmero es al azar, y todos los enlaces
tienen la misma fuerza y la misma probabilidad de romperse bajo la influencia de calor,
excepto los enlaces C-C del final de cadena y aquellos enlaces adyacentes a carbonos
terciarios. As pues, durante el craqueo trmico, el polietileno se descompone en un gran
nmero de compuestos parafnicos y olefnicos sin dejar apenas residuo slido si la
temperatura es lo suficientemente elevada.

Simha y colaboradores (Simha y col., 1958) propusieron un mecanismo para

explicar el proceso de descomposicin trmica de las poliolefinas y otros polmeros de
adicin. El mecanismo de descomposicin incluye los siguientes pasos:

Iniciacin: proceso unimolecular que consiste en la ruptura de un punto de la

cadena al azar o bien de las terminaciones de cadena, originando dos radicales libres
Propagacin: los radicales libres sufren reacciones de escisin dando lugar al
monmero:

CH CHX CH C HX
2
2

CH C HX
2

+ CH = CHX
2

Transferencia radicalaria: las reacciones de transferencia de hidrgeno pueden

ser de tipo intermolecular, en la cual un radical libre toma un hidrgeno de otra cadena,
y de tipo intramolecular, en la que la abstraccin se produce dentro de la misma cadena
del radical. En el craqueo trmico de polietileno la tranferencia de tipo intramolecular se
encuentra ms favorecida por la abundante presencia de tomos de hidrgeno en las
cadenas del polmero. La abstraccin de hidrgeno ocurre preferentemente en los
tomos de carbono terciarios y los productos formados resultan de la homlisis de los
50

Introduccin
enlaces C-C en la posicin al centro radicalario (Ahlstrom, 1976; Tsuge y col., 1980).
Esta reaccin forma especies olefnicas y fragmentos polimricos. Adems, tambin se
pueden formar radicales secundarios a partir de la transferencia de hidrgeno
intermolecular entre un radical primario y un fragmento polimrico.
-divisin: origina grupos olefnicos terminales y un radical primario.

CHX CH C X CH
2
2

C HX

+ CH = CX CH
2
2

Formacin de ramificaciones: se pueden formar ramificaciones por la

interaccin entre radicales secundarios o entre un radical primario y uno secundario.

Terminacin: esta ltima fase puede ocurrir a travs del modo bimolecular, entre
dos radicales primarios, o por desproporcin de radicales primarios.

Unin bimolecular:

CHX C H

+ C HX CH
2

CHX CH CHX CH
2
2

Desproporcin:

CH CHX C H
2
2

+ C HX CH CH
2
2

C H CHX CH
2
3

+ CHX = CH CH
2

Una vez formado el radical libre en el paso de iniciacin, o en cualquiera de los

otros pasos, pueden competir dos reacciones: la reaccin de propagacin y la
transferencia radicalaria.

De los resultados obtenidos por Oakes y colaboradores (Oakes y col., 1949) y

por Wall y colaboradores (Wall y col., 1954), se pudo concluir que en el caso del
polietileno la reaccin de transferencia radicalaria es la predominante. A bajas
temperaturas, tiene lugar preferentemente la transferencia de hidrgeno intramolecular
seguida por una escisin . A altas temperaturas, ocurren ms rupturas en la cadena del
51

Introduccin

polmero, originndose numerosos radicales primarios cortos, los cuales reaccionan a

alcanos favoreciendo la transferencia de hidrgeno intermolecular. Arnett y
colaboradores (Arnett y col., 1966) y Kuroki y colaboradores (Kuroki y col., 1982)
consideran que la reaccin de terminacin tiende a producirse a travs de la
combinacin de dos radicales, siendo la probabilidad de que esto ocurra 5-10 veces
mayor que la desproporcin.

2.5.2. Craqueo cataltico

2.5.2.1. Reacciones de los carbocationes sobre los centros activos del
catalizador
El craqueo cataltico de hidrocarburos tiene lugar en los centros cidos del
catalizador (Mordi y col., 1994). Cuando un hidrocarburo reacciona en la superficie de
estos catalizadores cidos, ocurren una serie de reacciones en las que intervienen
carbocationes y cuya velocidad depende de la naturaleza del carbocatin y de la
naturaleza y la fuerza del centro cido implicado en la reaccin. En la Figura 2.15 se
muestra la fuerza cida relativa necesaria para distintas reacciones. Dado que hay
evidencias de que una reaccin dada ocurre en un intervalo relativamente estrecho de
acidez de los centros cidos, la selectividad del catalizador puede controlarse ajustando
la acidez de los centros activos (Wojciechowski y col., 1986).

Reaccin

Isomerizacin cis trans

Isomerizacin de doble enlace

Isomerizacin de ion carbenio ternario

Transferencia de hidrgeno intermolecular

Polimerizacin
Ramificacin

Alquilacin
Craqueo

Necesidad creciente de centros cidos ms

fuertes

Figura 2.15. Fuerza relativa cualitativa de los centros cidos necesarios en las
reacciones de iones carbenio.

52

Introduccin
Los carbocationes se forman por reacciones que pueden agruparse en cuatro
grandes clases:

a)

Adicin de un catin a una molcula insaturada

b) Adicin de un protn a una molcula saturada

c)

Eliminacin de un electrn de una especie elctricamente neutra

d) Rotura heteroltica de una molcula

Independientemente del origen del carbocatin, una vez que se ha formado

puede evolucionar a travs de cinco procesos diferentes, aunque no todos son igual de
probables para cada carbocatin:

1. Isomerizacin de carga
La isomerizacin de los iones carbenio (iones formados por la adicin de un
protn a una olefina o por la eliminacin de un ion hidruro de una parafina) ocurre por
transferencia de hidrgeno a lo largo de la cadena hidrocarbonada. Un ejemplo de
reaccin de este tipo:
H
|
CH C CH
3
3
+

H
|
CH C C H
3
2
| +
H

2. Isomerizacin de cadena o esqueletal

La isomerizacin de cadena por desplazamiento de un grupo metilo da lugar a
iones carbenio altamente ramificados. La velocidad de estos procesos de transferencia
de grupos metilo suele ser unas 1000 veces menor que la de transferencia de hidrgeno
que tiene lugar en la isomerizacin de carga. En la siguiente secuencia se muestra un
ejemplo.
CH

CH

3
|
|
CH CH C H CH CH R CH C CH CH R C H C H CH CH R
3
2 +
2
2
3 +
2
2
2
2
+ 2

53

Introduccin

3. Transferencia de hidruro
Las reacciones de transferencia de hidruro entre alcanos e iones carbenio son
importantes en las reacciones de craqueo cataltico de hidrocarburos ya que son las
responsables del proceso de reaccin en cadena que ocurre una vez que se ha formado el
primer ion carbenio sobre la superficie del catalizador.
R H
1

R+
2

R +
1

R H
2

4. Transferencia de grupos alquilo

Estas reacciones de desplazamiento no se han demostrado directamente y, si
ocurren, no parecen tener consecuencias importantes en el craqueo cataltico.
R+
1

R R
2
3

R R
1
2

R+
3

5. Formacin y rotura de enlaces carbono-carbono

Los carbocationes son importantes intermediarios en las reacciones que implican
formacin y rotura de enlaces carbono-carbono. El proceso de craqueo es consecuencia
de los procesos de rotura de enlaces que ocurren sobre los catalizadores cidos, mientras
que los procesos de polimerizacin de olefinas, y la alquilacin de parafinas y
aromticos son ejemplos tpicos de reacciones de formacin de enlaces carbonocarbono. Las reacciones de desproporcin, que implican formacin y rotura de enlaces
carbono-carbono, son tambin una variante de estas reacciones. Este tipo de reacciones
vienen regidas por las siguientes reglas generales:

El enlace que se rompe est situado en posicin al tomo de carbono con la

carga positiva.

Los productos olefnicos son 1-olefinas y se transfieren a la fase gas, dejando

sobre la superficie del catalizador un ion carbenio de menor tamao.

El craqueo ocurre de forma que el ion carbenio dominante formado es lo ms

estable posible.

El ion carbenio formado puede volver a adsorberse sobre el catalizador o

isomerizarse para adoptar una configuracin ms estable o continuar
craquendose.

54

Introduccin
2.5.2.2. Mecanismos de craqueo cataltico en polmeros
Maegaard (1997) estudi el mecanismo de pirlisis cataltica del HDPE sobre
zeolitas utilizando la tcnica de microscopa electrnica de barrido. A travs de esta
tcnica pudo observar que a temperaturas cercanas a los 300C, el polmero fundido
llena el espacio entre partculas y, por tanto, llega a los centros activos de la superficie
externa de la zeolita. La reaccin en la superficie produce compuestos de menor peso
molecular que, si son lo suficientemente voltiles a la temperatura de reaccin, pueden o
bien difundir a travs de la capa de polmero, como productos, o bien pueden reaccionar
en los poros de la zeolita. Como resultado, la distribucin de productos refleja las
caractersticas de la zeolita con relacin a su sistema de poros y composicin qumica.

Lin y colaboradores (Lin y col., 2001) propusieron el siguiente modelo cinticomecanstico:

El polmero fundido, en contacto con las partculas de catalizador, forma un

complejo polmero/catalizador, inicindose la reaccin en la superficie del
catalizador.

Las reacciones de escisin generan compuestos de peso molecular intermedio,

como olefinas de cadena larga y precursores de iones carbenio. Los iones
carbenio alcanzan rpidamente una concentracin estacionaria. Los alcanos
pueden ser generados, va transferencia de hidrgeno, convirtindose
inicialmente en productos de cadena larga. En general, el nmero de centros
activos limita el nmero de precursores de iones carbenio.

Una vez que se han formado los compuestos de peso molecular intermedio,
pueden ocurrir reacciones que originen olefinas de cadena ms corta en
equilibrio con los iones carbenio superficiales, adems de alcanos, benceno,
tolueno y xileno (BTX) y coque. La mezcla en equilibrio de las olefinas e iones
carbenio reacciona posteriormente para producir los productos finales.

55

OBJETIVOS

Objetivos

El objetivo general del presente trabajo para optar al grado de Doctor es el

estudio sistemtico del proceso de pirlisis de polmeros con vistas a su utilizacin
como una alternativa viable para el reciclado de residuos plsticos. Con esta finalidad se
plantea la seleccin de diferentes sistemas polmero-catalizador y el estudio de su
comportamiento durante el proceso de pirlisis, desde distintos puntos de vista y
utilizando diferentes tipos de reactores.

Para la consecucin de estos objetivos generales se plantean los siguientes

objetivos especficos:

1. Puesta a punto de mtodos de sntesis y caracterizacin de diferentes slidos

cidos (HZSM-5, y dos MCM-41 con diferente relacin Si/Al) utilizados
habitualmente en la pirlisis cataltica de polmeros.
2. Estudio en termobalanza de la actividad que presentan los slidos cidos
sintetizados cuando actan como catalizadores del proceso de pirlisis cataltica
de diferentes polmeros (LDPE, PP, HIPS y un copolmero de EVA).
3. Estudio del papel que juega el rea superficial externa en materiales con elevada
superficie especfica, como el catalizador MCM-41, en la pirlisis de polmeros.
Estudio de la influencia de los procesos de desactivacin de los centros cidos
superficiales durante el proceso de pirlisis.
4. Estudio del efecto del tipo de contacto entre polmero/catalizador durante la
pirlisis cataltica.
5. Estudio de la posibilidad de utilizar tcnicas de pirlisis cataltica de polmeros
como herramienta de anlisis de copolmeros, mediante la seleccin de las
condiciones experimentales adecuadas y el diseo de modelos pseudocinticos
capaces de predecir el comportamiento del sistema.
6. Estudio de la viabilidad de utilizar la descomposicin cataltica de mezclas de
fuel y residuos plsticos en presencia de distintos catalizadores como va de
reciclado qumico. Con esta finalidad se pretende realizar estudios en
termobalanza, as como estudios en un reactor de lecho fijo.

59

MATERIALES
Y MTODOS

4.1. Catalizadores seleccionados

4.1.1. Catalizadores sintetizados en el presente trabajo
4.2. Tcnicas de caracterizacin de los materiales slidos cidos
4.2.1. Difraccin de Rayos X (DRX)
4.2.2. Microscopia electrnica de transmisin (TEM)
4.2.3. Microscopia electrnica de barrido (SEM)
4.2.4. Isotermas de adsorcin de nitrgeno
4.2.5. Fluorescencia de Rayos X (FRX)
4.2.6. Desercin trmica programada (DTP) de amoniaco
4.2.7. Resonancia magntica nuclear de Al27 y Si29
4.3. Caractersticas de los materiales empleados
4.3.1. Polmeros
4.3.2. Catalizadores
4.4. Tcnicas, condiciones experimentales y equipos empleados
4.4.1. Estudio de la actividad cataltica de los materiales
sintetizados
4.4.2. Condiciones experimentales empleadas en los distintos
trabajos

Materiales y Mtodos

4.1. CATALIZADORES SELECCIONADOS

En esta seccin se describen los mtodos de sntesis utilizados para la
preparacin de los diferentes catalizadores utilizados en este trabajo y se hace referencia
a otros catalizadores comerciales seleccionados. Las tcnicas de caracterizacin y las
propiedades fisicoqumicas y texturales de los diferentes materiales se describen en los
apartados posteriores.

4.1.1. Catalizadores sintetizados en este trabajo

4.1.1.1. Preparacin de la zeolita HZSM-5
La sntesis de la zeolita HZSM-5 con un tamao de cristal aproximado de 300
nm se llev a cabo mediante el procedimiento desarrollado por la International Zeolite
Association (IZA). El mtodo consta de dos etapas, la sntesis de un gel de siembra, y la
sntesis propiamente dicha de la zeolita (IZA web).

- Preparacin del gel de siembra (para la obtencin de 40 g de gel). En primer

lugar se prepara una disolucin mezclando 28.4 g de agua, con 0.552 g de hidrxido de
sodio y 4.7 ml de TPA-OH (hidroxido de tetrapropil amonio). A esta disolucin se le
adicionan 6.356 g de cido silcico, muy lentamente y con agitacin continua. Una vez
terminada la adicin se agita la mezcla resultante durante una hora a temperatura
ambiente, tras lo cual se deja envejecer a 100 C durante 16 horas. La composicin del
gel resultante es:

3.25 Na2O: Al2O3: 30 SiO2: 958 H2O

El gel de siembra tiene una textura de polvo y es de color blanco

- Preparacin del gel de sntesis (para la obtencin de aproximadamente 4 g de

producto). Se disuelven 0.44 g de hidrxido sdico y 0.515 g de aluminato de sodio en
43.39 g de agua. A esta disolucin se le agrega, poco a poco y bajo agitacin, 5.7 g de
cido silcico. Tras la adicin, se agita vigorosamente una hora a temperatura ambiente.
A continuacin, se adicionan 2.5 g del gel de siembra y se agita durante una hora mas.

63

Materiales y Mtodos

El gel resultante se introduce, para la cristalizacin, en un autoclave de acero

inoxidable con camisa de tefln a 150* C, durante 72 horas y en modo esttico.

El producto se recupera por filtracin y se lava con abundante agua destilada,

tras lo cual, se deja secar durante 24 horas a 105 C para que slido resultante pierda el
agua adsorbida. Por ultimo, se pulveriza el producto en un mortero de gata.

Para obtener la forma cida de la zeolita se introduce en una disolucin 1M de

NH4Cl a temperatura ambiente durante 48 h para que se produzca el intercambio inico.
A continuacin, se filtra y se lava con agua para eliminar el exceso de cloruros. Se seca
en la estufa a 105 C. Por ltimo, se calcina en aire a 500 C, durante 5 horas, para
obtener la forma cida del material por eliminacin de amonaco.

Las caractersticas de los reactivos utilizados en la sntesis se muestran en la

tabla 4.1.

Tabla 4.1. Reactivos empleados para la sntesis de la zeolita HZSM-5

Material
Hidrxido Sdico
Hidrxido de Tetrapropilamonio
cido silcico Hidratado
Aluminato de sodio Anhidro
Cloruro Amnico

Caractersticas
Perlas, pureza min 98%
Disolucin ~20%
Polvo, pureza min 99%
Polvo
Pureza 99%

Casa Comercial
Sigma- Aldrich
Fluka
Fluka
Sigma- Aldrich
Sigma- Aldrich

4.1.1.2. Preparacin del material MCM-41

La sntesis de MCM-41 se llev a cabo mediante el procedimiento desarrollado
por Aguado (Aguado y col. 2000). Se trata de un proceso sol-gel que consta de dos
pasos. En el primero, se genera un medio cido que favorece la reaccin de hidrlisis
entre la fuente de aluminio y la fuente se silicio y retrasa la condensacin de los
productos, evitndose as la precipitacin de las fases indeseadas del xido de aluminio.
En el segundo paso, se alcanza el punto del gel mediante el aumento del pH con la
adicin controlada de amonaco, el cul acelera la reaccin de condensacin de los
productos de la hidrlisis. Este proceso se lleva a cabo en presencia de un surfactante
(cloruro del hexadeciltrimetilamonio), sustancia que contiene la micela promotora para

64

Materiales y Mtodos

la sntesis del material. Finalmente, mediante la calcinacin, se obtiene el slido en su

forma cida. Por otra parte, un aumento en el contenido de aluminio durante la sntesis
conduce a la formacin de las fases de la micela con tamaos de poro que llegan a la
zona de microporos, lo que permite obtener materiales MCM-41 con diferentes tamaos
de poro.

En el presente trabajo, se prepararon dos materiales MCM-41, con distintas

relaciones masicas SiO2/AlO3 47 (MCM-41(47)) y 7 (MCM-41(7)), y por lo tanto con
distintas propiedades catalticas. Los reactivos usados para la sntesis ambos materiales
MCM-41 han sido los mismos y sus caractersticas se muestran en la tabla 4.2.

Tabla 4.2. Reactivos empleados para la sntesis de los materiales MCM-41

Material
Ortosilicato de Tetraetilo
Isopropxido de Aluminio
Cloruro Hexadecitrimetilamonio
cido Clorhdrico
Amonaco

Caractersticas
Polvo, pureza min 99%
Polvo, pureza min 98%
Disolucin 25%w
Disolucin 35%w
Disolucin 25%

Casa Comercial
Sigma- Aldrich
Sigma- Aldrich
Sigma- Aldrich
Sigma- Aldrich
Panreac

4.1.2.1.1. Preparacin del material MCM-41(47)

Este material aparece citado en las publicaciones que constituyen la presente
tesis doctoral como MCM-41a para ser diferenciado del otro material MCM-41
estudiado. Para su preparacin, inicialmente se preparan dos disoluciones con agitacin
suave: la disolucin A, formada por ortosilicato de tetraetilo e isopropoxido de
aluminio; y la suspensin B, compuesta por cloruro de hexadeciltrimetilamonio y cido
clorhdrico.

Disolucin A: 10.7 ml del tetraetilortosilicato y 0.33 g de isopropoxido de

aluminio
Suspensin B: 18.8 ml de cloruro del hexadeciltrimetilamonio y 3.33 g de
disolucin acuosa de cido clorhdrico al 35% en peso.

En primer lugar, la disolucin A se agrega a la suspensin B y la mezcla se agita

durante 75 minutos. A continuacin se adiciona la disolucin acuosa de amoniaco al 2%

65

Materiales y Mtodos

en peso, gota a gota, bajo agitacin y se deja a la mezcla resultante envejecer durante
una hora, con agitacin. En total se agregan 37 g de disolucin amoniacal.

La temperatura es un factor clave en la sntesis de este tipo de materiales, ya que

al variar este parmetro se modifican sus propiedades. Por lo tanto, para obtener un
producto con propiedades fisicoqumicas reproducibles, es importante mantener
constante la temperatura durante el proceso de sntesis. Para ello se ha trabajado en un
bao de agua termostatizado a una temperatura de 20 C.

En la ltima etapa, el producto slido se recupera por filtracin en un embudo

Buchner, se lava con abundante agua desionizada, se seca a 110 C durante 12 horas y,
finalmente se calcina para obtener la forma cida del material a 550 C, en atmsfera de
aire, durante 12 horas.

4.1.2.1.2. Preparacin del material MCM-41(7)

Este material aparece citado en las publicaciones como MCM-41b, o AlMCM-41 para ser diferenciado del MCM-41 descrito anteriormente. El mtodo de
obtencin es idntico al anterior, varindose solo las cantidades de algunos reactivos. Se
prepararon dos disoluciones, la disolucin A con mayor contenido de aluminio que en el
caso anterior, y la suspensin B:

Disolucin A: 10.7 ml del tetraetilortosilicato y 1.98 g de isopropxido de

aluminio
Suspensin B: 18.8 ml de cloruro del hexadeciltrimetilamonio y 3.33 g de
disolucin acuosa de cido clorhdrico al 35% en peso.
En primer lugar, la disolucin A se agrega a la solucin B y la mezcla se agita
durante 75 minutos. A continuacin, se adiciona 15 g de la disolucin acuosa de
amoniaco al 2% en peso, gota a gota, bajo agitacin y se deja a la mezcla envejecer
durante una hora, con agitacin.

De la misma manera que se hizo en la preparacin del MCM-41(47), es

importante, para la reproducibilidad de las propiedades del producto obtenido, mantener

66

Materiales y Mtodos

constante la temperatura durante la sntesis por lo que se trabaj a 20 C en un bao

termostatizado.

Por ltimo, el producto slido se recupera por filtracin en un embudo Buchner,

se lava con agua desionizada, se seca a 110 C, durante 12 horas y finalmente, se
calcina a 550 C, en atmsfera de aire, durante 12 horas, para obtener la forma cida del
material.

4.1.1.3. Zeolitas comerciales

En el presente trabajo se han estudiado, adems de los catalizadores sintetizados
segn los procedimientos descritos en la seccin anterior, varios catalizadores
comerciales como las zeolitas HUSY y HZSM-5, esta ltima designada en este trabajo
como HZSM-5c para diferenciarla del material sintetizado, que fueron suministradas
por Grace Davison, una zeolita H-Beta que fue suministrada por Sd-Chemie Inc. (HBeta 25), y un catalizador de equilibrio de FCC, que fue proporcionado por Repsol.

4.2.

TCNICAS

DE

CARACTERIZACIN

DE

LOS

MATERIALES SLIDOS CIDOS

Los distintos catalizadores estudiados, sintetizados segn los procedimientos
descritos en el apartado anterior, se caracterizaron mediante distintas tcnicas
instrumentales a fin de determinar sus propiedades fisicoqumicas y texturales. En esta
seccin se describen brevemente las tcnicas de caracterizacin utilizadas, que fueron
las siguientes:

- Difraccin de Rayos X
- Microscopa Electrnica de Transmisin
- Microscopa Electrnica de Barrido
- Isotermas de Adsorcin de Nitrgeno
- Fluorescencia de Rayos X
- Desorcin Trmica Programada de Amoniaco
- Resonancia Magntica Nuclear de Al27 y Si29
67

Materiales y Mtodos

En la siguiente seccin (4.3) se indican los resultados obtenidos para la

caracterizacin de cada material.

4.2.1. Difraccin de Rayos X (DRX)

La difraccin de rayos X permite determinar el tipo de estructura cristalina de
los slidos estudiados, incluso cuando se trata de estructuras cristalinas de composicin
qumica compleja y de baja simetra (Kraus, y col., 1965). La imperfeccin cristalina
natural de los materiales muestra diversos patrones de difraccin de rayos X, que se
representan en forma de bandas o lneas, las cuales al ser medidas con exactitud dan
informacin acerca de los defectos estructurales (Brindley y Brown, 1980).

Para el anlisis de difraccin por rayos X normalmente se utilizan radiaciones de

Cu, Co, Fe y Cr. Cada uno de ellos tiene diferente poder de difraccin al poseer
longitudes de onda caractersticas. Las de Cu son las ms utilizadas en anlisis de
zeolitas (Brindley y Brown, 1980).

Las medidas realizadas en este trabajo se llevaron a cabo en un aparato de DRX

modelo Seifert JSO-DEBYEFLEX 2002, que est provisto de un ctodo de cobre y un
filtro de nquel.

A ttulo de ejemplo, en la figura 4.1 se muestra un difractograma de rayos X

patrn de una zeolita A obtenido de la web de la International Zeolite Association
(IZA). En este difractograma se puede observar la presencia de mltiples bandas de
difraccin estrechas y bien definidas, que ponen de manifiesto el alto ordenamiento de
la estructura y la cristalinidad de este tipo de materiales. La comparacin de los
difractogramas obtenidos para los materiales sintetizados con los correspondientes
difractogramas patrn permite la correcta identificacin de dichos materiales.

68

Materiales y Mtodos

Figura 4.1. DRX de una Zeolita A

4.2.2. Microscopia electrnica de transmisin (TEM)

En la tcnica de microscopa electrnica de transmisin (TEM), se irradia una
muestra delgada con un haz de electrones de densidad de corriente uniforme, cuya
energa est dentro del intervalo de 100 a 200 keV. Parte de esos electrones son
transmitidos, otra parte son dispersados y otra parte da lugar a interacciones que
producen distintos fenmenos como emisin de luz, electrones secundarios, rayos X,
etc. Todas estas seales se pueden emplear para obtener informacin sobre la naturaleza
de la muestra (morfologa, composicin, estructura cristalina, estructura electrnica,
etc.). El microscopio electrnico de transmisin emplea la transmisin/dispersin de los
electrones para formar imgenes.

Para que se produzca la transmisin de electrones a travs de la muestra es

necesario que sta sea lo suficientemente delgada como para ser transparente a los
electrones. Es recomendable no utilizar muestras de ms de 100 nm de grosor ya que

69

Materiales y Mtodos

cuanto menor sea el espesor de la muestra, mejor calidad de imgenes se puede

obtener.

Figura 4.2. Microfotografa obtenida por TEM de la zeolita HZSM-5 comercial

En este trabajo se ha utilizado la tcnica de microscopia electrnica de

transmisin para determinar la morfologa de los catalizadores preparados. El
microscopio utilizado fue un JEOL, modelo JEM-2010 provisto de un sistema de
microanlisis mediante espectroscopia de dispersin de rayos-X (EDS) OXFORD. A
ttulo de ejemplo, en la figura 4.2 se muestra una microfotografa de la imagen de la
zeolita HZSM-5 comercial obtenida por TEM.

4.2.3. Microscopia electrnica de Barrido (SEM)

Esta tcnica consiste, principalmente, en hacer incidir un haz de electrones sobre
la muestra a estudiar y, mediante un detector apropiado, registrar el resultado de esta
interaccin. El haz se desplaza sobre la muestra realizando un barrido en las direcciones
x e y de tal modo que la posicin en la que se encuentra el haz en cada momento
coincide con la aparicin de brillo, proporcionalmente a la seal emitida, en un
determinado punto de una pantalla, con lo que se puede obtener una microfotografa de
la muestra estudiada.

70

Materiales y Mtodos

Las imgenes que se obtienen en el microscopio electrnico de barrido

corresponden a electrones secundarios o electrones retrodispersados emitidos tras la
interaccin con la muestra de un haz incidente de entre 5 y 30 KeV.

Figura 4.3. Imagen obtenida por SEM de la zeolita USY comercial

Las muestras que quieran ser investigadas mediante microscopa electrnica de

barrido deben ser secadas antes de ser introducidas en el microscopio, de otro modo la
baja presin existente en el mismo causar que el agua (y otros lquidos voltiles) se
evaporen, saliendo violentamente del espcimen y alterando la estructura del mismo.
As mismo, para que una muestra se pueda visualizar, debe ser conductora de la
electricidad ya que, de no ser as, se carga durante la irradiacin y desva el haz
electrnico incidente y, como consecuencia, aparecen distorsiones en la imagen. La
solucin a este problema, en el caso de materiales no conductores como las zeolitas,
consiste en recubrir la muestra con una pelcula conductora, de espesor comprendido
entre 10 y 25 nm.

La eleccin del material con el que se va a recubrir la muestra depende

fundamentalmente del tipo de estudio que se vaya a realizar. As, para la observacin de
imgenes de electrones secundarios, como es el caso del presente trabajo, el oro y el
oro-paladio son los materiales que conducen a los mejores resultados ya que, al ser
elementos pesados, producen mayor emisin. Cuando lo que se pretende es realizar un
estudio microanaltico, es recomendable emplear carbono.

71

Materiales y Mtodos

El equipo utilizado para realizar las microfotografas fue un JEOL modelo JSM840, con una magnificacin mxima de 300.000. En la figura 4.3 se puede observar una
imagen obtenida por SEM de la zeolita USY comercial utilizada en este trabajo.

4.2.4. Isotermas de adsorcin de nitrgeno

Las isotermas de adsorcin de nitrgeno a 77 K se realizaron con el objetivo de
determinar la superficie especfica, el tamao de poro y el rea externa de los diferentes
catalizadores estudiados. Los ensayos se llevaron a cabo en un equipo automtico de
adsorcin fsica de gases AUTOSORB-6 de la marca Quantachrome.

La superficie de los slidos es una regin singular, que es responsable o al

menos condiciona muchas de sus propiedades. Los tomos que se encuentran en ella no
tienen las fuerzas de cohesin compensadas y son responsables de las propiedades de
adsorcin que presentan los slidos.

Existen dos tipos de adsorcin: i) fisisorcin y ii) quimisorcin. La diferencia

fundamental entre ambas es que en el caso de la fisisorcin la especie adsorbida
(fisisorbida) conserva su naturaleza qumica, mientras que durante la quimisorcin la
especie adsorbida (quimisorbida) sufre una transformacin ms o menos intensa para
dar lugar a una especie distinta. En la adsorcin fsica, la sustancia adsorbida o
adsorbato interacciona con el slido adsorbente mediante fuerzas de interaccin
intermoleculares, mientras que en la adsorcin qumica se produce una reaccin qumica
que es la que da como resultado la unin entre el adsorbato y el adsorbente. En algunos
casos no es sencillo distinguir entre ambos tipos de adsorcin, ocurriendo, en algunas
ocasiones, situaciones intermedias.

En la mayora de los slidos la superficie no es totalmente plana, sino que

presenta rugosidades ms o menos pronunciadas o incluso porosidad. En el caso de los
slidos porosos, y muy especialmente en el caso de las zeolitas, la adsorcin ocurre
fundamentalmente en los poros. La IUPAC reconoce tres tipos de poros atendiendo a su
tamao: si son mayores de 50 nm se conocen como macroporos, si su dimetro est

72

Materiales y Mtodos

comprendido entre 2 y 50 nm se trata de mesoporos y si son menores de 2 nm, como es

el caso de los poros de las zeolitas, son microporos.

Figura. 4.4. Representacin esquemtica de los seis tipos de isotermas de adsorcin

(Garca y col, 2003)

La cantidad de gas adsorbido a una temperatura dada para distintas presiones

relativas de gas se conoce como isoterma de adsorcin. Las isotermas de adsorcin son
muy tiles para la caracterizacin de slidos porosos. La IUPAC reconoce 6 tipos de
isotermas de adsorcin (Sing y col., 1985), representadas de forma esquemtica en la
Figura 4.4. En ellas se representa la cantidad de nitrgeno adsorbido, V, frente a la
presin relativa, P/P0, siendo P la presin parcial del nitrgeno y P0 la presin de
saturacin del nitrgeno a la temperatura a la que se obtiene la isoterma.

La isoterma tipo I se caracteriza porque la adsorcin se produce a presiones

relativas bajas y es la que muestran los slidos microporosos. La isoterma tipo II es
caracterstica de slidos macroporosos o no porosos, tales como negros de carbn. La
isoterma tipo III ocurre cuando la interaccin adsorbato-adsorbente es baja. Este tipo de
isoterma se ha observado en adsorcin de agua en negros de carbn grafitizados. La
isoterma tipo IV es caracterstica de slidos mesoporosos. Presenta un incremento de la
cantidad adsorbida importante a presiones relativas intermedias y ocurre mediante un
mecanismo de llenado en multicapas. La isoterma tipo V, al igual que la isoterma tipo
III es caracterstica de interacciones adsorbato-adsorbente dbiles, pero se diferencia de
73

Materiales y Mtodos

la anterior en que el tramo final no es asinttico. La isoterma tipo VI es poco frecuente,

y se ha observado, por ejemplo, en la adsorcin de gases nobles en carbn grafitizado
(Garca y col., 2003).

La adsorcin de N2 a 77 K es la tcnica que se utiliza ms ampliamente para la

obtencin de isotermas de adsorcin debido a que permite cubrir todo el rango de
porosidad y a que el N2 puede interaccionar dbilmente con la mayora de slidos. Sin
embargo, cuando se utiliza para la caracterizacin de slidos con microporosidad
estrecha, que es la que presentan la mayora de las zeolitas, se obtienen valores menores
de los esperados debido a problemas difusionales (Garca y col, 2003). A ttulo de
ejemplo, en la Figura 4.5 se muestra una isoterma de adsorcin de N2 a 77 K tpica para
la zeolita HZSM-5. Como puede observarse, no se trata de una isoterma de tipo I, que es
la que presentan la mayora de las zeolitas, sino que muestra un ciclo de histresis bien
definido. Adems este ciclo de histresis aumenta a medida que crece el tamao del
cristal y la relacin slice/almina de la zeolita. Estudios realizados mediante difraccin
de neutrones han permitido comprobar que estos cambios se deben a cambios de fase en
el adsorbato (Garca y col, 2003). De hecho, estos autores defienden que el salto
observado en la isoterma de la Figura 4.5 corresponde con el cambio de densidad del N2
lquido a slido.

Figura 4.5. Isoterma de N2 a 77 K tpica de una zeolita HZSM-5 (Garca y col, 2003)
Se han desarrollado numerosos mtodos con el objetivo de estimar la superficie
especfica de las sustancias, siendo el mtodo BET el usado ms ampliamente (rea
BET). El mtodo BET (Brunauer, Emmett y Teller, 1938), se aplica a presiones
relativas tales que no haya ninguna condensacin capilar en micro y/o mesoporos

74

Materiales y Mtodos

(P/P0<0.35). La idea central del mtodo BET consiste en que, conocida la cantidad de
gas adsorbido necesaria para formar una monocapa y el rea que ocupa cada una de las
molculas adsorbidas, es posible estimar el rea superficial del slido. Para estimar la
cantidad de gas adsorbido necesario para la formacin de una monocapa se utiliza la
siguiente ecuacin:

C 1 P
1
1

=
+
W (( P0 / P ) 1) Wm C Wm C P0

(1)

donde C es una constante que est relacionada con la energa de adsorcin de la primera
monocapa, Wm es el peso del adsorbato en la monocapa y P/P0 es la presin relativa. De
la presentacin grfica de

1
W (( P0 / P ) 1)

frente a P/P0 se puede obtener el valor de

Wm. A partir de este valor se puede calcular el valor de la superficie total mediante la
ecuacin:

W NA
S t = m CS
M

(2)

donde N es el nmero de Avogadro (6.0221023 molecules/mol), M el peso molecular

del adsorbato y ACS es el rea transversal del adsorbato, que para el nitrgeno es de 16.2
2.
El rea BET del slido, S, se calcula a partir de la siguiente ecuacin:

S= St /w

(3)

donde St representa el rea total y w la masa de la muestra.

En el presente trabajo, para determinar el tamao de poro se emple el mtodo
BJH (Barret, Joyner y Halenda, 1951), que asume un modelo de poros de geometra
cilndrica. El mtodo considera la condensacin capilar en los poros usando la ecuacin
clsica de Kelvin. En cada poro, el exceso de adsorcin total viene dado por el grosor de
la capa superficial, t(P), ms un trmino; el poro se llena si la presin satisface:

Ln

P 2VL

P0
RTrc

(4)

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Materiales y Mtodos

donde rc es el radio de curvatura del poro, r es el tamao real del poro, y t(P) es el
espesor de la capa adsorbida en el poro antes de que haya tenido lugar la condensacin
capilar (rc = r t(P) ), T la temperatura de trabajo, R la constante de los gases, VL es el
volumen molecular del lquido y su tensin superficial. El mtodo BJH supone la
representacin grfica de la distribucin de tamao de poro frente a dV/dlog(r) estimada
mediante la aplicacin de la ecuacin de Kelvin para las diferentes presiones.

El rea externa de los materiales se determin mediante el mtodo t, utilizando

la ecuacin de Jura-Harkins para determinar el espesor de la capa de nitrgeno
adsorbida sobre la superficie del catalizador. Su aplicacin se realiz en un intervalo de
presiones relativas tal que la condensacin capilar en micro y/o mesoporos se ha
producido previamente (P/P0>0.5) y nicamente tiene lugar adsorcin en multicapa
sobre la superficie externa. El mtodo t consiste en la representacin lineal del volumen
de gas adsorbido frente a t, cuya pediente toma el valor de St/15.47:
St =

Vads * 15.47
t

(5)

donde t es un valor estadstico del grosor de la pelcula adsorbida obtenido segn la

ecuacin de Boer (6), y 15.47 es el factor de conversin del volumen del gas al volumen
del lquido:

13.99
t () =

log( P0 / P ) + 0.034

1/ 2

( 6)

Para calcular el rea superficial y el volumen de poro en el caso de los slidos

microporosos (HZSM-5), se emple el mtodo de Dubinin-Radushkevich (DR). Este
mtodo tiene la particularidad de ser vlido cuando los poros son del mismo orden de
magnitud que el tamao de las molculas de gas adsorbato. El mtodo desarrolla una
ecuacin emprica que puede aplicarse a materiales microporosos (la ecuacin fue
diseada para el estudio de carbones activos). Teniendo en cuenta el potencial de
adsorcin, A:

P
A = RTLn 0 = G
P

76

(7)

Materiales y Mtodos

donde A expresa el trabajo molar diferencial de adsorcin, R es la constante de los

gases, T la temperatura y P/P0 la presin relativa. La ecuacin de DubininRadushkevich (DR) tiene la siguiente forma:

A
W = W0 exp
E 0

(8)

donde W es la cantidad absorbida a una presin relativa P/P0 y a una temperatura T, W0

es el volumen de microporo limitante, E0 la energa caracterstica de adsorcin para el
gas de referencia y el coeficiente de afinidad, cuyo valor es la unidad cuando el
adsorbato es el gas de referencia.
Substituyendo la ecuacin (7) en la ecuacin (8) y aplicando logaritmos se
obtiene la ecuacin (9):
RT
LnW = LnW 0
E o

P0
Ln
P

(9 )

La representacin grfica de lnW en funcin de (ln(P/P0))2, cuando el slido

adsorbente es microporoso, proporciona una recta cuya ordenada al origen es el valor de
W0, volumen del microporo en el slido adsorbente.
Una vez obtenido el valor de W0 el rea superficial se puede calcular a partir de
las ecuaciones (2) y (3).

4.2.5. Fluorescencia de rayos X (FRX)

La espectroscopia de fluorescencia de rayos X (FRX) suele emplearse cuando se
desea conocer con rapidez la composicin elemental de una sustancia. Mediante esta
tcnica es posible determinar la existencia de elementos del Sistema Peridico, desde el
flor hasta el uranio, en muestras slidas, en polvos y en lquidos. Asimismo, mediante
la utilizacin de los patrones adecuados, es posible realizar el anlisis cuantitativo de los
elementos presentes.

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Materiales y Mtodos

El fundamento de esta tcnica consiste en la excitacin de la muestra por

irradiacin con el haz de un tubo de rayos X o una fuente radiactiva. En estas
condiciones, los elementos de la muestra, al ser excitados por la absorcin del haz
primario, emiten rayos X fluorescentes caractersticos, que se pueden identificar
mediante tablas y se cuantifican mediante la medida del rea de los picos de
fluorescencia.

En este trabajo se ha utilizado esta tcnica para determinar la relacin Si/Al de

los catalizadores estudiados, para ello se empleo un equipo de Philips modelo PW1480,
que incorpora un software de anlisis semicuantitativo UNIQUANT II.

4.2.6. Desorcin trmica programada (DTP) de amoniaco

La desorcin trmica programada (DTP) de amoniaco se utiliza para determinar
la acidez y la distribucin de la fuerza cida de materiales cidos. El fundamento de esta
tcnica consiste en tratar el catalizador con una corriente de amoniaco, que se adsorbe
en los centros cidos accesibles y a continuacin se somete al material a un programa
de calefaccin controlada. La desorcin del amoniaco que se produce al calentar la
muestra tiene lugar a mayor o menor temperatura en funcin de la fuerza cida de los
centros sobre los que ha sido adsorbido. La seleccin del amoniaco como adsorbato se
debe a sus caractersticas bsicas, que permiten su adsorcin en prcticamente todos los
centros cidos, aun siendo dbiles, y a su reducido tamao, que le permite alcanzar los
centros del interior de los poros de la zeolita.

El proceso de DTP de amoniaco consta de las siguientes etapas: desgasificacin,

adsorcin de amoniaco, desorcin del gas fisisorbido y desorcin trmica programada.
Inicialmente los catalizadores se encuentran en su forma cida. Estos se someten a un
tratamiento de desgasificacin con el fin de eliminar todas las sustancias fisisorbidas y
quimisorbidas en sus centros cidos. Tras la desgasificacin, se hace circular una
corriente de amoniaco producindose el proceso de adsorcin. A continuacin, a la
misma temperatura, se hace pasar una corriente de gas inerte con el fin de eliminar toda
sustancia fisisorbida en la superficie. Por ltimo, se somete a la muestra a un programa

78

Materiales y Mtodos

de temperatura, bajo una corriente de gas inerte, producindose entonces el proceso de

desorcin. Esta ltima etapa es la DTP propiamente dicha.

En el presente trabajo, las medidas de desorcin trmica programada de

amoniaco se realizaron en una termobalanza Netzsch TG 209, con el objetivo de
determinar la acidez y la distribucin de la fuerza cida de los catalizadores estudiados.
Las condiciones utilizadas en el programa de DTP se describen a continuacin:

Desgasificacin:
-

Caudal de 45 mL/min de N2

Rampa de calentamiento de 20 C a 500 C a 10 C/min

Isoterma a 500 C durante 30 min

Enfriamiento hasta 100 C a una velocidad de 10 C/min

Tratamiento con NH3:

-

Caudal de 35 mL/min de NH3

Isoterma a 100 C durante 30 min

Fisidesorcin de NH3 :
-

Caudal de 45 mL/min de N2

Desorcin: isoterma a 100C durante 60 min

Desorcin trmica programada:

-

Caudal de 45 mL/min de N2

Calentamiento de 100 C a 900 C a una velocidad de 10 C/min

La cantidad total de centros cidos existentes en el catalizador se calcula

mediante la siguiente expresin, donde la acidez se expresa en milimoles de amoniaco
por gramo de slido cido.
Acidez =

% masa perdida
1
1000 mmol
*
*
= mmol / g
100
1mol
PM NH 3

79

Materiales y Mtodos

donde % masa perdida representa la prdida de masa registrada por la termobalanza, en

porcentaje, en la etapa de desorcin trmica programada de amoniaco.

La etapa de DTP de amoniaco est caracterizada por la curva de prdida de peso

frente a la temperatura (curvas TGA). Si el material estudiado presenta diferentes tipos
de centros cidos, la curva derivada de la curva TGA (curva DTG) presentar diferentes
picos, correspondientes a la desorcin del amoniaco en cada tipo de centro (figura 4.6).
La temperatura correspondiente al mximo de desorcin de cada pico se encuentra
estrechamente relacionada con la fuerza cida de los centros y se considera
habitualmente como una medida directa de dicha fuerza con fines comparativos. Esta
tcnica, no obstante, presenta la limitacin de no poder diferenciar entre los centros
cidos de Brnsted y los de Lewis.

Para la determinacin de la acidez asociada a cada tipo de centro cido se midi

la prdida de peso asociada a cada pico de desorcin en la curva de DTG, leyendo
directamente sobre la curva de TGA. Como punto de referencia para las medidas de
prdida de peso se consider la temperatura (o el tiempo) para la que se observaba la
separacin entre los picos de la curva de DTG (figura 4.6).

0,014
%w
DTG

99,5

%w

99

0,012
0,01
0,008

98,5
0,006
98

0,004

97,5
97
100

0,002

200

300

400

500

0
600

T (C)
Figura 4.6. Curva DTG obtenida a partir de la DTP de NH3 para un material ZSM-5

80

DTG

100

Materiales y Mtodos

4.2.7. Resonancia magntica nuclear de Al27 y Si29 (RMN)

La resonancia magntica nuclear (RMN) fue descubierta durante la dcada de
1930 por Isidor Isaac Rabi y su grupo de investigacin de la Universidad de Columbia
[4], quienes desarrollaron la resonancia magntica de haces moleculares como tcnica
para estudiar las propiedades magnticas y la estructura interna de las molculas, los
tomos y los ncleos.

La espectroscopa de resonancia magntica nuclear se basa en la absorcin de

energa de una frecuencia determinada, en el intervalo de radiofrecuencias, asociada a
los cambios de orientacin del spin nuclear en presencia de un campo magntico fuerte.
Esta interaccin se ve influenciada por los ncleos vecinos, por lo que esta tcnica
permite obtener informacin sobre la estructura y geometra de la molcula.

La resonancia magntica utiliza algunas propiedades fundamentales de los

ncleos atmicos, en particular los momentos magnticos. Cuando se colocan en un
campo magntico externo potente, la direccin del momento magntico oscila o cambia
segn la direccin del campo, con una frecuencia proporcional a la fuerza del campo
externo. La resonancia magntica se produce cuando la fuerza del campo magntico se
manipula hasta que la frecuencia de la partcula coincide con la de la frecuencia
aplicada. Esto hace que el momento magntico de la partcula cambie de orientacin en
relacin al campo magntico externo, dando lugar a una seal detectable que revela la
estructura interna y la actividad de la especie que genera la seal, que puede abarcar
desde elementos qumicos hasta el cerebro humano.

En el caso de las zeolitas (silicatos y aluminosilicatos) y los zeotipos

(aluminofosfatos y silicoaluminofosfatos), la RMN de Al27 y Si29 da informacin sobre
el entorno local de los tomos en la red. Esta informacin complementa los datos de
difraccin de rayos X y permite la elucidacin estructural de nuevos materiales.

En el presente trabajo se ha utilizado un espectrmetro de RMN de

Transformada de Fourier de la marca Bruker modelo AC-300. En el equipo, el imn es
una bobina superconductora que produce 300 MHz. A ttulo de ejemplo en la Figura
4.7 se muestra un espectro tpico de Al27 de una zeolita HZSM-5. Como puede verse,
81

Materiales y Mtodos

presenta dos picos, resultado de los dos entornos en que puede encontrarse el Al en la
estructura de la zeolita, tetradrico y octadrico. En general, el aluminio hexacoordinado
presenta un pico a 0 ppm, mientras que el aluminio tetradrico aparece a 54 ppm
(Corma y col., 2000).

54.976

-0.476

150

125

100

75

50

25

ppm

-25

-50

-75

Figura 4.7. RMN Al27 de HZSM-5

En los espectros de RMN se representa el desplazamiento qumico que sufre el
material, que es funcin de la densidad electrnica del entorno en que se encuentra, y se
mide en unidades de partes por milln, ppm. El cero del espectro se toma
arbitrariamente como la seal singlete que da el tetrametilsilano, con lo que se pueden
comparar seales generadas por distintos materiales. La intensidad por su parte es
proporcional al nmero de tomos que sigue ese comportamiento.

4.3.

CARACTERSTICAS

DE

LOS

MATERIALES

EMPLEADOS
4.3.1. Polmeros
Para el estudio del comportamiento de los diferentes slidos cidos sintetizados
como catalizadores en el proceso de pirlisis cataltica de polmeros se seleccionaron
cuatro polmeros con diferentes propiedades. Los cuatro polmeros usados han sido:
polietileno de baja densidad (LDPE), polipropileno (PP), poliestireno de alto impacto
(HIPS), y un copolmero de etileno y acetato de vinilo (EVA).

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Materiales y Mtodos

Para el estudio de la influencia del rea superficial externa y de los procesos de

desactivacin de los centros cidos superficiales durante el proceso de pirlisis, se
emplearon tres polmeros, polietileno de baja densidad (LDPE), polipropileno (PP), y el
copolmero de etileno y acetato de vinilo (EVA).

Para el estudio de la viabilidad del uso de tcnicas de pirlisis cataltica como

va para la caracterizacin de polmeros se seleccion MCM-41 como catalizador y
diferentes polmeros, poliestireno de alto impacto (HIPS), poliestireno cristal (PS) y
polibutadieno (PB), y dos copolmeros SBS de composicin conocida, (Calprene 487, y
Solprene 416). Las caractersticas de todos estos polmeros segn los correspondientes
proveedores se muestran en la tabla 4.3.
Tabla 4.3. Propiedades fisicoqumicas de los materiales plsticos seleccionados
Densidad
g/cm3

ndice
Fluidez
g/10min

Mdulo Traccin
MPa

Estudio

LDPE 780R

0.923

20

115

A, B

PP Novolen 1100L

0.910

1500

A, B

HIPS Polystyrol 473D

1,05

12

1700

A, C, D

EVA Escorene UL15028C

0.950

150

13

A, B

PS Crystal Polystyrol 143E

1,043

10

3300

PB Polybutadiene JSR 830RB

0,909

7.8

Material

SBS Calprene 487

14

SBS Solprene 416

0.94

Fuel (VGO)

0.920

LDPE PG 7008

0.918

<0.5

D
2.7

D
E, F

7.7

200

E, F

A. Estudio de la actividad cataltica de los diferentes catalizadores sintetizados

B. Estudio del efecto de la elevada rea externa del MCM-41
C. Estudio de la influencia del contacto entre polmero/catalizador en la descomposicin
de HIPS en presencia de MCM-41
D. Desarrollo de un modelo pseudocintico
E. Estudio de la descomposicin de mezclas VGO/PE en termobalanza
F. Estudio de la evolucin de los gases generados en el proceso de descomposicin de
mezclas VGO-PE

83

Materiales y Mtodos

4.3.2 Catalizadores
Durante el desarrollo de la tesis, se han preparado tres catalizadores, una zeolita
ampliamente usada en la pirlisis cataltica de plsticos, la HZSM-5, y dos materiales
aluminosilicatos MCM-41 con dos relaciones Si/Al significativamente diferentes.

Tabla 4.4. Propiedades fisicoqumicas de los catalizadores

HZSM-5

MCM-41
(47)

Tamao de Poro
(nm)

0.51x0.55

2.4

1.7

Area BET (m2/g)

334

1136

Area Externa
(m2/g)

67

Propiedad

MCM-41 HZSM-5
(7)
comercial

USY

HBeta

FCC

0.51x0.55

0.74

0.66x0.67
0.56x0.56

-----

956

341

614

510

268

383

126

38

28

183

77

0.27

1.34

1.00

0.18

0.35

0.17

0.18

Relacin
SiO2/AlO2

24

47

22

4.8

25

0.97

Acidez Total
(mmol/g)

1.4

0.7

2.1

2.0

2.1

2.1

1.9

Acidez dbil
(mmol/g)

0.8

0.7

1.4

1.2

2.1

1.1

1.3

Acidez fuerte
(mmol/g)

0.6

-----

0.7

0.8

-----

1.0

0.6

165-385

138

155-550

166-466

154

190-370

156-632

A, B, C,
D, E

E, F

Volumen de Poro
(cm3/g)

T desorcion NH3
(C)
Estudio

A. Estudio de la actividad cataltica de los diferentes catalizadores sintetizados

B. Estudio del efecto de la elevada rea externa del MCM-41.
C. Estudio de la influencia del contacto entre polmero/catalizador en la descomposicin
de HIPS en presencia de MCM-41
D. Desarrollo de un modelo pseudocintico
E. Estudio de la descomposicin de mezclas VGO/PE en termobalanza
F. Estudio de la evolucin de los compuestos generados en el proceso de
descomposicin de mezclas VGO-PE
As mismo, tambin se ha trabajado con catalizadores comerciales, emplendose
para distintos estudios las zeolitas HZSM-5, HBeta, HUSY, y un catalizador de
84

Materiales y Mtodos

equilibrio FCC. En la Tabla 4.4 se recogen las principales propiedades fisicoqumicas

obtenidas de la caracterizacin de dichos materiales mediante la aplicacin de las
tcnicas descritas en la seccin 4.2 y el tipo de estudio donde han sido aplicados. Las
zeolitas HZSM-5 y HUSY fueron suministradas por Grace Davison, la zeolita HBeta
fue suministrada por Sd-Chemie Inc y el catalizador de equilibrio de FCC fue
proporcionado por Repsol YPF.

4.4. TCNICAS, CONDICIONES EXPERIMENTALES Y

EQUIPOS EMPLEADOS
El siguiente apartado se muestra dividido en dos secciones. En la primera se
describirn las diferentes tcnicas instrumentales y los equipos empleados en el
desarrollo de este trabajo, indicando a su vez en que publicacin han sido empleados. A
continuacin se describirn las condiciones experimentales empleadas para la
realizacin de cada uno de los estudios.

4.4.1. Tcnicas experimentales empleadas en el desarrollo de la

tesis.
4.4.1.1. Anlisis termogavimtrico (TGA)
El anlisis trmico engloba al conjunto de tcnicas analticas que estudian el
comportamiento trmico de los materiales. Cuando un material es calentado o enfriado,
su estructura y su composicin qumica sufren cambios: fusin, solidificacin,
cristalizacin, oxidacin, descomposicin, transicin, expansin, sinterizacin, etc.
Estas transformaciones se pueden determinar, estudiar y analizar, midiendo la variacin
de distintas propiedades de la materia en funcin de la temperatura. Entre estas tcnicas
se encuentra el anlisis termogavimtrico, que se basa en la medida del aumento o la
prdida de peso que sufre la muestra sometida a un programa de temperatura
controlado, en una determinada atmsfera, en funcin del tiempo o de la temperatura.
Los distintos equipos empleados han sido:

- Termobalanza Perkin Elmer Pyris 1 (Publicacin I). El equipo fue calibrado

segn las especificaciones del fabricante. Durante los ensayos se trabaj en atmsfera

85

Materiales y Mtodos

inerte con un caudal de nitrgeno de 57 mL/min, sometiendo a la muestra a un

calentamiento dinmico desde la temperatura ambiente hasta la temperatura deseada,
con una velocidad de calentamiento de 10 C/min. Para los distintos ensayos se
utilizaron unos 4 mg de muestra.
- Termobalanza Netzsch, modelo TG 209 (Publicacines II-VII). La balanza y el
termopar fueron calibrados siguiendo las instrucciones del fabricante, y las condiciones
experimentales fueron controladas mediante un ordenador que opera bajo entorno
Windows. Se trabaj en una atmsfera de nitrgeno y con un caudal de 45 STP mL/min.
En el portamuestras se emplearon, tanto en el caso de pirlisis trmica, como en el caso
de pirlisis cataltica, unos 4 mg de muestra.
- Termobalanza METTLER TOLEDO, modelo TGA/SDTA851e/LF/1600
(Publicacin V). Para la estimacin del porcentaje de coque formado en presencia de los
diferentes catalizadores utilizados en este trabajo tras un experimento de pirlisis
cataltica, se trataron los catalizadores coquizados en termobalanza en una atmsfera
oxidante, con una relacin He/O2 de 80:20, donde se calent desde 25-850 C a una
velocidad de calentamiento de 10 C/min. El equipo empleado fue calibrado segn las
especificaciones del fabricante.

4.4.1.2. Espectrometra FTIR conectada en lnea con un analizador

termogavimtrico (TGA/FTIR)
El anlisis cualitativo de los gases que se forman durante la descomposicin de
un polmero mediante los procesos de pirlisis trmica y cataltica se puede realizar
mediante una termobalanza acoplada en lnea a un espectrmetro de FTIR, tal como se
muestra en la figura 4.8. Este dispositivo permite analizar los gases procedentes de la
celda de TG mediante espectrometra infrarroja por transformada de Fourier (FTIR), de
tal forma que es posible observar simultneamente la perdida de peso y la evolucin con
el tiempo de los productos resultantes de la degradacin.

La conexin de la balanza y la celda para la de medida del gas de FTIR se

realiz mediante una lnea de transferencia flexible que puede calentarse hasta los 300
C para evitar la condensacin de los productos menos voltiles y garantizar al mximo
la transferencia cuantitativa de los productos gaseosos generados en la descomposicin

86

Materiales y Mtodos

que ocurre en la termobalanza. En los experimentos realizados, la lnea de transferencia

y la celda de medida de gases en el FTIR se mantuvieron a 200 C. El eqipo utilizado
fue:

Figura 4.8. Esquema del montaje TGA/FTIR

- Espectrmetro de FTIR Bruker-Tensor 27 (Publicacin I). Los espectros de
infrarrojos fueron adquiridos a una resolucin de 4 cm-1 y se realizaron 8 barridos por
espectro, generndose un espectro cada 16.54 s, que equivale aproximadamente a un
incremento de 2.8 C en el programa del TGA.

4.4.1.3. Experimentos en Reactor de lecho fijo

El reactor de lecho fijo utilizado (Publicacin VI) es un reactor vertical, donde
los gases entran por la parte inferior del sistema y salen por la superior, facilitando as la
eliminacin de los gases generados durante el experimento (Figura 4.9). La salida de los
gases se calent a 300 C para evitar la condensacin de los compuestos menos
volatiles. El reactor se calent mediante un horno elctrico conectado a un controlador
de la temperatura. La muestra se coloc en un cubilete de cuarzo, en el centro del
reactor, y se dispuso un termopar en contacto directo con la muestra para controlar la
temperatura del proceso. Antes de comenzar los experimentos, el sistema se purgaba
con nitrgeno durante 30 min, con un caudal de nitrgeno de 150 mL/min. Durante los

87

Materiales y Mtodos

ensayos de pirlisis se realizaron calentamientos dinmicos desde temperatura ambiente

hasta 550 C, con una velocidad de calentamiento de 5 C/min, y se recogieron las
diferentes fracciones de productos condensables y no condensables a intervalos de
temperatura de 50 C. Las sucesivas fracciones gaseosas generadas durante el
experimento se recogieron en bolsas de Tedlar. La composicin de las diferentes
fracciones recogidas a la salida del reactor se analizaron mediante un cromatografo de
gases conectado a un espectrmetro de masas Agilent 6890N GC-MD 5973N.

Figura 4.9. Diagrama del reactor de lecho fijo

Anlisis de los gases

Para el anlisis de los gases recogidos se us una columna GS-GasPro (30 m x
0.32 mm I.D.). El siguiente programa de temperatura empleado para la separacin de
los compuestos fue:

88

Temperatura del inyector 200 C

Gas portador: Helio

Volumen de muestra inyectada: 250 l

Materiales y Mtodos

Flujo de columna constante: 2 mL/min

Programa de temperatura del horno:

-

Temperatura inicial de la columna 35 C durante 5 min

Calentamiento hasta 170 C con una rampa de 5 C/min

Tiempo final 20 min;

La identificacin de los compuestos condensados se realiz con la ayuda de la

librera Wiley 275, que proporciona el propio programa de anlisis. Para mayor
seguridad en la identificacin de los productos, as como para la cuantificacin de los
mismos se utilizaron patrones de hidrocarburos gaseosos (Scout Special Gases), los
cuales fueron analizados con el mismo programa que las muestras. Los compuestos
utilizados como patrones, en orden creciente de tiempos de retencin, fueron: metano,
etano, eteno, propano, propeno, isobutano, n-butano, 1-buteno, 1,3-butadieno, trans-2buteno, isobuteno, cis-2-buteno, pentano, 1-butino, hexano, benceno y tolueno. En la
figura 4.10 se muestra, a ttulo de ejemplo, el aspecto de los cromatogramas tpicos
obtenidos para los gases en el caso de la pirlisis trmica y cataltica del PE, y en la
tabla 4.5 se muestra la asignacin de los principales picos del cromatograma.

El factor de respuesta (gramos de compuesto/rea de pico) se determin

mediante la inyeccin de diferentes masas (volmenes) de cada compuesto. La
cuantificacin de los compuestos gaseosos, dado que el nmero de compuestos
generados es muy superior al nmero de patrones, se realiz aplicando un factor de
respuesta medio para alcanos, alquenos y aromticos. Los gramos de compuesto
generados (mi), para cada uno de los compuestos presentes en la mezcla gaseosa
obtenida del proceso de descomposicin, fueron calculados mediante la siguiente
expresin:

mi =

reaxFR
xVtotal
Vinyectado

donde el rea es el valor obtenido de la integracin de los picos de cada compuesto, FR

es el factor de respuesta (g/rea), Vinyectado, representa el volumen de gas inyectado en el
cromatografo y Vtotal representa el volumen de gas contenido en la bolsa de tedlar. El

89

Materiales y Mtodos

volumen total de la bolsa fue determinado a partir del volumen de agua desplazado por
ese gas en una bureta invertida, despreciandose el error asociado al gas que puede
quedar disuelto en el agua.
2,E+07

2,E+07

1,E+07
Abundance

PE Trmico
PE Cataltico

1,E+07
1,E+07

8,E+06

6,E+06

4,E+06

2,E+06
0,E+00
0

10

15

20
t (min)

25

30

35

40

Figura 4.10. Cromatograma de gases obtenido en la descomposicin del polietileno

mediante pirolisis trmica y cataltica.

Tabla 4.5. Asignacin de los picos obtenidos en cromatografa de gases, la numeracin

de los picos hace referencia a la Figura 3.10
Pico
1
2
3
4
5
6
7
8

90

t (min)
1.659
2.207
4.703
10.023
11.189
12.194
16.943
18.079

Asignacin
Etano
Eteno
Propano
Propeno
Isobutano
Butano
1-buteno
1,3-butadieno

Materiales y Mtodos

4.4.2. Condiciones experimentales empleadas en los distintos

trabajos.
4.4.2.1. Publicacin I; Study of the influence of the characteristics of different
acid solids in the catalytic pyrolysis of different polymers.
La actividad cataltica de los distintos slidos cidos sintetizados en el presente
trabajo fue estudiada mediante anlisis termogavimtrico. Para ello se emple una
balanza Perkin Elmer Pyris 1 que permita determinar el intervalo de temperaturas en
que se produce la degradacin de diferentes polmetros en presencia y ausencia de los
catalizadores. En condiciones catalticas se trabaj siempre con un porcentaje de
catalizador del 20% y los polmetros estudiados fueron polietileno de baja densidad
(LDPE), polipropileno (PP), poliestireno de alto impacto (HIPS), y un copolmero de
etileno y acetato de vinilo (EVA).

El anlisis cualitativo de los gases que se forman durante la descomposicin de

un polmero mediante los procesos de pirlisis trmica y cataltica se realiz en una
termobalanza Netzsch TG 209 acoplada en lnea a un espectrmetro de FTIR BrukerTensor 27

4.4.2.2. Publicacin II; Study of the early deactivation in pyrolysis of polymers

in the presence of catalysts
En la descomposicin cataltica de diferentes polmeros en presencia de los
materiales MCM-41, se observ la existencia de una etapa inicial, previa a la
principal etapa de descomposicin, que se manifestaba por la aparicin de un pequeo
hombro en las curvas de DTG, y que podra estar relacionado con los centros cidos
superficiales. Este efecto fue solo visible en el caso de los catalizadores de elevada rea
superficial, como es el caso de los MCM-41. Para el estudio de la importancia de la
elevada rea superficial que presenta dicho catalizador MCM-41(7) en la pirlisis de
polmeros, y el anlisis de la rpida desactivacin que parecen sufrir estos centros
cidos superficiales durante el proceso de descomposicin cataltica de polmeros, se

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Materiales y Mtodos

seleccion uno de los MCM-41 (MCM-41(7)) y se realizaron ensayos de

termogavimetra en la termobalanza de Netzsch.

En los experimentos de descomposicin trmica y cataltica se calent desde

temperatura ambiente hasta 550 oC con una rampa de calentamiento de 10 oC/min. Por
otro lado, para el estudio de la influencia de la etapa inicial de descomposicin
observada, se aplicaron cuatro ciclos de calentamiento-enfriamiento a tres sistemas
diferentes: MCM-41/PE, MCM-41/PP y MCM-41/EVA. Durante los ciclos de
calentamiento-enfriamiento se calent con una rampa de 10 C/min y posteriormente el
sistema se enfri a 50 C/min. Las temperaturas mximas alcanzadas fueron de 300 C
para el caso de las muestras de MCM-41/PE, 245 C para el sistema MCM-41/PP y de
235 C para las mezclas con EVA, partindose en todos los casos de una temperatura de
50 C. En todos los experimentos, la temperatura mxima alcanzada fue siempre inferior
a la temperatura correspondiente al comienzo de la descomposicin del polmero
durante la descomposicin trmica, garantizndose as que los efectos observados
fueran debidos, exclusivamente, a la presencia del catalizador. Adems, estas
temperaturas fueron tambin inferiores a la temperatura de comienzo de la principal
etapa de descomposicin de los distintos polmeros.

Para evaluar la influencia de los ciclos de calentamiento-enfriamiento en la

actividad cataltica del catalizador, una vez terminados los ciclos, se detuvo el sistema y
se aadi polmero fresco con la finalidad de obtener un porcentaje de catalizador del
20% en peso y despus se realiz un experimento de pirlisis cataltica, donde se
calent desde la temperatura ambiente hasta 550 C con una velocidad de calentamiento
de 10 C/min.

4.4.2.3. Publicacin III; Characterization of high-impact polystyrene by

catalytic pyrolysis over Al-MCM-41: Study of the influence of the contact between
polymer and catalyst.
Durante el estudio de la descomposicin cataltica de poliestireno de alto
impacto (HIPS) en presencia de los catalizadores con mayor tamao de poro (MCM41), se observ la existencia de tres etapas diferentes de descomposicin, que no eran

92

Materiales y Mtodos

observadas en presencia de los otros slidos cidos con menor tamao de poro, y que
podra estar relacionada con la presencia de dos tipos de dominios en el copolmero,
dominios de poliestireno, y dominios de polibutadieno.

Para analizar la influencia del tamao de partcula del polmero en el proceso de

pirlisis trmica y cataltica, se moli una muestra de polestireno de alto impacto
(HIPS) empleando una granceadora IKA M20. Para facilitar la molienda del material,
evitando el uso de tiempos largos y el calentamiento excesivo del polmero, que podra
provocar su degradacin trmica, se aadi en la granceadora nitrgeno lquido, lo que
permiti refrigerar el material. A continuacin, el material obtenido se tamiz,
obtenindose las siguientes fracciones: 0.6-0.5 mm, 0.5-0.4 mm, 0.4-0.3 mm, 0.3-0.2
mm y menor de 0.2 mm.

Igualmente, para el estudio de la influencia del grado de contacto entre el

catalizador y el polmero, se prepararon muestras disolviendo los polmeros puros de los
que se compone el HIPS, poliestireno (PS) y polibutadieno (PB), en xileno. Este
disolvente fue seleccionado ya que permita disolver ambos polmeros. Una vez disuelto
el polmero, a la disolucin se le aadi el catalizador para obtener una mezcla con una
relacin del 20% w/w de catalizador, y la mezcla se agit al tiempo que se calentaba
para as eliminar el disolvente por evaporacin.

Tanto las muestras molidas y tamizadas como las obtenidas a partir de la

disolucin de xileno se analizaron por termogravimetra en una termobalanza Netzsch y
las diferentes muestras fueron pirolizadas en condiciones dinmicas, calentando desde
30 C a 550 C a una velocidad de calentamiento de 10 C/min. En el portamuestras se
colocaron cerca de 4 mg de muestra. Para el caso de las mezclas de polmerocatalizador, el polmero en polvo se mezcl cuidadosamente con el catalizador,
consiguiendo mezclas de cerca de un 20% en peso de MCM-41 (3.2 mg de polmero
con 0.8 mg de catalizador).

93

Materiales y Mtodos

4.4.2.4. Publicacin IV; Characterization of Styrene-Butadiene copolymers by

catalytic pyrolysis over Al-MCM-41
El comportamiento peculiar observado en la Publicacin III para el sistema
HIPS-MCM-41 puso de manifiesto la posibilidad de utilizar la pirlisis cataltica de
determinados polmeros como una herramienta para caracterizar la composicin de
copolmeros de butadieno y estireno, cuya composicin es difcil de determinar por
otros procedimientos. Para ello se seleccionaron dos copolmeros SBS proporcionados
por Dynasol y se estudiaron tambin muestras de PS y PB puros. As, los experimentos
de pirlisis cataltica de los copolmeros de butadieno-estireno realizados pusieron de
manifiesto que, en presencia de ciertos catalizadores, aparecan dos etapas de
descomposicin, que se asociaban a la descomposicin de los dominios de estireno y de
butadieno respectivamente, observndose una variacin en la importancia relativa de
dichas etapas segn el grado de contacto entre el polmero y el catalizador. En la

Publicacin IV se explor la posibilidad de la aplicacin de un modelo pseudocintico

capaz de reproducir de manera adecuada el comportamiento de los copolmeros de SBS
en la pirlisis cataltica en presencia de Al-MCM-41, que adems permitiera evaluar la
cantidad relativa del material que evoluciona por cada etapa.
Adems, de los anlisis convencionales, utilizando los polmeros y copolmeros
molidos, con el fin de garantizar un ntimo contacto entre los SBS y el catalizador, se
prepararon mezclas disolviendo los copolmeros puros en xileno. Una vez disuelto el
polmero, a la disolucin se le aadi el catalizador para obtener una mezcla de con una
relacin del 20% w/w de catalizador, y la mezcla se calent bajo agitacin para as
eliminar el disolvente por evaporacin, y obtener nuevamente un slido.

En este trabajo se utiliz anlisis termogavimtrico (TGA) para llevar a cabo el

estudio del comportamiento de los distintos sistemas durante el proceso de pirolisis, y
as poder desarrollar y aplicar un modelo pseudocintico a los datos obtenidos. Para ello
se emple una termobalanza Netzsch TG 209, donde se someti a la muestra a un
calentamiento desde la temperatura ambiente hasta 550 C, con una velocidad de
calentamiento de 10 C/min.

94

Materiales y Mtodos

4.4.2.5. Publicacin V; Characterization of vacuum gas oillow density polyethylene

blends by thermogravimetric analysis
Como se mencion anteriormente, hoy en da cada vez cobra ms importancia
una posibilidad alternativa de reciclado terciario, que se basa en el hecho de que es
posible disolver algunos polmeros en corrientes de gasleo de alto vaco (VGO) y usar
las unidades convencionales de FCC de las refineras para convertirlos en productos que
se encuentren en el rango de la gasolina. Como un estudio inicial, se analiz en una
termobalanza el comportamiento durante la descomposicin trmica y cataltica de
diferentes mezclas de VGO/PE, en la que se modific la proporcin del PE.

Las mezclas de VGO/PE se prepararon usando un mezclador Jankel & Kunkel

IKAVISC MR-F12. Para ello se trabaj manteniendo agitacin continua durante 120
minutos, a una temperatura de 120 C y con una velocidad de agitacin de 60 rpm. Se
utiliz LDPE y se prepararon muestras variando el porcentaje en peso de polietileno (1,
2.5, 5, 7.5, 10 %). La temperatura se seleccion al considerar que a 120 C el LDPE est
completamente fundido, lo que permiti obtener una mejor mezcla con el VGO.

El estudio del comportamiento de los distintos sistemas durante el proceso de

pirolisis se realiz mediante una termobalanza Netzsch TG 209 para determinar el
intervalo de temperaturas en que se produce la degradacin en presencia y ausencia de
catalizador, sometiendo a la muestra a un calentamiento desde temperatura ambiente
hasta 550C, con una velocidad de calentamiento de 10 C/min.

En primer lugar se estudi la pirlisis de las diferentes mezclas de VGO/PE,

tanto trmica como cataltica. En el caso de la descomposicin cataltica, en primer
lugar se estudi la pirlisis en presencia de catalizador de equilibrio FCC y se
estudiaron dos proporciones diferentes de catalizador, una relacin catalizador:polmero
7:1, que suele usarse en las refineras, y mezclas con una proporcin del 20% en peso en
catalizador, que es un valor frecuentemente usado en estudios bsicos de pirlisis
cataltica. Adems, con esta ltima relacin se estudio el comportamiento de las mezclas
en presencia de diferentes catalizadores comerciales (HZSM-5, HUSY, y HBeta) y del
material MCM-41(7), que es el catalizador ms activo de los sintetizados en el
laboratorio dentro de la presente investigacin.
95

Materiales y Mtodos

En este trabajo se realiz tambin una estimacin de la cantidad de coque que se

genera en el proceso mediante la oxidacin de los catalizadores coquizados obtenidos
tras el tratamiento de las mezclas VGO-PE, utilizando para ello una termobalanza y
atmsfera oxidante.

4.4.2.6. Publicacin VI; Study of the decomposition of Vacuum Gas Oils-Low

Density Polyethylene blends: evolution of the gases.
Durante la pirlisis trmica y cataltica de polmeros en condiciones dinmicas,
realizada con el equipo y las condiciones descritas en los apartados 4.4.1 y 4.4.2 de esta
memoria, se generan productos no condensables (gases), y condensables (lquidos y
ceras) cuya composicin se modifica segn transcurre en tiempo (y/o la temperatura) de
reaccin. En estas publicaciones se recogen los resultados del estudio de la evolucin de
la composicin de los productos generados durante la pirlisis trmica y cataltica de
PE, VGO y de una mezcla de VGO/PE al 10% de PE.
En este trabajo se ha utilizado el anlisis termogavimtrico (TGA) para llevar a
cabo un estudio inicial del intervalo de descomposicin que presentan los distintos
sistemas durante el proceso de pirlisis, realizado en condiciones dinmicas a una
velocidad de calentamiento de 5 C/min, con el fin de obtener informacin para poder
programar de manera adecuada la toma de muestras en los experimentos realizados en
el reactor de lecho fijo. Para ello se emple una termobalanza Netzsch TG 209,
sometiendo a la muestra a un calentamiento desde temperatura ambiente hasta 550 C.

Posteriormente se realizaron experimentos en el reactor de lecho fijo, en las

condiciones descritas en el apartado 4.4.1.4, donde se piroliz VGO, PE y una mezcla
de VGO-PE al 10% en peso de PE, tanto en ausencia como en presencia de catalizador
de equilibrio de FCC, con una relacin catalizador:material pirolizado de 7:1. Durante
los experimentos, se recogieron cada 50C, los productos no condensables (gases)
generados en bolsas tedlar. Las fracciones recogidas fueron posteriormente analizadas
mediante CG/MS en un equipo Agilent GCMS (GC 6890N-MD 5973N), lo que
permiti identificar los diferentes compuestos generados y analizar la evolucin de stos
con la temperatura.

96

CONCLUSIONES

Conclusiones

Las principales conclusiones obtenidas en el trabajo que se presenta en esta

memoria se muestran a continuacin, clasificadas segn la publicacin en la que
aparece reflejada.

Publicacin I Study of the influence of the characteristics of different acid solids

in the catalytic pyrolysis of different polymers.

1. En aquellos casos en que la estructura de la cadena de polmero es tal que no se

producen efectos estricos que dificultan su acceso al interior de los poros del
catalizador, los materiales plsticos ms reactivos son aquellos que presentan
mayor proporcin de carbonos terciarios.
2. La susceptibilidad de un polmero para ser afectado por la actividad cataltica de
los slidos cidos considerados disminuye conforme aumenta el tamao
molecular del polmero y la transversal media.
3. La actividad cataltica de los slidos estudiados aumenta al hacerlo la proporcin
de centros cidos y su rea especfica. As pues, el orden de actividad
encontrado ha sido:
LDPE, PP, HIPS, EVA: MCM-41(7) > MCM-41(47) > HZSM-5
MCM-41(47): PP > LDPE > EVA > PS
MCM-41(7): PP > LDPE > EVA > PS
HZSM-5: LDPE > PP > EVA > PS

Publicacin II Study of the early deactivation in pyrolysis of polymers in the

presence of catalysts.

1. Existe de una etapa inicial de pirlisis que depende de las caractersticas

qumicas y estructurales, tanto del polmero como del catalizador, y solo se
puede observar con claridad si el catalizador presenta una elevada rea
superficial, elevado tamao de poro y elevada acidez, que le permitan
proporcionar un elevado nmero de centros cidos superficiales, y por lo tanto
muy accesibles, que presenten actividad suficiente.

99

Conclusiones

2. Estos centros cidos, superficiales y suficientemente activos, se desactivan

rpida durante la etapa inicial de descomposicin.
3. Dicha etapa inicial es ms visible cuanto ms voluminoso es el polmero ya que,
en este caso, los impedimentos estricos que presenta le impiden acceder al
interior de los poros del catalizador y reacciona preferentemente en los centros
cido superficiales o ms accesibles.

Publicacin III Characterization of high-impact polystyrene by catalytic

pyrolysis over Al-MCM-41: Study of the influence of the contact between polymer and
catalyst.

1. En presencia de Al-MCM-41, el HIPS se descompone mediante tres etapas. Las

dos primeras etapas de descomposicin transcurren a temperaturas inferiores a
las temperaturas de pirlisis trmica obtenidas para los polmeros puros, PS y
PB, mientras que la tercera etapa de descomposicin ocurre a la misma
temperatura que la pirlisis trmica del PB puro.
2. La primera etapa est relacionada con la degradacin cataltica del material
segregado (PS, y HIPS) en la superficie del catalizador.
3. La segunda etapa de descomposicin, y principal, corresponde a la
descomposicin cataltica de los dominios de PS y parte de los dominios de PB.
4. Finalmente, la tercera y ltima etapa de descomposicin corresponde a la
degradacin por va trmica de los dominios de PB y de parte de los dominios de
PS que no habran sido descompuestos por la va cataltica.
5. La importancia relativa de cada etapa depende del grado de contacto que se
establece entre el polmero y el catalizador.

100

Conclusiones

Publicacin IV Characterization of Styrene-Butadiene copolymers by catalytic

pyrolysis over Al-MCM-41.

1. Se han desarrollado modelos pseudocinticos capaces de reproducir de manera

adecuada el comportamiento de los copolmeros y las mezclas de PB Y PS en la
pirlisis cataltica en presencia de Al-MCM-41.

Publicacin V Characterization of vacuum gas oillow density polyethylene

blends by thermogravimetric analysis.

1. El proceso de pirlisis de las mezclas de VGO/PE, tanto trmica como cataltica,

se produce en dos etapas, la primera asociada a la descomposicin del VGO y la
segunda debida al polietileno.
2. La temperatura de mxima velocidad de descomposicin es diferente a la que se
obtiene para los materiales puros, siendo mayores las diferencias en el caso del
proceso asociado a la descomposicin del PE.
3. Ambas etapas de descomposicin se ven afectadas por la presencia del
catalizador, reducindose la temperatura a la que se descomponen ambas
fracciones, siendo tambin mayor este efecto en el caso de la descomposicin de
la fraccin de PE.
4. En la descomposicin cataltica en presencia del catalizador de FCC con una
relacin 7:1 el catalizador ha rebasado la concentracin a la cual se observa el
efecto saturante, y todas las muestras presentan el mismo comportamiento,
independientemente de la proporcin de PE.
5. El efecto cataltico de los distintos catalizadores, con una concentracin del
20%, mostr que la actividad cataltica aumentaba al aumentar la acidez, el rea
BET, el rea externa y el tamao de poro, siendo el orden de actividad
encontrado:
HBeta > MCM-41(7) >HUSY >HZSM-5(c) FCC

101

Conclusiones

6. Segn la cantidad de coque formado sobre el catalizador durante el proceso de

pirlisis, la zeolita HZSM-5(c) y el catalizador de FCC de equilibrio son los
materiales que presentan menor tendencia a la formacin de coque, seguidos de
la zeolita HBeta y el MCM-41, y finalmente, el material que mas favorece la
formacin de coque es la zeolita HUSY.
7. La temperatura de oxidacin del coque es inferior en el caso de la zeolita HUSY
y el MCM-41 y es mxima para el FCC y la zeolita HZSM-5, presentando un
valor intermedio en el caso de la HBeta.
8. Teniendo en cuenta los datos obtenidos del estudio de la actividad cataltica, y
del estudio de la formacin de coque, y sin atender a cuestiones econmicas, se
puede concluir que el MCM-41 es el material que presenta mejores propiedades
fisicoqumicas para la pirlisis de mezclas de VGO/PE, ya que presenta una
elevada actividad cataltica, una baja tendencia a la formacin de depsitos de
coque, y una baja temperatura de regeneracin por oxidacin del coque.

Publicacin VI Study of the decomposition of Vacuum Gas Oils-Low Density

Polyethylene blends: evolution of the gases.

1. Los resultados obtenidos confirman la hiptesis previa de que el VGO antes de

descomponerse sufre un proceso de destilacin fraccionada.
2. Durante la pirlisis trmica de la mezcla de VGO-PE se observa un
comportamiento intermedio entre el comportamiento correspondiente al VGO y
al PE puro. Durante los intervalos de temperatura asociados a la descomposicin
del VGO no se generan gases, mientras que en los intervalos de temperatura
asociados con la descomposicin del PE, los n-alquenos son los compuestos
mayoritarios en la fase gaseosa formada.
3. En la pirlisis cataltica del VGO se observa la generacin de productos
gaseosos en el intervalo de 200-500C, siendo mxima en el intervalo de 250300C, lo que demuestra el efecto cataltico del catalizador de FCC, que
favorece la formacin de alcanos, siendo los iso-alcanos los compuestos
mayoritarios.

102

Conclusiones

4. En la pirlisis cataltica del PE se observa un incremento en la cantidad de gases

generados, con respecto al proceso trmico, cambiando la selectividad de estos
de n-alquenos, a iso-alcanos.
5. Durante la pirlisis cataltica de la mezcla de VGO-PE se recogieron gases en el
intervalo de 150-500 C, observndose un intervalo entre 250-300 C asociado a
la descomposicin del VGO, con una selectividad hacia iso-alcanos y una etapa
posterior, asociada con la descomposicin del PE. Adems, el comportamiento
de los gases generados en la degradacin de la mezcla sugiere que ambas etapas
trascurren de modo independiente.
6. En la pirlisis trmica de PE, el producto ms abundante dentro de los nalquenos es el 1-hexeno, mientras que en el proceso cataltico, el compuesto
mayoritario es el iso-butano.
7. En la descomposicin del VGO, donde solo se generaron gases mediante la
descomposicin cataltica, el compuesto mayoritario es el iso-pentano.
8. Durante la descomposicin cataltica de la mezcla de VGO-PE, en el intervalo
asociado a la descomposicin del VGO el compuesto mas favorecido es el isopentano, mientras que en el intervalo asociado a la descomposicin del PE, el
compuesto mayoritario es el iso-butano, lo que parece confirmar, que el proceso
de craqueo de los dos componentes de la mezcla evoluciona a travs de procesos
independientes.
9. Todos estos resultados confirman la viabilidad del reciclado de residuos
plsticos mediante la disolucin de los mismos en las corrientes convencionales
de alimentacin tpicas de las unidades de FCC de las refineras y el posterior
tratamiento de estas mezclas en dichas unidades o en otras similares, ya que la
presencia del polietileno parece no alterar significativamente la composicin de
los gases generados, y adems permite incrementar ligeramente la formacin de
compuestos tales como iso-butano, propano y butano, compuestos que forman
parte del gas licuado de petrleo (LP), que es uno de los combustibles
alternativos ms comunes usados hoy en da.

103

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112

PUBLICACIONES

I. Study of the influence of the characteristics of different acid solids in the

catalytic

pyrolysis

of

different

polymers,

Applied

Catalysis

A:

General, Volume 301, Issue 2, 2006, pp. 222-23.

II. Study of the early deactivation in pyrolysis of polymers in the presence of
catalysts, Journal of Analytical and Applied Pyrolysis, Volume 79, Issues 1-

2, 2007, pp. 443-449.

III. Characterization of high-impact polystyrene by catalytic pyrolysis over AlMCM-41: Study of the influence of the contact between polymer and catalyst,

Polymer Degradation and Stability, Volume 92, Issue 10, 2007, pp. 18671872
IV. Characterization of Styrene-Butadiene copolymers by catalytic pyrolysis over
Al-MCM-41, Journal of Analytical and Applied Pyrolysis, enviado.
V. Characterization of vacuum gas oillow density polyethylene blends by
thermogravimetric analysis, Polymer Degradation and Stability, Volume 93,

Issue 3, 2008, pp. 723-730

VI. Study of the decomposition of Vacuum Gas Oils-Low Density Polyethylene

blends: evolution of the gases, Polymer Degradation and Stability, enviado.

Publicacin I: Study of the influence of the characteristics of different acid solids

in the catalytic pyrolysis of different polymers, A. Marcilla, A. Gmez-Siurana and
D. Berenguer, Applied Catalysis A: General, Volume 301, Issue 2, (2006), Pages

222-23.

El proceso de pirlisis cataltica de polmeros en presencia de catalizadores

zeolticos se ve fuertemente afectado por caractersticas fisico-qumicas del propio
catalizador tales como la acidez, tamao de poro, superficie externa, as como por las
propiedades estructurales del polmero degradado. En el presente estudio se han puesto
a punto mtodos de sntesis de diferentes catalizadores slidos cidos. Los materiales
sintetizados se han caracterizado y se ha estudiado la influencia de dichas caractersticas
fisicoqumicas y texturales en el proceso de pirlisis de diferentes polmeros. Con este
objetivo se han seleccionado tres catalizadores, la zeolita ZSM-5 y dos MCM-41 con
distinta relacin Si/Al, y cuatro polmeros, LDPE, PP, HIPS, y un copolmero de EVA.
El estudio del comportamiento de los catalizadores en el proceso de pirlisis cataltica
se ha llevado a cabo en una termobalanza.

Los resultados obtenidos en este estudio permiten cubrir los siguientes

objetivos especficos:

o Puesta a punto de mtodos de sntesis y caracterizacin de diferentes slidos

cidos utilizados habitualmente en la pirlisis cataltica de polmeros.

o Estudio en termobalanza de la actividad que presentan los slidos cidos

sintetizados cuando actan como catalizadores del proceso de pirlisis
cataltica de diferentes polmeros.

Applied Catalysis A: General 301 (2006) 222231

www.elsevier.com/locate/apcata

Study of the influence of the characteristics of different acid

solids in the catalytic pyrolysis of different polymers
A. Marcilla, A. Gomez-Siurana, D. Berenguer *
Dpto. Ingeniera Qumica, Universidad de Alicante, Apdo. 99, 03080 Alicante, Spain
Received 29 September 2005; received in revised form 2 December 2005; accepted 7 December 2005
Available online 19 January 2006

Abstract
In this work, three catalysts with different chemical and physical properties were synthesized (one HZSM-5 zeolite and two ordered
mesoporous aluminosilicatesMCM-41a and MCM-41b) and tested for the pyrolysis of four samples of commercial polymers (LDPE, PP, PS and
EVA copolymer), using a thermobalance under nitrogen atmosphere at a heating rate of 10 8C/min. The catalysts were characterized using X-ray
powder diffraction, nitrogen adsorption at 77 K and 27Al and 29Si solid state nuclear magnetic resonance (NMR). The HZSM-5 zeolite showed the
lowest activity in the catalytic pyrolysis of the four polymers. The two mesoporous catalysts, with a greater pore size, were the most active
materials in the catalytic pyrolysis of the polymers, and the MCM-41b sample, with higher acidity, was the most active. The presence of MCM-41
samples during the pyrolysis of the high impact PS sample permits us to distinguish between different decomposition steps which are probably
related to the pyrolysis of PS and polybutadiene domains. This processes separation was not observed in absence of the catalyst. Thus, catalytic
pyrolysis of such samples in the presence of MCM-41 and other catalysts could be a promising technique to characterize this type of polymers.
# 2005 Elsevier B.V. All rights reserved.
Keywords: Catalytic pyrolysis; ZSM-5; MCM-41; TGA; FT-IR; Polymers

1. Introduction
The growth of welfare levels in modern society during the
past decades has brought about a huge increase in the
production of all kinds of commodities. Plastics have been one
of the materials with the fastest growth because of their wide
range of applications: packaging, agriculture, construction,
household, etc. Between 1991 and 2002, the per capita
consumption of plastics increased in Western Europe from 64 to
95 kg/year, with an average growth of 3% per year [1]. The
most common alternative for the management of these wastes
in Western Europe was deposition in landfills (75%) and
incineration (14%) [2]. However, the available space in landfill
is decreasing, whereas incineration is strongly rejected by
public opinion, due the risk of the possible emission of toxic
chemicals, mainly polychlorinated aromatic species (dioxins,
furans, etc.).

* Corresponding author. Tel.: +34 96 590 2953; fax: +34 96 590 3826.
E-mail addresses: antonio.marcilla@ua.es (A. Marcilla),
Desi.BM@ua.es (D. Berenguer).
0926-860X/$ see front matter # 2005 Elsevier B.V. All rights reserved.
doi:10.1016/j.apcata.2005.12.018

Different alternatives are currently beginning to be

considered for reducing the environmental impact of plastic
wastes. Primary or mechanical recycling consists of grinding
the plastics and producing new goods with the resulting
recycled material. This type of recycling has some limitations
due to the difficulties in processing mixtures of different
plastics. Moreover, the quality of the recovered material is
lower than that of fresh materials [3]. In the secondary
recycling, incineration, calorific energy is generated. The
calorific value of the plastics are comparable to that of fuels,
around 46 MJ/kg [4], but uncontrolled incineration can produce
different pollutants which are toxic at very low concentration.
Pyrolysis is a tertiary recycling process, where the polymer
sample is heated in an inert atmosphere causing the cracking of
the polymer backbone. The simplest method of plastic
feedstock tertiary recycling is thermal cracking, which
proceeds (in most cases) with low yields towards the
corresponding raw monomers, giving a complex mixture of
products with a low value as raw chemicals and mainly useful
as fuel. However, by plastic cracking over different solid
catalysts it is possible to obtain products with higher
commercial value and with a wider number of applications
[57].

A. Marcilla et al. / Applied Catalysis A: General 301 (2006) 222231

Zeolites show excellent properties as catalysts for the

pyrolysis of plastic waste. The catalyst causes an important
reduction in the decomposition temperature and allows more
valuable gaseous products to be obtained. HZSM-5 zeolite
has proved to be an efficient catalyst for catalytic degradation
of polymers because of its strong acidity for the carbon
carbon bond scission and unique pore structure to reduce
coke formation [8]. However, the pore size of the zeolites is
limited to a maximum value of about 1.0 nm, and in the case
of HZSM-5 the pore size is 0.5 nm, which hinders the access
of bulky molecules to the acid sites located inside the
channels.
The discovery in 1992 of MCM-41 silicates by Mobil has
opened the way to new zeotype molecular sieves with ordered
mesoporous channels system [9]. MCM-41 possesses highly
regular arrays of uniform-size pore channels ranging from 1.5
to 10 nm in size and large surface area. Nevertheless, the
utilization of MCM-41 in catalysis is now to some extent
restricted by its relative low acidity and low hydrothermal
stability, in comparison with those of microporous zeolites,
such as HZSM-5 and USY.
Since the discovery of the possible incorporation of
aluminium in the framework of MCM-41 [10,11], the interest
in the substituted material is growing. Tetrahedrally coordinated aluminium ions pave the way for the creation of Bronsted
acid sites solving, in this way, the problem of the low acidity
that present these materials.
In this work three catalysts have been synthesized:
HZSM-5 and two MCM-41 samples with different aluminium content incorporated in the structure, MCM-41a and
MCM-41b, being the Al content higher in MCM-41b. The
relationship of the physical and chemical properties of the
catalysts with their activity in the catalytic pyrolysis of four
commercial polymers (low density polyethylene (LDPE),
polypropylene (PP), high impact polystyrene (HIPS) and a
copolymer of ethylene and vinyl acetate (EVA)) has been
studied. The catalytic degradation of the polymers has been
followed using thermogravimetric analysis (TGA) and the
catalyst activity has been defined in terms of the decrease of
the decomposition temperature of the polymer caused by the
catalyst.
Some works regarding the catalytic pyrolysis of polymers in
the presence of zeolites or MCM-41 can be found in [58]. In
the present work, we focus on the comparison among the
different polymer structures and catalyst characteristics effect,
using a technique for pyrolysing the samplesTGA, which has
demonstrated its ability for showing details about the pathway
and the evolution of the process [1214]. In this way, the
catalytic pyrolysis of polymers appear as a promising way for
characterising polymers as well as catalyst. On the other hand,
the most of the bibliography related to the catalytic pyrolysis of
polymer is devoted to PE studies [68,12,14]; much less articles
are referred to the PP behaviour [6,24], and relatively few, to
EVA [28,29] or PS [25]. The preliminary results found in this
work suggests that this could be a very interesting tool in the
determination of the polybutadiene (PB) content in high impact
PS samples.

223

2. Experimental
2.1. Synthesis of catalysts
The HZSM-5 zeolite was synthesized following the method
proposed by the International Zeolite Association (IZA) [15],
whereas the two samples of MCM-41 were prepared according
the method reported in literature [16], modifying the amount of
aluminum isopropoxide used in each case as aluminium source,
in order to obtain two materials with different Si/Al ratio.
The NH4+ forms of the HZSM-5 sample were obtained by
ion exchange with 1 M NH4NO3 solution for 2 h at 70 8C, and
the protonated forms of the three catalysts were obtained by
calcining the NH4+ forms at 500 8C for 5 h.
2.2. Catalyst characterization
The X-ray diffraction (XRD) pattern were recorded using a
Seifert JSO-DEBYEFLEX 2002 X-ray powder diffractometer,
which employed Ni-filtered Cu Ka radiation. The Si/Al ratio
was measured by X-ray fluorescence (XRF) in a Philips, model
PW1480.
27
Al and 29Si solid state nuclear magnetic resonance spectra
(NMR) were recorded on a Fourier Transform Bruker, model
AC-300. The conditions for the 27Al were as follows: magnetic
field frequency 70.39 MHz; 408 pulse width 3.0 ms; sampling
delay 10 ms; sampling width 40,000 Hz; pulse delay 2 s;
spinning rate 3.6 kHz; standard material for chemical shift as
0 ppm, an aqueous solution saturated with Al(ClO4)3. The
conditions for the 29Si: magnetic field frequency 53.17 MHz;
408 pulse width 4.0 ms; sampling delay 200 ms; sampling width
12,000 Hz; pulse delay 15 s; spinning rate 3.6 kHz; standard
material for chemical shift as 0 ppm, Si(CH3)4 liquid.
N2 adsorption isotherms at 77 K were determined in an
automatic AUTOSORB-6 supplied by Quantachrome. The
adsorption curves of the isotherms were recorded and the
surface area measurements were done according to the BET
method. The pore size distributions were obtained applying the
BJH model with cylindrical geometry of the pores and using the
Harkins and Jura equation for determining the adsorbed layer
thickness (t) and the external surface area.
Temperature-programmed desorption (TPD) of ammonia
was performed in a Netzsch TG 209 thermobalance. The
samples were previously outgassed in a N2 flow of 45 ml/min
by heating at 500 8C with a rate of 10 8C/min, remaining at this
temperature for 30 min. After cooling to 100 8C, the acid sites
were saturated by treatment with an ammonia flow of 35 ml/
min for 30 min. The physisorbed ammonia was removed by
passing a N2 flow of 45 ml/min for 60 min at 100 8C. Finally,
the TPD measurements were carried out by heating the sample
in the N2 flow with a rate of 10 8C/min up to 900 8C. The acidity
of the materials was calculated using the weight loss observed
in the thermobalance at the TPD stage by the following
formula:
acidity

%mass loss
1
1000 mmol




mmol=g
100
MW NH3
1 mol

224

A. Marcilla et al. / Applied Catalysis A: General 301 (2006) 222231

Table 1
Characteristics of the commercial polymers
Material

LDPE 780R
PP Novolen
1100L
PS Polystyrol
495F-SB
EVA Escorene
UL15028CC
a

Density
(g/cm3)

Melt index
(g/10 min)

Table 2
Results of the characterization of the catalysts synthesized in this work
Vicat
point (8C)

Tensile
modulus
(Mpa)

0.923
0.910

20 (190/16)a
8 (230/2.2)

93
70

115
1500

1.050

9.5 (200/5)

90

2000

0.950

150 (125/0.3)

64

13

8C/kg.

Property
a

Pore size (nm)

d100 (nm)b
)c
a0 (A
Wall thickness (nm)d
BET area (m2/g) e
External surface area (m2/g) f
Pore volume (cm3/g) g
Si/Al ratioh
Acidity (mmol/g)i
T desorption NH3 (8C)j
Aloct/Altetra j
a

The first peak of the TGA derivate curve (DTG) identifies

the temperature of desorption from weak acid sites and the
second peak of desorption identifies strong acid sites (see
Fig. 5, as an example).

b
c
d
e
f
g

2.3. Catalyst testing

h
i
j

The catalytic activity of the three acid solids synthesized in

this work in the catalytic pyrolysis of polymers, was
investigated using thermogravimetric analysis (TGA) as
described in [17,18]. The equipment employed was a
Perkin-Elmer Pyris 1 Thermobalance. The balance and the
oven thermocouple of the equipment were calibrated following
the manufacturers instructions. Table 1 shows the main
characteristics of the four commercial polymers selected for
testing the catalyst activity.
Pure polymers as well as mixtures of powdered polymers
and catalyst of around 4 mg (3.2 mg of the polymer with 0.8 mg
of the catalyst) were pyrolyzed. The temperature was raised to
550 8C with a heating rate of 10 8C/min. During the
experiments, nitrogen flowed through the oven at a rate of
57 STP ml/min. For the PS and PS + catalyst systems, the
qualitative composition of the volatile products formed in the
thermobalance furnace were analysed using a Bruker Tensor 27
FT-IR spectrometer connected to the TGA (TGA/FT-IR)
through a transfer line heated to 200 8C to prevent condensation
of the decomposition products.

HZSM-5

MCM-41a

MCM-41b

0.51
0.55

2.4
3.39
3.92
1.52
1136
383
1.34
47
0.60
138
0.37

1.7
3.25
3.77
2.07
956
126
1.00
7
2.08
155550
0.70

334
67
0.27
24
1.36
165385
0.12

BJH (for MCM-41a, MCM-41b).

XDR. p
2d100/ 3.
a0-pore size.
N2 adsorption isotherms; BET method.
N2 adsorption isotherms; t method.
N2 adsorption isotherms; measured at P/P0 = 0.995.
XRF.
TPD of NH3.
NMR.

fact has also observed in the bibliography, and according to

Luan et al. [19], when different MCM-41 samples were
prepared by the same experimental procedure, but using
different amounts of the aluminium source in order to obtain
materials with different Si/Al content, the (1 0 0) peak was the
more intensive in all the cases, but the intensity of the other
peak decrease when the Si/Al ratio decreases, being practically
unappreciable when Si/Al = 2.5.
The coordination of the Al atoms in the materials was
investigated by 27Al NMR spectroscopy. The 27Al NMR spectra
(Fig. 2) contain two peaks: one at around 54 ppm, corresponding to Al tetrahedrally coordinated, and another near 0 ppm,
corresponding to octahedral Al species. The relatively low
intensity of the octahedral Al peak of HZSM-5 (Fig. 2c)
suggests that only a small part of the Al atoms are released from
the zeolite framework, so this is a very crystalline material.

3. Result and discussion

3.1. Catalyst characterization
All the catalysts synthesized and calcined to obtain the
protonated forms were characterized by XRD, nitrogen
adsorption isotherms at 77 K, NMR of 27Al and 29Si and
TPD of NH3. The results of the characterization are shown in
Table 2.
The observed XRD patterns of the calcined samples of
MCM-41a, MCM-41b and HZSM-5 correspond to those
usually observed with these materials [15,19] (Fig. 1).
Fig. 1 shows the existence of one diffraction peak for the
MCM-41b sample (i.e. the (1 0 0) peak), whereas for the MCM41a sample a shoulder next to the (1 0 0) peak also appear. This

Fig. 1. XRD patterns of the three catalysts studied in this work: (a) MCM-41a;
(b) MCM-41b and (c) HZSM-5.

A. Marcilla et al. / Applied Catalysis A: General 301 (2006) 222231

Fig. 2. 27Al NMR spectra of the three catalysts studied in this work: (a) MCM41a; (b) MCM-41b and (c) HZSM-5.

Fig. 3 shows the 29Si NMR spectra obtained for the three
acid solids. As can be seen, peaks at 109 ppm (MCM-41a and
MCM-41b) and at 115 ppm (HZSM-5) appear. In general, the
peaks at around 110 ppm can be assigned to the Si(OAl) units
in the amorphous MCM-41 framework, whereas the peaks at
around 115 ppm can be assigned to the crystallographically
orientated SiOSi bonds in the crystalline Si(OAl) units.
The nitrogen adsorption isotherms at 77 K for the three
calcined samples of the synthesized acid solids are shown in
Fig. 4. The samples MCM-41a and MCM-41b presents a type
IV isotherm, according the IUPAC classification, and this is
typical for a mesoporous material. It possesses a monomultilayer adsorption zone at low relative pressures, a distinct
jump of capillary condensation in mesopores at P/P0 = 0.10.4
and an almost constant adsorption zone at high relative
pressures due to multilayer adsorption on the particle surface.
Actually, MCM-41b presents a pore size in the range of
micropores (1.7 nm), but very near to the border between the
micropores and mesopores ranges (2 nm), and around three
times the corresponding the microporous HZM-5 zeolite.
Therofore, would not be strange the fact that this material
exhibits a N2 adsorption isotherm closer to the mesoporous than

Fig. 3. 29Si NMR spectra of the three catalysts studied in this work: (a) MCM41a; (b) MCM-41b and (c) HZSM-5.

225

Fig. 4. Nitrogen adsorption isotherms at 77 K and pore size distributions of the

three catalysts studied in this work: (a) MCM-41a; (b) MCM-41b and (c)
HZSM-5.

the microporous materials. On the other hand, the adsorption

isotherms corresponding to HZSM-5, indicate a lower
adsorption capacity. Likewise, the isotherm for the HZSM-5
sample does not show any trace of capillary condensation in the
mesopores, only a mono-multilayer adsorption or micropore
filling is observed. These isotherm seem to be of type I in the
IUPAC classification and are typical for microporous materials.
The observed evolution of the isotherms is also reflected in
the main textural properties derived from them: the BET
surface area, the external surface area, and specific pore volume
and the average pore size (see Table 2). Thus, the BET surface
area values dropped from 1136 m2/g (MCM-41a) to 334 m2/g
(HZSM-5), the total pore volumes (measured at P/P0 = 0.995)
from 1.34 cm3/g (MCM-41a) to 0.27 cm3/g (HZSM-5). Therefore, an increase in the aluminium content of the acid solid in
the case of MCM-41, has a strong influence on the textural
properties of the material finally obtained. The pore size results
are especially remarkable, since they indicate a change from
mesoporous materials (MCM-41a) to microporous ones
(Dp < 2.0 nm, IUPAC) in the case of the (MCM-41b), despite
that, as has been above-mentioned, MCM-41b shows the
typical behaviour of mesoporous materials. Fig. 4 also shows
the pore size distribution obtained from the corresponding
adsorption isotherm, applying the BJH method.
It is worth to comment that the results showed in Table 2 for
the external surface area of the materials by application of the tmethod would be influenced by the mesoporous nature of the
MCM-41 and, therefore, part of the mesoporous surface would
be accounted as external surface area, allowing values
abnormally high. In spite of this observation, the external
surface areas reported by the t-method have a valuable
comparative value and, on the other hand, this part of the
mesoporous surface would also be a very accessible surface,
as in the external surface case, as compared to the microporous
area.
According to [20], the ammonia TDP spectra of MCM-41
would present at least three different peaks: at low-, mediumand high-temperature (around 217, 2804501 and 600 8C,
respectively), which are attributed to weak Bronsted and Lewis

226

A. Marcilla et al. / Applied Catalysis A: General 301 (2006) 222231

Fig. 5. DTG and TGA curves from NH3 TPD of the three catalysts studied in
this work.

In the present work, the above-commented high-temperature

peak has been only observed in the MCM-41b sample (i.e. that
with higher aluminium contents), but not in the MCM-41a
sample. However, the previous assignment must be considerated with some caution because the experimental procedure
does not permit any confirmation, and the possibility that the
high-temperature TPD peak is related to dehidroxilation
process also exists.
As can be seen in Table 2, the principal differences between
HZSM-5 zeolite and MCM-41a are the higher pore size and the
greater surface area of MCM-41a, whereas HZSM-5 zeolite
displays a greater acidity. In the case of the MCM-41b sample,
the decrease of the Si/Al ratio the produces a considerable
increase of the acidity, and it allows us to have a material with
physical properties similar to the MCM-41a but with improved
acid properties.
3.2. Catalytic activity

sites, to medium to strong acidic Bronsted sites, and to strong

Lewis sites, respectively. The low-temperature peak is wellknown for many types of zeolites. With medium pore zeolites,
as HZSM-5, is assigned to ammonia bound weakly to Lewis
sites, whereas with large pore zeolites and MCM-41, is caused
by desorption of ammonia from weak Bronsted sites, despite a
contribution of weak Lewis sites to the low-temperature peak
cannot be ruled out. However, this technique does not allow to
distinguish between Bronsted and Lewis acid sites, and only the
assignement to weak acid sites, leading to low temperature NH3
TDP peaks, and strong acid sites, corresponding to higher
temperatures of NH3 TDP peaks. In this way, Marcilla et al.
[21] reports the existence of NH3 TDP peaks at 166 and 416 8C
corresponding, respectively, to the weak and strong acid sites of
a HZSM-5 zeolite. In good agreement with the previous
comments, Fig. 5 shows the DTG curves obtained in the TPD of
ammonia for the three materials studied in this work. As can be
seen, all the catalysts, except MCM-41a, present two types of
acid sites (i.e. two peaks): weak sites at low temperature of
desorption (at around 165 8C), and strong sites, characterized
by ammonia desorption at high temperatures (at around 385 8C
for HZSM-5, and 550 8C for MCM-41b). According to some
authors [22], the assignment of the peak appearing at lower
temperature is associated to the desorption of ammonium
coming from NH4+(NH3)n associations, which can vary from
n = 1 to 3. Fig. 5 shows that MCM-41b presents the higher
acidity, although this is mainly due to the weak acid sites.
However, the strength of the strong sites for this material is
greater than for the rest of catalysts (Table 2). On the other
hand, MCM-41a presents the smaller acidity.
Despite the previous comments, the assignment of the hightemperature peak (maximum at around 500600 8C) is a point
of discussion [20]. According to Kosslick [20], the ammonia
TPD patterns show a high temperature peak at around 600 8C
which is suggested to be originated from strong Lewis sites.
These authors suggested that, in a secondary step, these sites readsorb ammonia molecules related by the decomposition of the
NH4+ ions of Bronsted acid sites at lower temperatures. Above
550 8C, ammonia is desorbed again from the strong Lewis sites.

3.2.1. Catalytic pyrolysis of LDPE

Fig. 6a shows the TGA curves obtained for the pyrolysis of
LDPE and four mixtures of LDPE with the different catalysts
studied in this work. Fig. 6b shows the corresponding derivative
curves (DTG curves). As can be seen, the decomposition of

Fig. 6. (a) TGA and (b) DTG curves obtained in the thermal pyrolysis of LDPE
and in the catalytic pyrolysis in the presence of the different catalysts.

A. Marcilla et al. / Applied Catalysis A: General 301 (2006) 222231

227

Table 3
Difference between temperature of maximum speed of decomposition observed
in thermal and catalytic process, for different systems polymer + catalyst
Polymer

DTHZSM-5

DTMCM-41a

DTMCM-41b

LDPE
PP
PS
EVA

85
61
0
18

96
109
13
30

116
122
12
64

LDPE always occurs in a single peak (typical of this polymer,

i.e. [23]), although the initial tail is more pronounced in the
presence of the catalysts, especially in the case of the MCM41b. In all the cases, the presence of the catalysts affects the
decomposition process, considerably reducing the temperature
of maximum decomposition rate (Fig. 6b). Table 3 shows the
decrease of the temperature of maximum reaction rate in the
thermal and catalytic process, for the three catalysts studied in
this work. According to Fig. 6 and Table 3, the catalyst with
higher activity is the MCM-41b. This material presents the
higher acidity and a high pore size (Table 2). The following
catalyst in decreasing order of activity is MCM-41a, which
presents a high BET area and a large pore size, but its low
acidity noticeably reduces the catalytic activity in comparison
with the previous materials. Finally, the catalyst with the lowest
activity is the HZSM-5 zeolite, that in spite of its relatively high
acidity, has the lowest pore size (pores included in the rank of
the microporosity), which limits the diffusion of the reactants to
the active sites.
3.2.2. Catalytic pyrolysis of PP
Polypropylene (PP) is a polymer whose chains present a
greater cross-sectional area than LDPE, due to the presence of
the methyl group substituent on alternate carbon atoms of the
chain. The presence of these methyl groups increase the number
of tertiary carbons in the molecule, thus increasing the
reactivity of the chain [24], and its temperature of thermal
degradation is, therefore, lower than the corresponding to
LDPE. However, the presence of the methyl groups also
introduces a certain steric hindrance, which can affect the order
of activity of the different catalysts with respect to that observed
in the catalytic pyrolysis of LDPE.
Fig. 7a shows the TGA curves obtained for the thermal and
catalytic pyrolysis of PP. As was observed in the case of LDPE
(Fig. 6a), all the catalysts produce a noticeable reduction of the
temperature of decomposition. Table 3 shows the corresponding differences between the temperature of maximum decomposition rate in the thermal and catalytic processes. As can be
seen, the reduction of the temperature obtained with zeolite
HZSM-5 is lower than that observed in the catalytic pyrolysis of
LDPE. This shows that, in these cases, the increase of the
reactivity of polymer due to the increase of the number of
tertiary carbon atoms is counteracted by the increase of the
transversal area of the polymer, that hinders the access of the PP
chains to the interior of micropores. On the other hand, the
decrease of the temperature observed in the presence of MCM41a and MCM-41b is higher than that observed in the catalytic
pyrolysis of LDPE in the presence of these catalysts. In this

Fig. 7. (a) TGA and (b) DTG curves obtained in the thermal pyrolysis of PP and
in the catalytic pyrolysis in the presence of the different catalysts.

case, it therefore seems evident that, the size of the pores of the
catalyst is high enough to permit the access of polymeric chains
to the interior of the pores, and the catalytic effect on the tertiary
carbon atoms may take place over a large extent. In this case,
the MCM-41b causes, as in the case of the LDPE, a marked
initial tail in the pyrolysis process.
3.2.3. Catalytic pyrolysis of PS
The existence of the phenyl groups which appear as
substituents in the PS chains makes this polymer a macromolecule with important steric hindrances, in comparison with
LDPE or PP.
Fig. 8a and b shows the TGA and DTG curves obtained for
the thermal and catalytic pyrolysis of PS. As can be clearly
seen, the activity of all the catalysts studied in this work is
noticeably influenced by the voluminosity of the polymer. This
diminishes the activity of acid solids, in some cases, as for
HZSM-5 zeolite, until the point of practically not displaying
catalytic activity on the pyrolysis of PS. Table 3 shows the
corresponding decrease of the temperature of maximum
decomposition rate for the different acid solids studied. As
can be seen, only a low decrease can be observed for MCM-41
materials.

228

A. Marcilla et al. / Applied Catalysis A: General 301 (2006) 222231

Fig. 8. (a) TGA and (b) DTG curves obtained in the thermal pyrolysis of PS and in the catalytic pyrolysis in the presence of the different catalysts. (c) FT-IR
spectrogram corresponding to the gas generated at the temperature of maximum decomposition rate in the thermal pyrolysis of PS. (d) FT-IR spectrogram
corresponding to the gas generated in the thermal and catalytic pyrolysis of PS in the region between 3200 and 2300 cm1: (A) PS; (B) PS + MCM-41a; (C)
PS + MCM-41b and (D) PS + HZSM-5. (e) FT-IR spectrogram corresponding to the gas generated in the thermal and catalytic pyrolysis of PS in the region between
880 and 600 cm1: (A) PS; (B) PS + MCM-41a; (C) PS + MCM-41b and (D) PS + HZSM-5.

In agreement with [25], the above-mentioned steric

hindrance is high enough to block the access of macromolecules to the interior of the pores, thus reducing the
potential catalytic effect of the porous solid. In this work,
only a slight reduction of the temperature of decomposition,

sensibly inferior to the values obtained for the LDPE and the
PP cases, has been observed in the presence of the materials
with greater pore size (Table 2), i.e. those containing
MCM-41 structures. This fact is, obviously, related to the
possibility of these materials of drastically reduce the steric

A. Marcilla et al. / Applied Catalysis A: General 301 (2006) 222231

hindrances which limits the access of the polymers to the

inner of pores [26].
Nevertheless, in spite of the low activity of the catalysts
studied, Fig. 8b shows that the presence of the catalyst has a
marked role. Up to three different processes can be observed in
the presence of the MCM-41 materials, and the process begins
at lower temperatures than in the thermal pyrolysis. This
premature beginning can also be observed in the previous cases
(LDPE, Fig. 6b and PP, Fig. 7b) and gives rise to a widening of
the corresponding DTG curves. It seems, therefore, that the
premature beginning of the decompositions reactions may be
related to the acid sites located on the surface of the material
[14,24]. In fact, according to [27], the influence of the acid sites
located on the external surface and in the pore mouth region of
zeolites cannot be ignored, although the concentration of these
acid sites is assumed to be smaller, generally 35% of the total
acid sites.
It must be observed that the PS sample used in this work
corresponds to a high impact PS (HIPS), composed by PS
domains and polybutadiene (PB) domains. Therefore, the
existence of different reaction steps, at around 420 and 450 8C,
respectively, in the pyrolysis of HIPS in the presence of MCM41a and MCM-41b reveals that probably these catalysts permit
a distinction between the pyrolysis of PS and PB domains. The
main decomposition step (at around 420 8C) can be related to
the PS domains decomposition, whereas the last decomposition
step (at around 450 8C) can be related to the decomposition of
the PB domains. The small size of the narrow pores of the
HZSM-5 zeolite can be responsible of the almost absence of
catalytic effect with the voluminous molecules of PS, being, for
the same reason, this material incapable of distinguish between
the PB and PS fractions in the HIPS sample studied in this work.
Considering the hypothesis that the external surface acid
sites are responsible for the premature start of the decomposition process, it is possible to justify the catalytic behaviour of
the different materials. Thus, MCM-41b is the material that
allows the degradation to begin at lower temperatures (259 8C).
This can be due to the fact that, despite MCM-41a presents area
noticeably higher than the rest of catalysts (see Table 2), MCM41b maintains high values of the external mesoporous surface
area together with the highest acidity. The following catalyst, in
decreasing activity order, is MCM-41a, which displays an
external surface area six times higher than that of the HZSM-5
zeolite (Table 2). Thus, the premature beginning of the process
in the presence of HZSM-5 is noticeably lower as compared
with the other materials. The surface area of HZSM-5 is much
lower than that of the other catalysts, its weak acid sites strength
is similar to that of the MCM-41 samples, and shows a
noticeable acidity of strong acid sites (i.e. ammonia TDP peak
at higher temperature in Fig. 5). Therefore, the absence of the
premature beginning of the process in presence of HZSM-5
suggests the relevance of the accessibility of the acid sites for
the preliminary steps of the catalytic pyrolysis.
For PP, the broad decomposition region at the initial
decomposition stage has been observed for MCM-41b, but not
in the presence of MCM-41a. As has been commented
previously, the values of the external surface area obtained from

229

the t-method in the case of the mesoporous MCM-41 samples

would also include some part of the mesoporous surface.
Therefore, the differences in the external surface area are not at
all conclusive. The higher surface (i.e. N2 adsorption capacity,
see Fig. 4 and Table 2) of the MCM-41a is counteracted by the
higher acidity of the MCM-41b. According to Fig. 5, the
ammonia TPD peaks reflects that, in addition to the presence of
the high temperature peak observed for MCM-41b, the two
MCM-41 samples contain similar strength acid sites, being
slightly weaker for MCM-41a (in Fig. 5, peaks at 138 and
150 8C for MCM-41a and MCM-41b, respectively). However,
the acidity of the MCM-41b sample is noticeably higher, thus
revealing the existence of higher number of acid sites.
Therefore, the combination of both parameters is required to
explain the behaviour observed. This type of behaviour has
been previously reported by other authors [25], that observed
the highest activities for the pyrolysis of a mixture of PP and PE
for zeolites having a higher proportion of external acid sites.
In order to assess with more detail the influence of the
different catalysts in the pyrolysis of PS, the gases generated at
the temperature of the maximum decomposition rate have been
qualitatively analysed using TGA/FT-IR.
Fig. 8c shows the FT-IR spectrum corresponding to the gas
generated at the temperature of maximum decomposition rate
in the thermal pyrolysis of PS. The absorption band at
3074 cm1 reveals the presence of a high number of aromatic
compounds and the bands at 771 and 695 cm1, corresponding
to the substitution of aromatic rings, indicate the presence of a
monosustituted aromatic compound (styrene). On the other
hand, the band at 3024 cm1 is related to the presence of
olefins, whereas the bands at 29642873 cm1 correspond to
the asymmetrical and symmetrical tension of alkanes, being
these bands those of smaller intensity. According with [25,28],
the products evolved in the pyrolysis of PS include a high
number of aromatic hydrocarbons, as well as different alkanes
and olefins, being more abundant the aromatic compounds and
olefins. Moreover, according to Serrano et al. [25], in the
thermal pyrolysis exists a selectivity towards aromatic
hydrocarbons, especially towards styrene, whereas in the
catalytic pyrolysis a selectivity exists towards benzene.
The comparison among the FT-IR spectra corresponding to
the gas evolved in the thermal and catalytic process reveals the
existence of a noticeable level of similarity, but also some
interesting differences. Fig. 8d shows a magnification of the
32002300 cm1 region of the FT-IR spectra obtained in the
thermal pyrolysis of PS and in the pyrolysis in the presence of
the different catalysts. It is possible to observe that the catalytic
process, shows, in comparison with the thermal pyrolysis, a
clear decrease of the bands corresponding to aromatic
compounds (3074 cm1) and olefins (3024 cm1) and an
increase of the bands of tension of alkanes (29642873 cm1).
The same tendency can be seen in Fig. 8e, where a
magnification of the region of 900600 cm1 is shown: the
spectra corresponding to the gas evolved in the catalytic process
shows a notable decrease of the bands corresponding to
monosustituted aromatic rings (771 and 695 cm1), whereas
the bands of absorption of benzene increase (671 and

230

A. Marcilla et al. / Applied Catalysis A: General 301 (2006) 222231

653 cm1), being the more intense of the spectrum. Thus, it can
be concluded that, in good agreement to [25], the presence of
the acid solid changes the selectivity of the process toward
benzene instead of styrene, but also decrease the olefins yield
and increase the alkanes formation. The case of the HZSM-5
zeolite is worth to emphasizing, that in spite of not modifying
the temperature of maximum decomposition rate of PS, clearly
modifies the composition of the gases. Thus, as with the rest of
the catalysts, notably diminishes the bands of absorption of
aromatic and olefins (Fig. 8d) and shows more selectivity
towards benzene (Fig. 8e). However, it maintains some
similarity to the thermal process, as in the case of the alkanes
formation (Fig. 8d).
3.2.4. Catalytic pyrolysis of EVA
Ethylene vinyl acetate (EVA) copolymers are formed by
structural units from ethylene and vinyl acetate (VA). Therefore, some steric hindrances, related to the presence of the
acetoxi groups, which appear as substituents of the polymeric
chains, can be expected. Fig. 9a shows the TGA curves obtained
for the thermal and catalytic pyrolysis of EVA and Fig. 9b
shows the corresponding DTG curves.
According to [29], the thermal degradation of EVA
copolymers shows an initial step, which involves the formation

of acetic acid, followed by a second step, which involves the

degradation of the main chain, with little evidence of
interaction between the ethylene and VA units.
As Marcilla et al. [30] observed, the temperature of
maximum weight loss for the first decomposition step
undergoes almost no modification, and appears approximately
at the same temperature despite the presence of the catalyst,
whereas the second decomposition step is clearly affected by
the presence of acid catalysts. However, the presence of
catalysts clearly modifies the behaviour of the first process,
that starts earlier and proceeds over a wider temperature
range. This behaviour has been already described in [31,32].
According to Fig. 9a, the most effective catalysts in this step
are MCM-41b and MCM-41a. As has been described in the
PS case, this premature initiation of the decomposition may
be related to the presence of the acid sites in the external
surface of the catalyst.
On the other hand, the second weight loss, corresponding to
the decomposition of PE domains and of the polyene residue
after the evolution of VA groups, is affected by the presence of
each catalyst and a shift to lower temperatures can be observed.
According to [30], when increasing the vinyl acetate content,
the polymer becomes less susceptible to the catalytic action of
acid solids. The EVA selected for this work contains 27.5% of
VA and, coherently, the catalysts studied exercise an influence
noticeably lower than that obtained for LDPE cracking.
Table 3 shows the differences observed between the
temperatures of maximum decomposition rate in the thermal
and catalytic process. As can be seen, the catalysts with a
greater pore size are the most active (MCM-41b and MCM41a), being the MCM-41b, which presents higher acidity, the
most active.
4. Conclusions

Fig. 9. (a) TGA and (b) DTG curves obtained in the thermal pyrolysis of EVA
and in the catalytic pyrolysis in the presence of the different catalysts.

The results obtained in this work clearly show that the

catalytic pyrolysis of the polymer process depends on the
chemical and physical characteristics of the catalysts, as well as
on the chemical and structural nature of the polymers.
The activity of the acid solids is determined by the
corresponding pore size. In fact, the catalytic role of the acid
sites will only be observed if the reactant molecules access to
the active sites located in the interior of the pores.
The other factor determining the catalytic activity of these
materials is the acidity, and the results obtained show that the
activity of the solid acid catalyst increases as the acidity
increases.
With respect to the influence of the polymer characteristics,
the importance of the catalyst pore size increases with the crosssectional area of the polymer. In this way, the reactivity of a
certain polymer over the acid solid surface is the result of two
counteracted effects: the number of tertiary carbon atoms which
increases the reactivity and the steric hindrance of the
constituents, which decreases the activity.
Finally, it is possible to emphasize the role that the acid sites
of the surface of the catalyst seem to play, witch appear to be
related to the premature start of the decomposition process.

A. Marcilla et al. / Applied Catalysis A: General 301 (2006) 222231

According to the previous statements, the activity order

found for the different polymer + catalyst systems is the
following:





LDPE, PP, PS, EVA: MCM-41b > MCM-41a > HZSM-5.

MCM-41: PP > LDPE > EVA > PS.
Al-MCM-41: PP > LDPE > EVA > PS.
HZSM-5: LDPE > PP > EVA > PS.

Finally, the results obtained in this work, demonstrate the

effectiveness of use of the catalytic pyrolysis of polymers using
TGA, not only as a technique for studying this type of
processes, but also as a powerful tool for characterising
polymers and catalyst. In this way, it appears as a promising
procedure for the determination of the polybutadiene (PB)
content in high impact PS samples, which cannot be easily
know by other analytical techniques.
Acknowledgements
Financial support for this investigation has been provided
by the Spanish Comision de Investigacion Cientfica y
Tecnologica de la Secretara de Estado de Educacion,
Universidades, Investigacion y Desarrollo and the European
Community (FEDER refunds) (CICYT PPQ2004-02187) and
by the Generalitat Valenciana (project GRUPOS03/159).
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[16] D.P. Serrano, J. Aguado, J.M. Escola, Micropor. Mesopor. Mater. 34
(2000) 43.
[17] A. Marcilla, M.I. Beltran, F. Hernandez, R. Navarro, Appl. Catal. A Gen.
2781 (2004) 37.
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[20] H. Kosslick, G. Lischke, B. Parlitz, W. Storek, R. Fricke, Appl. Catal. A
Gen. 184 (1999) 49.
[21] A. Marcilla, M.I. Beltran, F. Hernandez, R. Navarro, Appl. Catal. A Gen.
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Publicacin II: Study of the early deactivation in pyrolysis of polymers in the

presence of catalysts, A. Marcilla, A. Gmez-Siurana and D. Berenguer, Journal of
Analytical and Applied Pyrolysis, Volume 79, Issues 1-2, (2007), Pages 443-449

Durante el estudio del comportamiento de los catalizadores en el proceso de

pirlisis cataltica (Publicacin I), se observ cmo los materiales que presentan una
elevada rea superficial as como una elevada acidez, como es el caso del material
MCM-41(7), mostraban un comportamiento no observado anteriormente por otros
autores. Las curvas de prdida de peso obtenidas en la descomposicin de los diferentes
polmeros presentaban un hombro a bajas temperaturas, siendo ste ms importante
conforme aumentaban los impedimentos estricos asociados a los sustituyentes laterales
del polmero. Para estudiar este efecto se seleccion el catalizador MCM-41(7) y se
realizaron experimentos en termobalanza donde se realizaron sucesivos ciclos de
calentamiento/enfriamiento con el fin de comprobar si este inicio prematuro del proceso
afectaba a la actividad del catalizador de cara a la etapa principal del proceso. Tras los
ciclos de calentamiento/enfriamiento, se realiz un experimento completo de pirolisis
hasta 550 C, observndose que la importancia relativa de este hombro disminua
sensiblemente y que la temperatura de mxima velocidad de descomposicin para la
etapa principal de degradacin aumentaba.

Los resultados obtenidos en este estudio permiten cubrir los siguientes

objetivos especficos:

o Estudio del papel que juega el rea superficial externa en materiales con
elevada superficie especfica, como el catalizador MCM-41, en la pirlisis de
polmeros. Estudio de la influencia de los procesos de desactivacin de los
centros cidos superficiales durante el proceso de pirlisis.

II

J. Anal. Appl. Pyrolysis 79 (2007) 443449

www.elsevier.com/locate/jaap

Study of the early deactivation in pyrolysis of polymers in

the presence of catalysts
A. Marcilla *, A. Gomez-Siurana, D. Berenguer
Dpto. Ingeniera Qumica, Facultad de Ciencias, Universidad de Alicante, Apartado 99, 03080 Alicante, Spain
Received 20 June 2006; accepted 2 February 2007
Available online 9 February 2007

Abstract
In this work, the early degradation step of the pyrolysis of some polymers in the presence of certain catalysts has been studied using
thermogravimetric analysis (TGA). Three commercial polymers (PE, PP and EVA) and three catalysts were studied (ZSM-5, MCM-41a, and
MCM-41b), and the MCM-41a catalyst has been selected for the analysis of the earlier steps of the pyrolysis process carried out in the presence of
catalysts. Several cycles of heatingcooling were performed using a thermobalance, in order to analyze the influence of the first stages of
decomposition on the activity of the more accessible active sites involved. In this way, the behaviour of the polymercatalyst mixtures (20% (w/w)
of catalyst) was studied and compared with that observed in the corresponding thermal degradation as well as in the pyrolysis in the presence of
catalysts, in a single heating cycle.
The results obtained clearly show the existence of an early degradation step. For a polymercatalyst system with low steric hindrances such as
PE-MCM-41, this early degradation step causes a noticeable decrease of the catalyst activity for the main decomposition step (i.e., cracking of the
chain). The decrease of the catalytic activity is lower for a polymercatalyst system with higher steric restrictions, as occurs in the EVA-MCM-41
degradation process. However, in this case, the catalyst activity in the first decomposition step (i.e., the loss of the acetoxi groups) is noticeable
decreased after one pyrolysis run, thus reflecting that the active sites involved are mainly the most accessible ones.
# 2007 Elsevier B.V. All rights reserved.
Keywords: Pyrolysis; Catalysts; Deactivation; PP; EVA; HZSM-5; MCM-41

1. Introduction
The rapid growth of the range of applications of plastics:
packaging, agriculture, construction, household, etc., has
turned these materials into a serious environmental problem
since plastics comprise 10 wt% (>30 vol.%) of municipal solid
waste.
Pyrolysis is one of the promising alternatives to dumping or
incineration for the treatment of plastic wastes, where the
polymer sample is heated in an inert atmosphere causing the
cracking of the polymer backbone. The thermal cracking of
polymers produces a very complex mixture of products, which
may be used as fuel but has low value as a source of chemicals.
However, by plastic cracking over different solid catalysts
(pyrolysis in the presence of catalysts) it is possible to obtain

* Corresponding author. Fax: +34 965903826.

E-mail address: antonio.marcilla@ua.es (A. Marcilla).
0165-2370/$ see front matter # 2007 Elsevier B.V. All rights reserved.
doi:10.1016/j.jaap.2007.02.002

products with higher commercial value and with a wider

number of applications [13].
Modern cracking uses zeolites as catalysts [15], which
cause an important reduction in the decomposition temperature
and allow more valuable gaseous products to be obtained.
However, the pore size of the zeolites is limited to a maximum
value of about 1.0 nm, which hinders the access of bulky
molecules to the acid sites located inside the channels. MCM41 is a catalyst, member of the relatively new family of
mesoporous materials, first synthesized in 1992 by Beck et al.
[6], which possesses highly regular arrays of uniform size pore
channels ranging from 1.5 to 10 nm and a large surface area,
thus improving the accessibility to the active sites located in the
inner of the mesopores [6].
Coke formation and its retention inside the pores is the main
cause of deactivation of zeolite and aluminosilicates catalysts
in hydrocarbon processing. Deactivation of these catalysts in
the pyrolysis of polymers in the presence of catalysts is mainly
due to active site poisoning and pore blockage by coke

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A. Marcilla et al. / J. Anal. Appl. Pyrolysis 79 (2007) 443449

deposition [7]. Both coking rate and coke composition depend

on a variety of parameters such as the characteristics of
the catalyst pore structure, the characteristics of the acid
sites, the nature of the reactant and the operating conditions
[8,9].
The study of the pyrolysis of polymers in the presence of
catalysts using thermogravimetric analysis (TGA) shows a
early degradation step of the process for some polymercatalyst
systems. This process causes a widening of the corresponding
peaks in the derivative of TGA curves (DTG curves), and in
some cases, the appearance of a shoulder [10]. This early
degradation step of the decomposition reactions is related to the
acid sites located on the surface of the material [11,12]. In fact,
according to bibliography [13], the influence of the acid sites
located on the external surface and in the pore mouth region of
zeolites cannot be ignored, although the concentration of these
acid sites is assumed to be smaller, generally 35% of the total
acid sites.
As an example, previous works on the pyrolysis of EVA in
the presence of catalysts [12,14] showed that, despite the
presence of some catalyst advances noticeably at the beginning
of the pyrolysis of the first step of EVA pyrolysis, the
corresponding temperature of maximum reaction rate i.e., the
peak temperature in the DTG curves remains almost
unaltered, thus suggesting a possible simultaneous deactivation
of the active sites involved in the early degradation step, and
consequently the overall process ends at the same temperature
as in the absence of catalyst.
In a previous work [10], a comparative study of the
behaviour of different solid acid catalysts in the pyrolysis of
different polymers was performed. In that work, a possible
influence of some catalysts in the initial degradation steps of
some polymers was observed. A hypothesis was suggested
that the active sites located on the external surface of the
catalyst or, in the case of mesoporous materials, the more
easily accessible active sites, would be involved in these
processes. On the other hand, as previously mentioned, some
studies about the pyrolysis of EVA over different catalysts
[12,14] also suggested that these active sites would undergo
deactivation processes simultaneous with their participation
in the above-mentioned earlier degradation steps. Therefore,
this work is focused on the study of the initial stages of the
pyrolysis in the presence of catalysts of three selected
polymers, with the main objective of validating the
hypothesis previously suggested. In this way, TGA studies
were carried out, and four cycles of heatingcooling were
performed in order to analyze the influence of the first stages
of decomposition on the activity of the active sites involved.
Three polymers (Polyethylene, PE, polypropylene, PP and an
ethylenevinyl acetate copolymer, EVA) were selected, and
three catalysts were studied (ZSM-5, MCM-41a, and MCM41b). Then, MCM-41a was selected to study this phenomenon in more detail. The behaviour of polymer-catalyst
mixtures (20% (w/w) of catalyst) was studied and compared
with that observed in the corresponding thermal degradation
as well as in the pyrolysis in the presence of catalysts, in a
single heating cycle.

2. Experimental
2.1. Materials
Table 1 shows the main characteristics of the commercial
polymers (polyethylene, PE, polypropylene, PP, and an
ethylene-vinyl acetate copolymer, EVA) selected in this work.
The nominal vinyl acetate (VA) content of the EVA copolymer
was 27% (w/w). The catalysts used were ZSM-5, MCM-41a
and MCM-41b, prepared in accordance with the method
reported in literature [15,16]. The main characteristics of these
catalysts are summarized in Table 2. As can be seen, in the case
of the MCM-41a, the low value of the Si/Al ratio produces a
material with high acidity. This material also presents a high
pore size and a large surface area, typical of this type of material
[10].
Pure polymer or copolymer samples as well as the
corresponding mixtures with 20% (w/w) catalyst were
pyrolysed under the experimental conditions described in the
next section.
2.2. Equipment and experimental conditions
The pyrolysis experiments were carried out in a Netzsch TG
209 thermobalance controlled by a PC under the Windows
operating system. The atmosphere used was nitrogen with a
flow rate of 45 STPml/min. The balance and the oven
thermocouple of the equipment were calibrated following the
manufacturers instructions. Pure polymers as well as mixtures
of powdered polymers and a catalyst of around 4 mg (3.2 mg of
the polymer with 0.8 mg of the catalyst) were pyrolysed.
In the pyrolysis in the absence of catalyst as well as in the
pyrolysis runs in the presence of catalyst in a single heating
cycle, the temperature was raised to 550 8C with a heating rate
of 10 8C/min. On the other hand, for studying the influence of
the initial decomposition steps in the overall process, four
cycles of heatingcooling were applied to the polymer + catalyst system studied. The heatingcooling cycles have been
performed under N2 atmosphere, in the thermobalance
equipment, which is provided with a cooling system, and
involve a heating rate of 10 8C/min and a cooling rate of 50 8C/
min. The initial and final temperatures were 50300 8C for the
PE mixtures, 50245 8C for the PP mixtures, and 50235 8C for
the EVA mixtures, respectively. In each heating run,
temperature was raised to a value below the temperature
corresponding to the apparent beginning of the thermal
decomposition of each polymer. All the heatingcooling runs
Table 1
Characteristics of the commercial polymers
Material

Density
(g/cm3)

Melt index
(g/10 min)a

Vicat
point
(8C)

Tensile
modulus
(MPa)

LDPE 780R
PP Novolen 1100L
EVA Escorene UL15028CC

0.923
0.910
0.950

20 (190/16)
8 (230/2.2)
150 (125/0.3)

93
70
64

115
1500
13

8C/kg.

A. Marcilla et al. / J. Anal. Appl. Pyrolysis 79 (2007) 443449

445

Table 2
Characteristics of the three catalysts used
Property
a

Pore size (nm)

BET area (m2/g) b
External surface area (m2/g) c
Pore volume (cm3/g) d
Si/Al ratioe
Acidity (mmol/g)f
Acidity weak acid sites f
Acidity strong acid sitef
Tdesorption NH3 (8C)f weak
acid sites
Tdesorption NH3 (8C)f strong
acid sites
Aloct/Altetra g
a
b
c
d
e
f
g

HZSM-5

MCM-41a

MCM-41b

0.51  0.55
334
67
0.27
24
1.36
0.82
0.54
165

1.7
956
126
1.00
7
2.08
1.39
0.69
155

2.4
1136
383
1.34
47
0.60
0.60

138

385

550

0.12

0.70

0.37

BJH.
N2 adsorption isotherms; BET method.
N2 adsorption isotherms; t method.
N2 adsorption isotherms; measured at P/P0 = 0.995.
XRF.
TPD of NH3.
NMR.

have been performed under the same experimental conditions

above described.
In order to evaluate the influence of the heatingcooling
cycles on the activity of the catalyst, an experiment was
performed, where the pyrolysis run was stopped when the
fourth cycle was ended and more fresh polymer was added in
order to once more achieve a 20% (w/w) catalyst mixture; then
the pyrolysis in the presence of catalysts was carried out in the
thermobalance, from 50 to 550 8C at 10 8C/min.
3. Results and discussion
According to bibliography [17,18], the first step in the
pyrolysis of a polymer in the presence of catalysts consists in
the cracking of the polymeric chains over the catalyst surface,
leading to oligomers, with higher possibilities for access to the
active sites located in the inner part of the catalyst pores, where
the complete degradation of the oligomers occurs. However,
most articles referring to [17,19] or not referring to [18,20,21]
this initial step do not report any noticeable loss of weight
associated to the oligomer formation, and the references are few
where a two-step process is considered [22]. In fact, according
to the results obtained in the present work, the existence of an
initial step involving the formation of volatile compounds
seems to be very dependent on the chemical and structural
characteristics of the polymer and the catalyst.
Fig. 1 shows the TGA and DTG curves obtained for the
pyrolysis of PP in the presence of the two different MCM-41
samples as well all in the presence of HZSM-5 zeolite. The
behaviour of these systems was discussed and compared
elsewhere [10], and here only the relative importance of the
initial decomposition step is emphasised. According to Table 2,
the main differences between the two MCM-41 samples
(MCM-41a and MCM-41b) are related to the respective BET
area and pore size (BET area 956 and 1136 m2/g and pore size

Fig. 1. TGA and DTG curves obtained in the pyrolysis of PP in the absence of
catalyst and in the pyrolysis in the presence of the different catalysts [10].

of 1.7 and 2.4 nm, respectively) and the acidity (2.08 and
0.60 mmol/g, respectively). The main characteristics of the
HZSM-5 sample were BET area of 334 m2/g, pore size of
0.51 nm  0.55 nm and acidity of 1.36 mmol/g [10]. According to these values, the higher specific surface and pore size of
MCM-41b favours the increase of the activity of this sample,
but the higher acidity of MCM-41a results in a higher activity,
as can be seen in Fig. 1, and as discussed elsewhere [10]. On the
other hand, the lower specific surface of HZSM-5 leads as a
consequence to the lower activity of this material in comparison
with the two MCM-41 samples.
According to the results of Fig. 1, the tail appearing at
temperatures below the peak temperature would suggest, for the
three catalysts, the existence of an initial step, and this is
specially marked in the presence of MCM-41a. This behaviour
reflects a clear influence of the catalyst characteristics, and
suggests that this can be only clearly observed if the catalyst
possesses a certain combination of pore size, specific surface
and acidity which lead to the existence of a high enough number
of very accessible active sites with also high enough acidity.
Fig. 2 shows the TGA and DTG curves obtained in programmed
thermal desorption of NH3, in the conditions described
elsewhere [10] for the catalysts reported in Fig. 1. The first
peak i.e., the peak at lower temperatures corresponds to the
NH3 desorption from the weak acid sites, whereas the second

Fig. 2. DTG and TGA curves from NH3 TPD of the three catalysts studied by
[10].

446

A. Marcilla et al. / J. Anal. Appl. Pyrolysis 79 (2007) 443449

peak corresponds to NH3 desorption from stronger acid sites.

The respective peak temperatures indicate the relative strength
of the acid sites. As can be seen, the strength of the weak acid
sites is similar for the three catalysts; but MCM-41b does not
possess strong acid sites, and the strength of the strong acid sites
of MCM-41a is noticeably higher for MCM-41a than for
HZSM-5. Table 2 shows the acidity associated to each type of
acid sites for each material. As can be seen MCM-41a possesses
the higher acidity. Therefore, the two main characteristics of
this material i.e. high acidity and high accessibility support
its role in the earlier stage of the pyrolysis in the presence of
catalysts. The behaviour observed for MCM-41b shows that the
only presence of accessibility is not enough for enhancing the
early step of the pyrolysis process. On the other hand, neither
high acidity nor strong acid sites are enough, as the behaviour of
HZSM-5 shows, and the simultaneous presence of high
accessibility properties is also needed.
Therefore, according to the previous comments, MCM-41a
has been selected for the detailed study of the early degradation
step of the pyrolysis in the presence of catalysts process. As
shown in Table 2, this material has high acidity and very
accessible active sites. Fig. 3 shows the TGA and DTG curves
corresponding to decomposition in the absence of catalyst and
the MCM-41a-pyrolysis of PE, PP and EVA. As can be seen, the
DTG curves corresponding to the pyrolysis of PE and PP in the
presence of catalysts (Fig. 3a and b) exhibit a shoulder at
temperatures below the temperature of maximum reaction rate
i.e., the peak temperature indicating the existence of an
initial reaction step with some weight loss, i.e. involving the
generation of volatile compounds, which is different to the
main reaction step, despite the fact that both are clearly
overlapped. This shoulder does not appear in the curves
corresponding to the thermal processes curves and, therefore, it
can be concluded that the catalyst must be involved in the
reactions generating the shoulder. As the comparison between
the curves corresponding to the pyrolysis in the absence and in
the presence of catalysts of each polymer shows (Fig. 3a and b),
and in good agreement with bibliography [2325], the presence
of the catalyst causes a noticeable decrease in the temperature
of maximum reaction rate for the main decomposition step (see
Table 3). Therefore, despite the clear appearance of an early
degradation step, no conclusion can be extracted in relation to
the above-mentioned eventual deactivation processes from the
curves shown in Fig. 3a and b and only the role of the catalyst in
the early beginning of the decomposition can be emphasised.
Fig. 3c shows the TGA and DTG curves corresponding to
the decomposition of EVA in the absence and in the presence of
catalysts. As in the previous case, a shoulder appears in the
DTG peak, corresponding to the first decomposition step and
associated to the participation of the catalyst in the early
degradation step of the process. However, some differences
with respect to the PE and PP cases can be observed. It is well
known that whereas the decomposition of PE and PP in the
absence and in the presence of catalysts show a single main
decomposition step [26], the decomposition of EVA proceeds
through two main decomposition steps [12,2729], which
involve, respectively, the vinyl acetate groups (VA groups) loss

Fig. 3. TGA and DTG curves obtained for the pyrolysis in the absence of
catalyst and in the presence of MCM-41a catalytic pyrolysis at 10 8C/min of (a)
PE, (b) PP and (c) EVA.

Table 3
Temperature of maximum decomposition rate for the main decomposition steps
of the different systems studied
Sample

Experiment

T (8C)

PE
PE-MCM-41
PE-MCM-41

Thermal
Conventional pyrolysis
Pyrolysis after 4 cycles-polymer addition

473
358
386

PP
PP + MCM-41
PP + MCM-41

Thermal
Conventional pyrolysis
Pyrolysis after four cycles-polymer addition

462
340
356

EVA
EVA + MCM-41
EVA + MCM-41

Thermal
Conventional pyrolysis
Pyrolysis after 4 cycles-polymer addition

353468
353406
353405

A. Marcilla et al. / J. Anal. Appl. Pyrolysis 79 (2007) 443449

and the cracking of the polymeric chain resulting from the

previous step. These two steps are reflected in the weight loss of
the TGA curves and in the peaks of the corresponding DTG
curves of Fig. 3c. According to bibliography [12], a shift of the
second decomposition step towards lower temperatures appears
as a consequence of the presence of the catalyst, whereas no shift
in the temperature peak of the first decomposition step can be
observed (see Table 3). As in the cases of PE and PP, the early
beginning also appears in the degradation of EVA in the presence
of catalysts. However, in this case, the reaction step affected by
the early beginning is not the cracking of the chain, but the loss of
VA groups. Therefore, it can be concluded that the catalyst also
acts in the first step of EVA degradation, provoking a widening of
the corresponding interval of reaction temperature. Moreover,
the temperature of maximum rate for the first step results almost
unchanged, thus suggesting that the active sites involved in the
process undergo some deactivation process. Nevertheless,
despite this eventual deactivation, related to the participation
of the catalyst in the VA groups loss, the catalyst maintains
enough activity to reduce the temperature of the second
decomposition step, where the polymeric chain is cracked
(see Table 3). Considering the voluminous nature of the VA
groups, the hypothesis that the active sites involved are the more
accessible ones can be suggested.
Therefore, there are two aspects to be studied and assessed:
(a) the influence of the external active sites in the early
beginning of the decomposition process and (b) the eventual
deactivation of these active sites. The first question will be
clarified through the comparison among the behaviours of
different polymer + catalyst systems, and applying the methodology described in the previous section for performing
several consecutive heatingcooling cycles. The second
question will be solved considering the behaviour during these
cycles together with the study of the case where fresh polymer
was added, and then the pyrolysis is continued until 500 8C, in
comparison with the pyrolysis runs in the presence of catalyst,
in a single heating cycle.
3.1. Influence of the external active sites in the early
beginning of the decomposition process
The comparison between Fig. 3a and b shows that the initial
degradation step in the pyrolysis in the presence of catalysts is
more pronounced for the PP decomposition than in the case of
PE. This fact could be related to the high number of tertiary
carbon atoms in the PP chains, which results in a more reactive
polymer [10,30]. However, the case of the pyrolysis of EVA in
the presence of catalysts, also with high number of tertiary
carbons, deserves a separate discussion. Unlike PE and PP,
whose degradation occurs in a main single step, as mentioned
above, the EVA pyrolysis involves two steps. Moreover,
according to bibliography [12], the peak temperature of the first
step is almost not affected by the presence of the acid solid.
Therefore, there are two possibilities:
(a) The chemical processes involved in the early degradation
step of EVA pyrolysis are similar to those occurring in the

447

cases of PE and PP. In other words, the weight loss observed

before the DTG peak related to the first step of EVA
decomposition is a result of the same chemical reactions in
both cases. However, this hypothesis does not seem very
feasible, because it implies that the catalytic cracking of the
chain could start before the VA groups loss, and this is not
supported by experience [14,27,29].
(b) The active sites of the catalyst are also involved in the step
of VA groups loss. Therefore, the catalytic phenomenon
observed in this case is somewhat different than those
involved in the cases of PE and PP, not corresponding to the
cracking reactions of the main chain, but also involving the
availability of very accessible active sites with enough
acidity. According to the bibliography, this seems to be the
more probable hypothesis, as shown by the composition of
the gas evolved during the first step of EVA pyrolysis (i.e.,
mainly acetic acid). Therefore, the results obtained show
that the process of loss of the VA groups loss also
undergoes the early degradation step.
3.2. Eventual deactivation of the active sites in the early
beginning of the pyrolysis process in the presence of
catalysts
Fig. 4 shows the TGA curves obtained in the heating
cooling cycles performed for each polymer + catalyst system.
For each polymer, the final temperature of the heating cycles is
different (300 8C for the PE mixture, 245 8C for the PP mixture,
and 235 8C for the EVA mixture), and has been selected below
the temperature where the pyrolysis in the absence of catalyst
starts, in order to ensure that the weight loss observed could
only be attributed to the catalyst presence. As can be seen, for
the three polymers, the weight loss obtained in the first heating
cycle is higher than that obtained in the next cycles. This fact
can be explained considering that the active sites involved in
this process deactivate quickly, resulting in a material with less
capacity for its catalytic role in the following cycles. In other
words, considering that the existence of deactivation simultaneous to the initial step occurs.
The analysis of the different heatingcooling cycles shown
in Fig. 4 indicates that the weight loss associated to the initial
step starts at lower temperatures in the first cycle than in those
following. Table 4 shows the temperatures of the starting point
of the weight loss associated to the first and to the following
heating cycles. Despite the fact that the low temperature
observed for the first cycle could be related to the elimination
of some adsorbed water on the catalyst, a clear decrease of the
starting temperature for the degradation process can be
observed, thus suggesting that deactivation readily occurs.
Moreover, the weight loss observed in each cycle is noticeably
lower in the case of EVA than in the cases of PE and PP. This
behaviour is in good agreement with the fact that the
degradation step affected by the early degradation step
involves lower weight loss in the case of EVA, where only
the 27% corresponding to the VA groups is pyrolysed, in
contrast to the case of PE and PP, where 100% of polymer may
react.

448

A. Marcilla et al. / J. Anal. Appl. Pyrolysis 79 (2007) 443449

Fig. 5. TGA and DTG curves corresponding to the pyrolysis in the absence and
in the presence of catalyst experiments performed in different conditions for (a)
PE, (b) PP and (c) EVA.

Fig. 4. TGA curves corresponding to the heatingcooling cycles of (a)

PE + MCM-41, (b) PP + MCM-41 and (c) EVA + MCM-41.

Table 4
Temperatures corresponding to the starting point of the weight loss in the first
and in the following heating cycles for the different polymers studied
Polymer

PE
PP
EVA

T (8C)
Cycle 1

Cycle 2

Cycle 3

Cycle 4

89
90
70

208
174
162

217
176
167

225
181
175

Fig. 5 shows the DTG curves corresponding to the following

pyrolysis runs: (i) pyrolysis in the presence of catalysts, in a
single heating cycle, (ii) pyrolysis in the presence of catalysts
after the four heatingcooling cycles, with addition of fresh
polymer, and (iii) pyrolysis in the absence of catalyst, performed
as described in Section 2. As can be seen, for the three polymers,
the shoulder appearing before the peak of the DTG curves (the
only peak in the cases of PE and PP and the first peak in the case of
EVA), which has been related to the early degradation step, is
clearly diminished after the heating cycles. This behaviour again
indicates that simultaneous deactivation processes occur,
provoking a noticeably loss of the activity of the catalyst after

A. Marcilla et al. / J. Anal. Appl. Pyrolysis 79 (2007) 443449

the heatingcooling cycles, when the fresh polymer is added and

the pyrolysis process is completed.
In the cases of PE and PP, when the pyrolysis in the presence
of catalysts is completed until the complete degradation of the
polymer, the catalyst losses part of its activity after the heating
cooling cycles, as compared with the pyrolysis in a single
heating cycle (see the corresponding peak temperatures in
Table 3), thus corroborating the previous comments. However,
in the case of EVA, the capacity of the catalyst to decrease the
temperature of the second decomposition step results almost
unmodified by the successive heatingcooling cycles. PE and
PP could access the most of the active sites, i.e. those located on
the external surface, as well as those located at the opening of
the pores or mesopores and in the inner parts of the catalyst.
However, before the VA group loss, the EVA chains can only
access the more accessible active sites (simplifying, the
external active sites), but leaving unaltered the less
accessible active sites, which therefore remain untouched for
the main decomposition step.
In good agreement with the previous comments, the
decrease of the activity, or in other words, the importance of
the deactivation process, is noticeably higher for PE than for PP.
As has been previously suggested, this behaviour can be
explained considering that the lower steric hindrances
associated to the PE chains could favour the access to the
polymer chains to less accessible active sites, perhaps some
located in the inner part of pores, thus resulting in an increase of
the deactivation of these acid sites. On the other hand, in the
case of EVA the higher steric hindrances associated to the VA
groups make access to the less exposed of the more
accessible active sites more difficult, resulting in a lower loss of
activity. For the second decomposition step, (which according
to bibliography [12,14], and in agreement with Figs. 3c and 5c
and Table 3, proceeds through a catalytic mechanism), these
steric effects would be enhanced by the crosslinking
phenomena, suggested by some authors [31], occurring before
the second step of EVA decomposition.
4. Conclusions
The pyrolysis of polymers in the presence of catalysts could
involve the existence of an initial degradation step, depending
on the chemical and structural characteristics of the polymer
and the catalyst. The behaviour observed suggests that this step
can only be clearly observed if the catalysts possesses a certain
combination of pore size, specific surface and acidity which
leads to the existence of a high enough number of very
accessible active sites and with a high enough acidity. On the
other hand, the relative importance of the early beginning of the
process seems to be increased as the reactivity of the polymer
chains increase: i.e., when the number of tertiary carbon atoms
increases. In the case of the pyrolysis of EVA in the presence of
catalysts, the active sites of the catalyst seem to be also involved
in the VA groups loss process.
The results obtained suggest that deactivation processes
occur simultaneously to the initial step. The more accessible
active sites, involved in such processes, are quickly deactivated,

449

resulting in a noticeable effect in the activity of the catalyst

versus the main decomposition step. On the other hand, the role
of these active sites, as well as the corresponding deactivation
process seems to be increased as the steric hindrances
associated to the polymer structure decreases.
Acknowledgements
Financial support for this investigation has been provided by
the Spanish Comision de Investigacion Cientfica y Tecnologica de la Secretara de Estado de Educacion, Universidades, Investigacion y Desarrollo and the European
Community (FEDER refunds) (CICYT CTQ2004-02187),
and by the Generalitat Valenciana (project ACOMP06/162).
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[23] A. Marcilla, A. Gomez, A.N. Garca, M.M.J. Olaya, Anal. Appl. Pyrol. 64
(2002) 85.
[24] A. Marcilla, A. Gomez, J.A. Reyes-Labarta, Kinetic Model. Polym. 42
(2001) 8103.
[25] A. Marcilla, A. Gomez, J.A. Reyes-Labarta, A. Giner, Polym. Degrad.
Stab. 80 (2) (2003) 233.
[26] H. Bockhorn, A. Hornung, U. Hornung, J. Anal. Appl. Pyrol. 50 (1999) 77.
[27] B.J. McGrattan, Appl. Spectrosc. 48 (12) (1993) 1472.
[28] A. Marcilla, A. Gomez, S. Menargues, J. Anal. Appl. Pyrol. 74 (1-2)
(2005) 224.
[29] A. Marcilla, A. Gomez, S. Menargues, Polym. Degrad. Stab. 89 (1) (2005)
145.
[30] A. Marcilla, A. Gomez, S. Menargues, R. Ruiz, Polym. Degrad. Stab. 88
(3) (2005) 456.
[31] B.-A. Sultan, E. Sorvik, J. Appl. Polym. Sci. 43 (1991) 1761.

Publicacin III: Characterization of high-impact polystyrene by catalytic pyrolysis

over Al-MCM-41: Study of the influence of the contact between polymer and
catalyst, A. Marcilla, A. Gmez-Siurana, J.C. Garca Quesada and D. Berenguer,
Polymer Degradation and Stability, Volume 92, Issue 10, (2007), Pages 1867-1872

El estudio de la descomposicin cataltica del poliestireno de alto impacto

(HIPS) en presencia de los catalizadores con elevado tamao de poro, como los MCM41 (Publicacin I), mostr la existencia de tres etapas diferentes de descomposicin, que
no aparecan en presencia del resto de slidos cidos, con menor tamao de poro, como
la zeolita ZSM-5, y que pareca estar relacionada con la descomposicin, en etapas
diferentes, de dos tipos de dominios presentes en el polmero, los dominios de
poliestireno y los dominios de polibutadieno. Adems, la importancia relativa de dichas
etapas pareca depender en gran medida del grado de contacto entre las partculas del
polmero y las partculas del catalizador. Para estudiar este efecto en mayor profundidad
se moli y tamiz una muestra de HIPS, para obtener fracciones con diferente tamao
de partcula, y se estudio el comportamiento de dichas fracciones en presencia del
catalizador MCM-41(7) mediante termogravimetria.

Los resultados obtenidos en este estudio permiten cubrir los siguientes

objetivos especficos:

o Estudio del efecto del tipo de contacto entre polmero/catalizador durante la

pirlisis cataltica.

III

Polymer Degradation and Stability 92 (2007) 1867e1872

www.elsevier.com/locate/polydegstab

Characterization of high-impact polystyrene by catalytic pyrolysis

over Al-MCM-41: Study of the influence of the contact
between polymer and catalyst
A. Marcilla, A. Gomez-Siurana, J.C. Garca Quesada, D. Berenguer*
Dpto. Ingeniera Qumica, Universidad de Alicante, Apdo. 99, 03080 Alicante, Spain
Received 8 March 2007; received in revised form 26 June 2007; accepted 28 June 2007
Available online 20 July 2007

Abstract
In this work, the particular behaviour of a commercial high-impact polystyrene (HIPS) during the catalytic pyrolysis over Al-MCM-41 has
been studied. The results obtained in a thermobalance showed differences in the number and/or the relative importance of the reaction steps
involved in the pyrolysis, depending on the polymer particle size, which can be related to the differences in the nature of the polymeric phase
being decomposed in each stage. Moreover, the relative importance of each step is very dependent on the particle size, revealing differences in
the distribution of the different copolymer domains (i.e., styrene and butadiene domains) when the different particle size samples are mixed with
the catalyst. The type of contact of the pure PS and PB polymers has also been studied revealing that, contrary to other results in literature, the
catalyst may have an important effect both on the PS and PB pyrolysis. The results obtained showed that catalytic pyrolysis of these polymers
could be a powerful tool for providing a fast and simple method for the characterization of copolymers of styrene and butadiene units.
2007 Elsevier Ltd. All rights reserved.
Keywords: Catalytic pyrolysis; Al-MCM-41; HIPS; PS; PB; TGA

1. Introduction
High-impact polystyrene (HIPS) is a typical rubber-toughened polymeric material basically prepared by the free-radical
polymerisation of styrene in the presence of a dissolved rubber
like polybutadiene (PB) to improve the impact strength and
toughness of glassy polystyrene (PS). Typically, the PB content
is in the range of 3e10 mol%. Major applications of HIPS
include packaging, containers, appliance parts, housewares,
and interior parts in household electronics. At present, HIPS
competes with acrylonitrileebutadieneestyrene terpolymer
(ABS) and is gradually replacing ABS markets with comparable properties and lower costs. Current research issues are
focused on the development of high-performance HIPS such

* Corresponding author. Tel.: 34 96 590 2953; fax: 34 96 590 3826.

E-mail addresses: antonio.marcilla@ua.es (A. Marcilla), desi.bm@ua.es
(D. Berenguer).
0141-3910/$ - see front matter 2007 Elsevier Ltd. All rights reserved.
doi:10.1016/j.polymdegradstab.2007.06.016

as transparent, glossy, chemical-resistant, high-impact strength,

and flame-retardant grades [1].
Because HIPS is composed of multicomponent and multiphase polymeric materials, with glassy and rubbery phases,
end-use properties are dependent on many variables, such as
the molecular weight (MW) and molecular weight distribution
(MWD) of the polymerised PS and rubber used, the composition and concentration of rubber, the particle size and the particle size distribution of the rubber-dispersed phase, the
rubber-phase volume, the degree of grafting, and crosslinking
[2e5]. That is to say, the properties of the HIPS depend
mainly on the proportion of PB, data that the suppliers do
not usually facilitate.
Zeolites and aluminosilicates such as Al-MCM-41 show
excellent properties as catalysts for the pyrolysis of plastic
and plastic waste. The catalyst causes an important reduction
in the decomposition temperature and allows more valuable
gaseous products to be obtained [6]. On the other hand, thermogravimetric analysis (TGA) has been extensively used to

A. Marcilla et al. / Polymer Degradation and Stability 92 (2007) 1867e1872

1868

study the decomposition of polymers for years. The information provided by this technique has allowed kinetic data to
be obtained, and the effect of the polymer structure, composition and operating variables on the pyrolysis process to be
studied [7e9]. In a previous work [7], the pyrolysis of HIPS
in the presence of Al-MCM-41 showed an unexpected behaviour, with three different decomposition steps. In this work, the
influence of the polymer particle size and the effectiveness of
the intimate contact between the polymer and the catalyst is
demonstrated.
Some authors study the catalytic pyrolysis process focusing
on the influence of the nature of the contact of the catalyst and
the polymer, however, this factor has not been extensively
studied [10,11]. Due to the bulky nature of the polymer molecules, a determinant factor in the catalytic pyrolysis is the
type of catalystepolymer contact. The dispersion phenomena
in the catalystepolymer mixtures could lead to mass transfer
limitations that are characteristic of the heterogeneous catalysis. In this way, a procedure to ensure that the catalyst is
uniformly dispersed and that therefore a good contact exists
between the polymer and the catalyst, consists in mixing
solutions of the polymer in an adequate solvent with the solid
catalyst, and after evaporating the solvent, to obtain very
homogeneous solid mixtures with a very effective contact
between both solids.
In order to assess the nature of the phases being decomposed in each degradation step of a HIPS copolymer, in this
work, dynamic pyrolysis runs of mixtures of Al-MCM-41
and different polymers and copolymers involving styrene
and butadiene as monomers have been performed in a TGA
equipment. The results obtained permitted the nature of the
processes involved in each step of decomposition to be better
known, and suggest the possibility of using TGA as a fast tool
in order to characterize different styreneebutadiene copolymers, such as HIPS.

state nuclear magnetic resonance spectra (NMR), N2 adsorption isotherms at 77 K, and temperature-programmed desorption (TPD) of ammonia, using the equipment and
experimental conditions described elsewhere [7]. Table 2
shows the physicochemical and structural characteristics of
Al-MCM-41.

2.2. Experimental equipment

Thermogravimetric runs were performed in a Netzsch TG
209 thermobalance. The sample temperature was measured
with a thermocouple directly at the crucible, i.e., very close
to the sample. A temperature calibration procedure was
performed, in accordance with the equipment recommendations, and the different samples were pyrolyzed through experiments in dynamic conditions carried out from 30 to 550  C at
10  C min1 under a nitrogen flow of 30 ml min1 (STP).
Samples of around 4 mg were pyrolyzed in the TGA equipment. For the catalystepolymer mixtures, the polymer was
thoroughly mixed with around 20% of powdered Al-MCM41 (i.e., 3.2 mg of the polymer with 0.8 mg of the catalyst).
In order to analyse the influence of the particle size in the
thermal and catalytic pyrolysis, a HIPS sample was powdered
using a IKA M20 grinder. Liquid nitrogen was used to cool the
material, facilitating its grinding and avoiding the thermal degradation of the polymer. Size fractions in the range of 0.6e0.5,
0.5e0.4, 0.4e0.3, 0.3e0.2 mm and less than 0.2 mm were
collected.
For the study of the influence of the contact between the
catalyst and the polymer, different samples were prepared dissolving the pure polymer (PS or PB) in xylene. Afterwards, the
catalyst was added and mixed with this solution, and finally
the solvent was eliminated by evaporation.
Table 2
Characteristics of AleMCM-41

2. Experimental
2.1. Materials
Three commercial polymers were selected: High-Impact
Polystyrene 473 D and crystal Polystyrene 143E, both supplied by BASF, and Polybutadiene 830 JSRRB supplied by
Dynasol. The corresponding characteristics, as provided by
the supplier, are shown in Table 1.
Al-MCM-41 was prepared according to a method reported
in the literature [12], and was characterized by X-ray diffraction (XRD), X-ray fluorescence (XRF), 27Al and 29Si solid

Property

MCM-41

Pore size (nm)a

d100 (nm)b
)c
a0 (A
Wall thickness (nm)d
BET area (m2/g)e
External surface area (m2/g)f
Pore volume (cm3/g)g
Si/Al ratioh
Acidity (mmol/g)i
T desorption NH3 ( C)j
Aloct/Altetraj

1.7
3.25
3.77
2.07
956
126
1.00
7
2.08
155e550
0.70

a
b

Table 1
Characteristics of the commercial polymers
Material
HIPS Polystyrol 473D
PS Crystal Polystyrol 143E
PB Polybutadiene JSR 830RB

c
d

Density
(g/cm3)

Melt index
(g/10 min)

Tensile modulus
(MPa)

1.05
1.043
0.909

12
10
3

1700
3300
7.8

e
f
g
h
i
j

BJH.
XDR.
p
a0 2d100 = 3.
a0 e pore size.
N2 adsorption isotherms: BET method.
N2 adsorption isotherms: t method.
N2 adsorption isotherms: measured at P/P0 0.995.
XRF.
TPD of NH3.
NMR.

A. Marcilla et al. / Polymer Degradation and Stability 92 (2007) 1867e1872

3. Result and discussion

Fig. 1 shows the normalized weight loss curves (NTGA
curves), as well as the corresponding derivative curves
(DNTG curves) for the thermal and Al-MCM-41 catalytic
pyrolysis of HIPS, as provided by the supplier, and for the
Al-MCM-41 catalytic pyrolysis of the different size fractions
obtained after being powdered and sieved. The NTGA curves
show the representation of (w  wc)/(w0  wc) versus the temperature, where w weight of sample at time t, w0 weight of
sample at t 0, and wc weight of catalyst, obtained in the
thermobalance as the weight of the residue at the final temperature. All the NTGA curves corresponding to the thermal
pyrolysis of the different size fractions are completely coincident, and also coincide with that obtained for the material in
pellets, as provided by the supplier. Therefore, only one case
(the pelletised material) is shown. However, in the presence
of Al-MCM-41 as a catalyst, important differences can be
observed.
The comparison between the NTGA and DNTG curves
corresponding to the thermal and catalytic pyrolysis of the
non-powdered sample, i.e., in its pelletised commercial
form, shows curves almost coincident, thus suggesting that
there is almost no effect of the catalyst on the pyrolysis
process. This behaviour is in good agreement with the bibliography, where the steric hindrances related to the voluminous
phenyl groups of PS are considered as the reason for the
1

(a)

0,9
0,8

(w-wc)/(w0-wc)

0,7
0,6
0,5

HIPS -0,2 mm
HIPS 0.3-0.2 mm
HIPS 0.4-0.3 mm
HIPS 0.5-0.4 mm
HIPS 0.6-0.5 mm
HIPS in Pellets
Thermal HIPS

0,4
0,3
0,2
0,1
0

50

150

250

350

450

T (C)

(b)

0,02

DNTG

0,015

HIPS -0,2
HIPS 0.3-02
HIPS 0.4-0.3
HIPS 0.5-04
HIPS 0.6-0.5
HIPS Pellets
Thermal HIPS

0,01

0,005

0
200

250

300

350

400

450

500

T (C)
Fig. 1. (a) NTGA curves and (b) DNTG curves obtained in the thermal and
Al-MCM-41 catalytic pyrolysis of the different size fractions of HIPS.

1869

low activity of the zeolites and related materials in the pyrolysis of PS [13,14]. Surprisingly, a very different behaviour was
observed when the polymer was powdered, and the single peak
observed in the DNTG curve for the Al-MCM-41 catalytic
pyrolysis of the commercial HIPS form turns into a threepeak curve (i.e., a three-step process), with different relative
importance depending on the size of the HIPS particles. Considering, as an example, the DNTG curve corresponding to the
catalytic pyrolysis of the 0.6e0.5 mm fraction of HIPS
(Fig. 1b), a main peak at a temperature slightly lower than
that corresponding to the commercial sample, a wide tail at
lower temperatures, and a marked shoulder at a higher temperature can be observed. In a previous work [7], the comparison
of the respective peak temperatures with those corresponding
to the decomposition of the pure polymers [15,16] suggested
the possibility that the main peak is related to the PS domain
decomposition, whereas the shoulder is related to the decomposition of the PB domain. With respect to the series of HIPS
samples pyrolyzed, it can be observed that the small peak (or
shoulder) at high temperatures shifts to lower temperatures as
the particle size decreases, and its relative intensity decreases.
The second peaks (i.e. the intermediate temperature peaks)
clearly show an evolution similar to that described for the
small peak at the higher temperatures. The peak at the lowest
temperature appears at the same temperature, regardless of the
particle size, but its intensity increases with decreasing particle
size.
In order to obtain more insight into the observed behaviour,
different experiments were run with pure PS and pure PB, as
well as with samples of both polymers varying the type of catalyst/polymer contact.
Fig. 2 shows the NTGA and DNTG curves corresponding
to the thermal and Al-MCM-41 catalytic pyrolysis of a pure
PS sample. Two different catalytic runs have been performed:
using a physical mixture of pure PS and Al-MCM-41, and
using a mixture of Al-MCM-41 and a solution of pure PS in
xylene, where the solvent was completely removed by evaporation prior to the pyrolysis run, both mixtures being prepared
according to the procedure described in Section 2. In this way,
a considerable increase in the intimate contact between the
polymer and the catalyst in the mixture prepared from the xylene solution can be expected. As can be seen, the temperatures of maximum degradation rate (i.e., the DNTG-peak
temperatures) corresponding to the thermal process and the
catalytic pyrolysis of the physical mixture are 408 and
401  C, respectively. This similarity between both temperatures has been the reason for the hypothesis found in the bibliography [13,14] that there is not any influence of the catalyst
in the PS pyrolysis. However, as Fig. 2b reflects, when using
a catalyst such as that studied in this work, the shape of the
DNTG peaks for both processes are quite different: the curve
corresponding to the catalytic process shows a shoulder at low
temperatures and occurs in a wider temperature interval,
whereas the curve corresponding to the thermal pyrolysis is
very symmetrical and occurs in a narrow interval of temperature. These differences indicate that, despite the fact that the
peak temperatures are very similar the catalyst plays a certain

A. Marcilla et al. / Polymer Degradation and Stability 92 (2007) 1867e1872

1870

(a)

1
0,9
0,8

(w-wc)/(w0-wc)

0,7
0,6
0,5
0,4
0,3
Thermal PS
Catalytic PS in Pellets
Catalytic PS in Xylene

0,2
0,1
0

50

150

250

350

450

550

350

450

550

T (C)

(b)

0,03

Thermal PS
Catalytic PS in Pellets
Catalytic PS in Xylene

0,025

DNTG

0,02
0,015
0,01
0,005
0

50

150

250
T (C)

Fig. 2. (a) NTGA curves and (b) DNTG curves corresponding to the thermal
and Al-MCM-41 catalytic pyrolysis of a pure PS sample. The two catalytic
runs correspond to a PSeAleMCM-41 physical mixture and a PSeAle
MCM-41 mixture prepared from a PSexylene solution.

correspondingly the possibilities for the occurrence of the catalytic reaction, decreasing with the temperature of the process.
Fig. 3 shows the NTGA and DNTG curves corresponding
to the thermal and Al-MCM-41 catalytic pyrolysis of a pure
PB sample. Similar to the previous experiments, the catalytic
pyrolysis of a physical mixture of pure PB and Al-MCM-41
and a mixture prepared from a solution of PB in xylene,
have been performed. As can be seen, the DNTG-peak temperatures corresponding to the thermal process and the catalytic
pyrolysis of the physical mixture are very close, at around
458 and 444  C, respectively. As in the case of the PS, a certain
effect of the catalyst is observed. However, in the case of the
pyrolysis of the PB Al-MCM-41 mixture obtained from the
PBexylene solution two peaks appear at around 354 and
443  C, respectively. This result suggests that, in this case,
the intimate contact between the polymer and the catalyst permits the degradation of a fraction of PB (around 60% of the
polymer) at lower temperatures, through a catalytic pathway,
whereas the rest of the polymer decomposes in a thermal
way, at higher temperatures. This behaviour can be explained
considering that, when the catalyst surface is covered with the
polymer, under certain conditions where very effective contact
degree is possible, the more accessible catalytic active sites
could permit the catalytic effect on a certain part of the polymer. However, the fraction of polymer which is not in direct
contact with the catalyst evolves through a thermal pathway.

(a)

1
0,9
0,7
0,6
0,5
0,4
0,3
Thermal PB
Catalytic PB in Pellets
Catalytic PB in Xylene

0,2
0,1
0

50

150

250

350

450

550

350

450

550

T (C)

(b)

0,05
Thermal PB
Catalytic PB in Pellets
Catalytic PB in Xylene

0,045
0,04
0,035
0,03

DNTG

role in the PS decomposition. This conclusion is corroborated

by the results corresponding to the catalytic pyrolysis of the
sample prepared from the PSexylene solution. As can be
seen in Fig. 2b, the peak temperature of the DNTG curve corresponding to the pyrolysis of the PS Al-MCM-41 mixture
obtained from the PSexylene solution shows that the process
occurs at a noticeably low temperature (315  C), thus revealing that, if the possibility of an intimate contact between the
polymer and the catalyst is allowed, and if the catalyst structural characteristics are appropriate, the catalyst has a marked
effect on the pyrolysis of PS, despite the steric hindrances related to the phenyl groups. In this case, the relatively high pore
size and BET area of Al-MCM-41 guarantees good possibilities for its acting as a catalyst, and the sample preparation procedure permits the excellent contact between the polymer and
the catalyst.
Therefore, in accordance with the previous comments, the
comparison among the curves shown in Figs. 1 and 2 suggests
that the first DNTG peak corresponding to the catalytic pyrolysis of the powdered HIPS samples could correspond to the
catalytic pyrolysis of the PS fraction. This peak approaches
the thermal pyrolysis peak as the particle size of the sample
increases, becoming the limiting case of the pelletised sample,
which shows a single peak, almost coincident with the thermal
peak. Thus it seems that, as the particle size decreases, the
quality of the polymerecatalyst contact increases, and

(w-wc)/(w0-wc)

0,8

0,025
0,02
0,015
0,01
0,005
0

50

150

250

T (C)
Fig. 3. (a) NTGA curves and (b) DNTG curves corresponding to the thermal
and Al-MCM-41 catalytic pyrolysis of a pure PB sample. The two catalytic
runs correspond to a PB-MCM-41 physical mixture and a PBeAleMCM-41
mixture prepared from a PBexylene solution.

A. Marcilla et al. / Polymer Degradation and Stability 92 (2007) 1867e1872

Nevertheless, another explanation for this behaviour could be

the catalyst deactivation. PB pyrolysis yields high amount of
coke [17,18], that may block the access to the rest of the polymer to the active sites of the MCM-41.
The thermal and catalytic pyrolysis of a mixture containing
90% of pure PS and 10% of pure PB (w/w), prepared from
a solution of both polymers in xylene has been performed,
and compared to the thermal decomposition of a physical mixture of both polymers. The corresponding NTGA and DNTG
curves are shown in Fig. 4. As can be seen, the thermal pyrolysis of the pellet mixture shows two decomposition stages,
corresponding to the independent decomposition of each polymer, but the thermal pyrolysis of the sample prepared from the
xylene solution shows a single peak with a shoulder at high
temperatures, corresponding to overlapping of the simultaneous degradation of both fractions. The DNTG curve corresponding to the catalytic decomposition of the PSePB
mixture prepared in xylene shows the presence of two peaks,
clearly separated, at temperatures of 340 and 445  C, which
can be related to the above-mentioned catalytic pyrolysis of
the PS fraction (with eventually some contribution of the
part of the PB) and the rest of the PB fraction, respectively.
From these results, it is clear that the first peak observed in
the curves of Fig. 1 can be ascribed to the catalytic pyrolysis
of the PS present in the HIPS, and the third peak to the PB.

(a)

1
0,9

(w-wc)/(w0-wc)

0,8
0,6
0,5
0,4
0,3
Thermal PSPB in Xylene
Thermal PSPB in Pellets
Catalytic PSPB in Xylene

0,2
0,1
50

150

250

350

450

550

T (C)

(b)

0,025
Thermal PSPB in Xylene
Thermal PSPB in Pellets
Catalytic PSPB in Xylene

DNTG

0,02
0,015
0,01
0,005
0

But, to ascribe the intermediate peak other considerations

must be taken into account. The flow properties of the two
polymers and their behaviour in the grinding process have
an important role in the pyrolysis behaviour of the different
particle size samples. PS is a brittle thermoplastic polymer
with a relative high facility of flow (see Table 1) as compared
to the elastomer PB. During the grinding it is likely that the PS
(easier to grind) concentrates in the smaller particle size fractions, whereas the PB domains (combined with PS) are likely
to remain in the larger particles (i.e. those more resistant to the
grinding). The small PS and HIPS and PB particles may interact more intensely with the catalyst as their particle size is reduced. Accordingly, the behaviour of the HIPS samples as
a function of the particle size is now clearer. The observed increase of the intensity of the first peak agrees with the increasing amount of PS in the small particle size fractions. The
second decomposition step can be related to the catalytic pyrolysis of the PS fraction of the HIPS particles, despite the
fact that part of the PB fraction of these particles can also decompose through this step. Therefore, the shift of the second
peak to lower temperatures and the decrease in its intensity
is consistent with its higher content of PS (although it also
contains some PB), and the flow properties of this fraction still
containing PB (consequently flowing with higher difficulty
than the PS fraction). This fraction decreases as the particle
size decreases. Finally the third peak corresponds to the PB
domains, and is more apparent in the larger particles, as a consequence of the above-mentioned processes.
4. Conclusions

0,7

1871

The results obtained in this work have proved that when the
polymer/catalyst contact is good enough the MCM-41 has an
important effect on the decomposition of both PS and PB. An
assignment of the different processes involved in the AlMCM-41 catalytic pyrolysis of a powered HIPS sample to
the different decomposition steps observed by TGA has been
suggested. The first decomposition step seems to be related
to the cracking of PS particles segregated from the HIPS during the grinding. The second step is the main decomposition
and seems to be related to the catalytic pyrolysis of the PS
fraction and part of the PB of the HIPS particles. Finally,
the third decomposition step seems to be associated with the
pyrolysis of the fraction not yet decomposed, and corresponding to the remaining PB fraction.
The results obtained in this work show that this behaviour
can be exploited to develop a tool for the characterization of
PB PS copolymers.
Acknowledgement

50

150

250

350

450

550

T (C)
Fig. 4. (a) NTGA curves and (b) DNTG curves corresponding to the thermal
and Al-MCM-41 catalytic pyrolysis of a mixture of pure PS and PB. Two thermal runs are shown: for the physical PS and PB mixture and for the mixture
prepared from the corresponding solutions in xylene. The catalytic run corresponds to the mixture prepared from the respective solutions.

Financial support for this investigation has been provided

by the Spanish Comision de Investigacion Cientfica y Tecnologica de la Secretara de Estado de Educacion, Universidades, Investigacion y Desarrollo and the European
Community (FEDER refunds) (CICYT PPQ2004-02187) and
by the Generalitat Valenciana (project GRUPOS03/159).

1872

A. Marcilla et al. / Polymer Degradation and Stability 92 (2007) 1867e1872

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Marcilla A, Hernandez MaR, Garca AN.
contact effectivity and the heating rate influence on the HDPE pyrolysis.
Journal of Analytical and Applied Pyrolysis 2007;79(1e2):424e32.
Serrano DP, Aguado J, Escola JM, Rodrguez JM. Influence of nanocrystalline HZSM-5 external surface on the catalytic cracking of polyolefins.
Journal of Analytical and Applied Pyrolysis 2005;74:353e60.
Aguado J, Serrano DP, Escola JM. A solegel approach for the room temperature synthesis of Al-containing micelle-templated silica. Microporous and Mesoporous Materials 2000;34:43e54.
Serrano DP, Aguado J, Escola JM. Catalytic cracking of a polyolefin
mixture over different acid solid catalysts. Industrial and Engineering
Chemistry Research 2000;39:1177e84.
Serrano DP, Aguado J, Escola JM. Catalytic conversion of polystyrene
over HMCM-41, HZSM-5 and amorphous SiO2eAl2O3: comparison
with thermal cracking. Applied Catalysis, B: Environmental
2000;25:181e9.
San Miguel G, Aguado J, Serrano DP, Escola JM. Thermal and catalytic
conversion of used tyre rubber and its polymeric constituents using PyGC/MS. Applied Catalysis, B: Environmental 2006;64:209e19.
Jakab E, Blazso M, Faix O. Thermal decomposition of mixtures of vinyl
polymers and lignocellulosic materials. Journal of Analytical and Applied Pyrolysis 2001;58e59:49e62.
Strakhov VM. Coke and Chemistry, USSR: Koks i Khimiya 2005;2:35e44.
Xia L, Hong-qiang L, Zhen-guo Z, De-min D. Iron and steel
2006;41(6):17e21.

Publicacin IV: Characterization of Styrene-Butadiene copolymers by catalytic

pyrolysis over Al-MCM-41, A. Marcilla, A. Gmez-Siurana, J.C. Garca Quesada,
and D. Berenguer, Journal of Analytical and Applied Pyrolysis, enviado.

Los resultados obtenidos del estudio de de la descomposicin cataltica del

poliestireno de alto impacto (HIPS) en presencia del MCM-41(7) (Publicacin III)
sugieren la posibilidad de utilizar tcnicas de pirlisis cataltica similares a las aplicadas
hasta el momento para el estudio de la pirlisis trmica y cataltica de polmeros para
llevar a cabo la caracterizacin de copolmeros de poliestireno-polibutadieno, en la que
la determinacin exacta de la composicin del copolmero no es sencilla, como es el
caso de los SBS. Para ello se desarroll y aplic un modelo pseudocintico que permite
evaluar la cantidad relativa del polmero que evoluciona a travs de cada etapa de
descomposicin, que podra ser usado para determinar la composicin de copolmeros y
mezclas de PS y PB, dato que normalmente no facilitan los distribuidores.

Los resultados obtenidos en este estudio permiten cubrir los siguientes

objetivos especficos:

o Estudio de la posibilidad de utilizar tcnicas de pirlisis cataltica de

polmeros como herramienta para la caracterizacin de copolmeros,
mediante la seleccin de las condiciones experimentales adecuadas y el
diseo de un modelo pseudocintico capaz de predecir el comportamiento
del sistema.

IV

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Contents lists available at ScienceDirect

Journal of Analytical and Applied Pyrolysis

journal homepage: www.elsevier.com/locate/jaap

Characterization of styrenebutadiene copolymers by catalytic pyrolysis

over Al-MCM-41
A. Marcilla, A. Gomez-Siurana *, J.C. Garca Quesada, D. Berenguer
Dpto. Ingeniera Qumica, Universidad de Alicante, Apdo. 99, 03080 Alicante, Spain

A R T I C L E I N F O

A B S T R A C T

Article history:
Received 5 May 2008
Accepted 18 August 2008
Available online xxx

In this work, the Al-MCM-41 catalytic pyrolysis of styrenebutadiene copolymers in a thermobalance has
been studied. The behaviour of such copolymers and the corresponding to high impact polystyrene
(HIPS), physical blend of PS and PB with a given grafting degree, has been compared, and the importance
of the degree of contact between the catalyst and the different polymer domains has been pointed out.
Different particle size copolymer particles have been mixed with the catalyst, and in addition, samples
have been prepared by solving the copolymer and mixing it with the catalyst, thus assuring an intimate
contact. Different decomposition steps which can be related to the degradation of the different domains
of the copolymer (polystyrene (PS) and polybutadiene (PB)) have been observed, despite the
decomposition processes of the PB and PS domains are not completely independent, showing certain
interaction. The importance of to carefully controlling, dening and characterizing the experimental
conditions of catalytic pyrolysis of PSPB experiments in order to generalize or to extend the results
obtained in such experiments is clearly demonstrated, and pseudokinetic models capable of reproducing
the amount of material evolving trough each decomposition step have been suggested. The possibility of
combining the two criteria: (1) the assignment of each decomposition step and (2) the application of a
pseudokinetic model is suggested as a potential tool for the characterization of the composition of
commercial copolymers or mixtures of PB and PS, once the adequate calibration runs have been
performed.
2008 Elsevier B.V. All rights reserved.

Keywords:
Catalytic pyrolysis
Al-MCM-41
Styrenebutadiene copolymers
Characterization
TGA

1. Introduction
High impact polystyrene (HIPS) is a multiphase system with a
polystyrene (PS) rigid matrix with dispersed polybutadiene (PB)
rubber particles that enhance the impact properties of the blend.
Typically, the PB content is in the range of 310 mol.%. HIPS is
widely used for numerous applications in our daily life. Major
applications of HIPS include packaging, containers, appliance parts,
household goods and interior parts in household electronics. At the
present time, HIPS competes with acrylonitrilebutadienestyrene
terpolymer (ABS) and is gradually replacing ABS markets with
comparable properties and lower costs. Current research issues are
focused on the development of high-performance HIPS such as
transparent, glossy, chemical-resistant, high impact strength, and
ame-retardant grades [1].
Because HIPS is composed of multicomponent and multiphase
polymeric materials, with glassy and rubbery phases, end-use

* Corresponding author. Tel.: +34 96 590 2953; fax: +34 96 590 3826.
E-mail address: antonio.marcilla@ua.es (A. Gomez-Siurana).

properties are dependent on many variables, such as the molecular

weight (MW) and molecular weight distribution (MWD) of the
polymerized PS and rubber used, the composition and concentration of the rubber, the particle size and the particle size distribution
of the rubber-dispersed phase, the rubber-phase volume, the
degree of grafting, and crosslinking [25]. In accordance with
the previous remarks, the properties of HIPS mainly depend on the
proportion of PB, data that suppliers do not usually facilitate.
SBS copolymers may have a similar styrene/butadiene composition but have a very different molecular structure where blocks of
monomers form the polymer molecule contrarily to the HIPS
where the two polymers are physically mixed with possible
different grafting degrees. Dynasol (http://www.dynasolelastomers.com/) manufactures styrenebutadienestyrene (SBS) block
copolymers that ow like thermoplastics at processing temperatures and behave like reinforced elastic rubbers under normal
application conditions. These materials have a teleblock structure
based on a linear or star-branched exible polybutadiene central
block with rigid polystyrene end-blocks.
The great advantage in the application of these copolymers is
the fact that no vulcanisation is required for a three-dimensional

0165-2370/$ see front matter 2008 Elsevier B.V. All rights reserved.
doi:10.1016/j.jaap.2008.08.010

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network to be formed and thus provide the reinforced properties

typical of chemically cross-linked rubbers. These types of products
are widely used in adhesive applications and as compatiblizers.
Different catalysts can be used in the pyrolysis of polymers and
may cause an important reduction in the decomposition temperature thus yielding more valuable gaseous products [6]. The most
habitual catalysts employed in polymer catalytic pyrolysis are
zeolites and aluminosilicates as MCM-41 due to their specic size
porous structure and their acidity. On the other hand, thermogravimetric analysis (TGA) has been extensively used to study the
decomposition processes of polymers for years. The information
provided by this technique has allowed kinetic data to be obtained,
and the effect of the polymer structure, composition and operating
variables on the pyrolysis process to be studied [79].
In a previous work [10] the catalytic pyrolysis of HIPS was
studied. In that work, a peculiar behaviour was observed when the
polymer was pyrolized in the presence of Al-MCM-41, showing the
existence of a three-step process, each one with different relative
importance depending on the size of the HIPS particles. An
assignment of the different reaction steps involved in the process
was suggested, and the rst decomposition step was related to the
cracking of PS particles segregated from the HIPS during the
grinding of the samples. The second step is the main decomposition step and seems to be related to the catalytic pyrolysis of the PS
fraction and perhaps of some part of the PB of the HIPS particles.
Finally, the third decomposition step could be associated with the
pyrolysis of the fraction not yet decomposed, corresponding to the
remaining undecomposed PB fraction, which would correspond
with the major part of the initial PB fraction.
In this work, dynamic pyrolysis runs of mixtures of Al-MCM-41
and different polymers and copolymers involving PS and PB have
been performed in TGA equipment. The main objective of the
present paper has been focused on the comparison between the
HIPS behaviour, which has been extensively studied elsewhere
[10], and the SBS copolymers behaviour. The great effect of the
catalyst/copolymer contact degree has been studied, and the
importance of the methodology for the preparation of the catalystcopolymer mixture used as sample in the TGA run has been
demonstrated.

copolymer with 30% of styrene content, most of this forming a

polystyrene block which gives the polymer a thermoplastic
behaviour. It develops properties of vulcanised rubber yet does
not require vulcanisation.
Al-MCM-41 was selected as a catalyst for the pyrolysis process,
and was prepared according to the method reported in the
literature [11], and characterized by X-ray diffraction (XRD), X-ray
uorescence (XRF), 27Al and 29Si solid state nuclear magnetic
resonance spectra (NMR), N2 adsorption isotherms at 77 K, and
temperature-programmed desorption (TPD) of ammonia, using the
equipment and experimental conditions described elsewhere [7].
Table 2 shows the physicochemical and structural characteristics
of Al-MCM-41.
2.2. Experimental equipment
Thermogravimetric runs were performed in a Netzsch TG 209
thermobalance swept with nitrogen with a ow rate of
30 ml min1 (STP). The sample temperature was measured with
a thermocouple directly at the crucible, i.e., very close to the
sample. A calibration procedure was performed each day using
internal standards (aluminium, nickel and perkalloy). Experiments
in dynamic conditions were carried out from 30 to 550 8C at
10 8C min1. In the catalytic experiments, HIPS was mixed with
powdered Al-MCM-41, and samples of around 4 mg (3.2 mg of the
polymer with 0.8 mg of the catalyst) were pyrolized.
It is important to take in consideration the fact that, despite the
overall shape of the TGA and DTG curves will be similar, certain
shift is expected towards higher temperatures when the catalyst is
reused (and therefore partially deactivated), and towards lower
temperatures when the catalyst amount increases. Moreover,
some details of the TGA curves may be modied as the catalysts are
deactivated [12], and a saturating effect could appear up to high
loads of catalysts [13]. Therefore, the experimental conditions
must be carefully controlled in order to ensure the reproducibility
of the results.
3. Result and discussion
3.1. Analysis of the HIPS behaviour

2. Experimental
2.1. Materials
Three commercial polymers were selected: High-Impact
Polystyrene 473 D (HIPS) supplied by Basf and two SBSs, Calprene
416 and Calprene 487, supplied by Dynasol. The corresponding
characteristics, as provided by the supplier, are shown in Table 1.
Calprene1 487 is a thermoplastic copolymer butadiene/styrene
(45/55), polymerized in solution. It has a radial structure and is
extended with 40 phr (parts per hundred parts of resin) of
parafnic oil. This product is presented in pellet form and has very
adequate ow properties for compounding articles intended for
injection. Calprene1 416 is a radial styrenebutadiene block
Table 1
Characteristics of the commercial polymers
Material

HIPS Polystyrol 473D

SBS Calprene 416
SBS Calprene 487
a
b

At 200 8C.
At 190 8C.

Density

Melt index

(g/cm3)

(g/10 min)

Tensile modulus
(MPa)

1.05
0.94
0.96

12
0.5a
14b

1700
2.7

Fig. 1 shows the normalized weight loss curves (NTGA curves)

obtained in the thermobalance and the corresponding derivative
curves (DNTG curves) for the thermal and catalytic pyrolysis of
HIPS, as provided by the supplier, and for the catalytic pyrolysis of
the different size fractions obtained after powdering and sieving
Table 2
Characteristics of the catalyst used
Property

Al-MCM-41

Pore size (nm)a

BET area (m2/g)b
External surface area (m2/g)c
Pore volume (cm3/g)d
Si/Al ratioe
Acidity (mmol/g)f
Acidity weak acid sitesf
Acidity strong acid sitef
Tdesorption NH3 (8C) acid sitesf
Aloct/Altetrag

1.7
956
126
1.00
7
2.08
1.39
0.69
155550
0.70

a
b
c
d
e
f
g

BJH.
N2 adsorption isotherms; BET method.
N2 adsorption isotherms; t method.
N2 adsorption isotherms; measured at P/P0 = 0.995.
XRF.
TPD of NH3.
NMR.

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In this work, a pseudokinetic model has been developed in

order to quantify the amount of material which evolves through
each reaction step, avoiding the uncertainty related to the direct
reading in the experimental curves. Such model permits to
quantify the inuence of the particle size and the polymer
catalyst contact degree in the catalytic pyrolysis process. Moreover, if an adequate calibration procedure is applied, and the
adequate experimental conditions (i.e., the optimum particle size,
type of catalyst, catalyst:polymer ratio, etc.) are selected, the
results obtained when such a model is applied to the experimental
NTGA and DNTG data, in combination with the assignment of the
different reaction steps, could be exploited as a tool for a fast
estimation of the styrene:butadiene ratio.
The suggested model consists in a series of consecutive
reactions, and considers that the PS fraction of the copolymer
decomposes in two steps in a catalytic way, whereas the
decomposition of the PB fraction is not affected by the presence
of the catalyst and decomposes in a thermal way. In this way, for a
PSPB copolymer such as HIPS, the following three-reaction
scheme has been considered, in good agreement with the threestep process shown in Fig. 1b. As commented above, the PS and PB
domains are considered to be independently decomposed; the PS
domains are catalytically decomposed through the rst two
reaction steps, and the PB domains are thermally decomposed
in the third reaction step. Therefore, the reaction scheme applied is
K C1

P!a1 GC1 1  a1 P 
K C2


P !a2 GC2 1  a2 PC2

Fig. 1. (a) NTGA and (b) DNTG curves obtained in the thermal and Al-MCM-41
catalytic pyrolysis of the different size fractions of HIPS.

the samples. The NTGA curves show the representation of w 

wc =w0  wc versus the temperature, where w weight of
sample at time t (or temperature T), w0 weight of sample at
T = 100 8C, when the major part of the water adsorbed in the
catalyst has been removed, and wc weight of catalyst, obtained
in the thermobalance. wc has been considered as the weight of the
residue at the nal temperature. In this way, the amount of coke
formed over the catalyst at the end of the process has been
considered as negligible [14]. The DNTG curves correspond to the
derivate of the NTGA curves. All the TGA curves corresponding to
the thermal pyrolysis of the different size fractions are completely
coincident, and also coincide with that obtained for the material in
pellet form, as provided by the supplier.
As can be seen in Fig. 1, a noticeable inuence of the HIPS
particle size in the Al-MCM-41-catalytic pyrolysis behaviour can
be observed. This inuence has been studied in a previous work
[10], where a detailed analysis of this behaviour was performed
and compared with the behaviour of the pure PS and PB polymers.
As a conclusion, the following assignment of each reaction step
was proposed:
 The rst step, at around 325 8C, corresponds to the catalytic
cracking of the lower size particles of PS segregated during the
grinding process.
 The second step, at temperatures between 350 and 425 8C, would
correspond to the catalytic cracking of larger HIPS particles and
may include the PS domains of the grafted chains.
 The third decomposition step (i.e. the shoulder at around 440 8C)
has been related to the thermal cracking of the rest of material,
not decomposed in the previous steps, and mainly corresponds
to the thermal pyrolysis of the PB domains.

KT


!G2
PC2

(R-1)
(R-2)
(R-3)

where (R-1) and (R-2) represent the rst and the second reaction
step respectively, corresponding to two successive processes
where the catalytic pyrolysis of the PS fraction occurs, and (R-3)
represents the third stage, corresponding to the thermal pyrolysis


and PC2
are the materials resulting after the
of the PB fraction. PC1

represents the
(R-1) and (R-2) processes, respectively. PC2
copolymer, once the main part of the PS domains have already
reacted. GC1 and GC2 represent the volatile compounds evolved in
(R-1) and (R-2), respectively, and KC1 and KC2 are the respective
specic rate constants. a1 and a2 are the stoichometric coefcients

,
(in mass units) for the formation of GC1 and GC2 from P and PC2
respectively, and can be related to the PS content of HIPS. a1
indicates the fraction of P which evolves through (R-1) and a2 is the

which evolves through (R-2). G2 represents
fraction of PC1
the volatile compounds evolved in (R-3), and corresponds to the
overall mass of PC2, which decomposes without any solid residue
formation.
According to (R-1), (R-2) and (R-3), the following differential
equations can be written:
dX P
K C1 XPn1
dt

(1)

dX PC1
n2
1  a1 K C1 XPn1  K C2 XPC1
dt

(2)

dX PC2
n2
n3
1  a2 K C2 XPC1
 K T XPC2
dt

(3)


and
where XP, XPC1* and XPC2* represent the mass fraction of P, PC1

, respectively, in the mixture being decomposed, expressed in
PC2
catalyst-free basis. Therefore, at the initial time, t = 0, XP = 1 and
XPC1* = XPC2* = 0, and the evolution with the time of the mass
fraction of the mixture, w, calculated as w X P X PC1 X PC2 can

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Fig. 2. Comparison between the experimental and calculated DNTG curves for the
catalytic pyrolysis of the different particle size samples of HIPS.

be calculated once Eqs. (1), (2) and (3) are solved. n1, n2 and n3 are
the reaction orders of (R-1), (R-2) and (R-3), respectively. The
respective rate constants, KC1, KC2 and KT, can be modelled in
accordance with the Arrhenius law:


E
K i K i0 exp  i
RT

(4)

where Ki0 is de preexponential factor and Ei the activation energy

corresponding to the reaction characterized by the specic rate
constant Ki. The following objective function has been applied in
order to calculate the optimal values of the parameters of the
model (i.e., a1, a2, KC10, KC20, KT0, EC1, EC2, ET, n1, n2 and n3) that
better t the experimental NTGA and DNTG data simultaneously:

F:O:

nexp
X

i1

dwexp;i
dT

Fig. 3. (a) NTGA and (b) DNTG curves obtained in the thermal and Al-MCM-41
catalytic pyrolysis of the different size fractions of Calprene 487.


dwcalc;i 2
dT




dwcalc;i
max dT

(5)

where wexp;i and wcalc;i are, respectively, the experimental and

calculated mass fraction of the mixture being decomposed,
expressed on a catalyst-free basis.
Fig. 2 shows the comparison between the experimental and
calculated NDTG curves corresponding to the different powdered
HIPS samples. As can be seen, in all the cases, the proposed model
provides a very satisfactory t of the experimental data. According
to Fig. 1, the amount of HIPS which evolves through each reaction
step depends on the particle size of the pyrolized sample.
Therefore, these differences must be reected in the values of
the a1 and a2 parameters calculated by the application of the model
described above. Table 3 shows the calculated values of such
stoichometric values for the different size samples. As can be seen,
as the size of the particles decreases, the amount of HIPS which
evolves through the rst reaction step increases, which is in good
agreement with the experimental observations. Thus, calculating
the percentages of PS and PB from the values of the parameters a1
and a2, and considering that PB domains only decompose through
(R-3), the calculated PB content decreases as the particle size of the
Table 3
Calculated values for the stoichometric parameters corresponding to the
application of the reaction scheme (R-1)(R-3) to the different size fractions of HIPS
Sample (mm)

a1

a2

0.60.5
0.50.4
0.40.3
0.30.2
<0.2

0.170
0.288
0.410
0.394
0.387

0.652
0.738
0.764
0.831
0.917

pyrolyzed sample decreases, indicating that the previous hypothesis that the PB domains only decompose thermally through (R-3)
is a coarse simplication of the HIPS behaviour, and some kind of
interface exists, where the pyrolysis of the PS and PB domains may
simultaneously occur.
3.2. Analysis of the Calprene 487 behaviour
Fig. 3 shows the NTGA and the DNTG curves corresponding to
the thermal and catalytic pyrolysis of the different size fractions of
Calprene 487. As in the HIPS case, the curves corresponding to the
thermal pyrolysis of the powdered samples were equal to those
corresponding to the thermal pyrolysis of the material in pellets. As
Fig. 3 reects, the DNTG curves corresponding to the thermal
pyrolysis of Calprene 487 and the catalytic pyrolysis of this
copolymer in the form of pellets are also very similar, showing two
decomposition peaks. The rst one appears at around 293 8C in the
thermal case, but in the catalytic process appears at around 260 8C.
This peak corresponds to the elimination of the oil. According to
the NTGA curves, the oil content of Calprene 487 is 27.6% by
reading in the NTGA thermal pyrolysis curve, and 30.3% by reading
in the NTGA catalytic pyrolysis curve of the pellet material. The
nominal oil content is 40/(100 + 40)  100 = 28.6%.
Fig. 3 also shows the NTGA and DNTG curves corresponding to
the different runs with the selected particle size of polymer. All the
curves present very similar behaviour regardless of the particle
size. The rst peak corresponding to the oil evolution occurs at
slightly lower temperatures (around 260 8C) and in a shorter range
of temperatures when the polymer was powdered and pyrolized in
the presence of catalyst. On the other hand, the second peak
observed in the previous cases exhibits splitting and another peak
appears at intermediate temperatures around 398415 8C.

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Fig. 4. NTGA and DNTG curves obtained in the Al-MCM-41 catalytic pyrolysis of a
mixture prepared from a xylene-solution of Calprene 487.

In accordance with the above-described assignment of the

decomposition steps, in the catalytic pyrolysis of PSPB copolymers
[10], the second peak of the catalytic pyrolysis curves of Calprene
487, which appears at around 398415 8C, depending on the particle
size of the polymer, is mainly related to the catalytic decomposition
of the PS domains, and the third peak, which appears at around
466 8C, is mainly related with the thermal decomposition of the PB
domains. On the other hand, the set of experiments carried out
reveals the importance of the contact between the polymer and the
catalyst. It seems that a signicant improvement has been achieved
by grinding the polymer, but the behaviour seems to be somewhat
independent of the particle size. Contrarily to the case of HIPS, where
the particle size had a signicant effect, in this case a good contact
degree is attainable by grinding even for the larger particles. In order
to obtain a better insight into the effect of the degree of contact,
another type of experiment was done by preparing a xylene solution
of the polymer and mixing it with the catalyst to obtain the same
catalyst to polymer ratio as in the previous experiments. The results
obtained are shown in Fig. 4. The three peaks previously observed
appear again, but now a great difference is observed with respect to
the powdered copolymer. The rst peak is somewhat reduced,
probably as a consequence of a likely oil loss in the sample
preparation process. On the other hand, the two peaks at higher
temperatures are more separated and the central peak increases
markedly, showing a very different interaction with the catalyst. It
seems as if the polybutadiene domains with no interaction with the
catalyst are less than the nominal polybutadiene content thus
indicating the presence of mixed domains containing butadiene that
present a certain interaction with the catalyst and decompose with
the polystyrene domains. On the other hand, the comparison
between the behaviour observed for HIPS and for Calprene 487, and
among the different samples of Calprene 487 (in pellets, grinded and
from a xylene solution) not only reects the great importance of the
contact degree between the plastic and the catalyst, but also that of
the original plastic chemical structure and of the procedure used for
mixing the plastic and the catalyst. As can be seen in Fig. 4, as the
possibility of the different domains in the copolymer to establish an
intimate contact with the catalyst increases (as in the case of the
sample prepared from the xylene solution), the reaction steps
involved in the process are better differentiated.
In order to quantify the peak areas, a kinetic model has been
applied. In this case, the original copolymer has been considered as
a mixture of the oil and the pure styrenebutadiene copolymer,
P. An initial stage has been considered, corresponding to the oil
elimination:
K Oil

Oil!G0

(R-4)

Fig. 5. Comparison between the experimental and calculated DNTG curves for the
catalytic pyrolysis of the 0.60.5 mm particle size fraction of Calprene 487 and for
the sample prepared from a xylene-solution of this copolymer.

where G0 represents the products generated as a consequence of

the oil pyrolysis. The reaction scheme applied considers that the
elimination of the oil through the reaction (R-4) proceeds in a
parallel way to the reactions (R-5) and (R-6) corresponding to the
degradation of P:
KC

P!aG1 1  aP

(R-5)

KT

P  !G2

(R-6)

In order to apply this reaction scheme, an additional parameter,

a, has been considered and calculated in order to represent the

amount of oil in the copolymer. In this way, the mass fraction of the
mixture, on a catalyst-free basis, can be calculated as
w X oil X P X P , and at t = 0, Xoil = a, XP = 1  a and XP* = 0.
Thus, the calculation of the following parameters a, KC0, KT0, EC, ET,
n1 and n2, corresponding to the copolymer pyrolysis, plus the
additional parameters corresponding to the oil elimination (a, and
three additional kinetic parameters for the oil pyrolysis process)
allows the quantication of the process. a represents the mass
fraction of oil in the Calprene 487 sample.
Fig. 5 shows the comparison between the experimental and the
calculated curves for the MCM-41-catalytic pyrolysis of the 0.6
05.5 mm size fraction of Calprene 487. This case has been selected
as an example, considering that, in good agreement with the fact
that the curves corresponding to the different particle size
fractions studied show very similar shapes, the pseudokinetic
parameters and the quality of the t must also be very similar.
Fig. 5 also shows the comparison between the calculated and
experimental curves corresponding to the sample prepared from
the xylene-solution and Table 4 shows the corresponding
calculated values for the kinetic parameters. As can be seen, a
very satisfactory t is obtained in both cases and the agreement
between the calculated and the experimental curves is very
satisfactory. Moreover, the calculated oil content from the 0.6
0.5 mm curve also agrees satisfactorily with the nominal value. As
in the HIPS case, if we calculate the PS and PB percentages, some
Table 4
Calculated values for the stoichometric parameters corresponding to the
application of the reaction scheme (R-4)(R-6) to the 0.60.5 mm size fraction
of Calprene 487 and to the sample prepared from the xylene-solution of this
copolymer
Sample

% Oil = 100a

0.60.5 mm
Xylene-solution
Nominal Value

0.309
0.237

0.375
0.244

30.9
23.7
29

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G Model

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A. Marcilla et al. / J. Anal. Appl. Pyrolysis xxx (2008) xxxxxx

Fig. 8. Comparison between the experimental and calculated DNTG curves for the
catalytic pyrolysis of the 0.60.5 mm particle size fraction of Calprene 416 and for
the sample prepared from a xylene-solution of this copolymer.

Fig. 6. (a) NTGA and (b) DNTG curves obtained in the thermal and Al-MCM-41
catalytic pyrolysis of the different size fractions of Calprene 416.

deviation with respect to the nominal values is obtained, thus

reecting the fact that the PS and PB pyrolysis are not independent
processes at all. This fact is also reected in the stoichometric
parameters calculated from the curves corresponding to the
sample prepared from the xylene-solution, where the parameter a
also reects the above-mentioned loss of oil.
3.3. Analysis of the Calprene 416 behaviour
Fig. 6 shows the NTGA and the DNTG curves corresponding to
the thermal and catalytic pyrolysis of the different size fractions
of Calprene 416. As in the previous cases, the curves corresponding to the thermal pyrolysis of the powdered samples were equal
to those corresponding to the thermal pyrolysis of the material in

pellets. In this case, the differences between the curves

corresponding to the thermal and catalytic pyrolyses are less
marked than for HIPS or Calprene 487, and, as in the case of
Calprene 487, all the curves corresponding to the catalytic
pyrolysis of the powdered samples follow very similar pathways.
All the DNTG curves show a main decomposition peak with a
shoulder at around 400 8C, below the temperature of maximum
decomposition rate, which is in the range of 466473 8C. In
accordance with the previous statements, the shoulder at lower
temperatures has been related to the catalytic decomposition of
the PS domains, and the main peak with the thermal decomposition of the PB domains.
As has been pointed out, in this case, lower differences between
the behaviour of the sample in pellets and grinded have been
observed. Therefore, as in the case of Calprene 487, the pyrolysis of
a sample prepared a xylene solution of the polymer mixed with the
catalyst has been performed to obtain the same catalyst to polymer
ratio as in the previous experiments. Results obtained are shown in
Fig. 7. As can be seen, a noticeable improvement in the separation
of the NDTG-peaks is achieved, once again reecting the
importance of the type of contact between the polymer and the
catalyst, as well as the structure of the sample and the procedure
used for mixing the plastic with the catalyst.
In this case, the kinetic model applied for the quantication of
the process only involves the two-reaction scheme dened by (R5) and (R-6). (R-5) represents the catalytic pyrolysis of the PS
domains, and (R-6) represents the thermal pyrolysis of the PB
domains. This model has been applied to the 0.60.5 mm fraction
of Calprene 416, as representative of the catalytic pyrolysis of each
one of the Calprene 416 samples, grinded or in pellets, analyzed
and to the sample prepared from the xylene-solution. Fig. 8 shows
the results obtained, and Table 5 shows the calculated corresponding values of the stoichometric coefcient. As in the previous cases,
the amounts of decomposed fractions through each step provided
by the model are not coincident with the nominal PB and PS
contents provided by the supplier, thus indicating that the
decomposition of the PS and PB domains are not independent
processes.

Table 5
Calculated values for the stoichometric parameters corresponding to the
application of the reaction scheme (R-5) and (R-6) to the 0.60.5 mm size fraction
of Calprene 416 and to the sample prepared from the xylene-solution of this
copolymer

Fig. 7. NTGA and DNTG curves obtained in the Al-MCM-41 catalytic pyrolysis of a
mixture prepared from a xylene-solution of Calprene 416.

Sample

0.60.5 mm
Xylene-solution

0.164
0.596

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G Model

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A. Marcilla et al. / J. Anal. Appl. Pyrolysis xxx (2008) xxxxxx

4. Conclusions

Acknowledgements

The results obtained in this work clearly indicate the importance

of variables as the structure of the copolymer, the ow characteristics and the contact of the different domains with the pore
structure and the active sites of the catalyst in the particular
behaviour of the catalytic pyrolysis of PSPB copolymers. The coarse
assignment of the reaction steps carried out suggests that the
amount of material decomposed through each decomposition step
not only depends on the percentage of each monomer in the
copolymer. The existence of certain interface where the decomposition of both types of domains occurs simultaneously has been
pointed out. In this way, it is very important to control the
experimental conditions used to carry out the catalytic pyrolysis
experiments of such systems in order to ensure the reproducibility of
the results and to permit to valuable conclusions.
In the particular case of the SBS copolymers, noticeable
differences in the behaviour have been observed when the
polymer and the catalyst were physically mixed as compared to
the case when a sample from a suspension of the catalyst in a
xylene solution of the polymer is prepared. In fact, in this case,
where the contact degree is improved, the differences among the
reactions steps are noticeably increased.
Finally, the possibility of exploiting the Al-MCM-41 catalytic
pyrolysis of styrenebutadiene copolymers as a procedure for the
approximate determination of the composition of such copolymers
could be considered, but with the aid of adequate standards.

Financial support for this investigation has been provided by

the Spanish Comision de Investigacion Cientca y Tecnologica
de la Secretara de Estado de Educacion, Universidades, Investigacion y Desarrollo and the European Community (FEDER refunds)
(CICYT PPQ2004-02187), Generalitat Valenciana (ACOMP06/162
and ACOMP/2007/094), and University of de Alicante; Grupo de
Procesado y Pirolisis de Polmeros (VIGROB099).
References
[1]
[2]
[3]
[4]
[5]
[6]
[7]
[8]
[9]
[10]
[11]
[12]
[13]
[14]

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M. Fisher, G.P. Hellman, Macromolecules 29 (1996) 24982509.
L. Rios-Guerrero, H. Keskkula, D.R. Paul, Polymer 41 (2000) 54155421.
D.P. Serrano, J. Aguado, J.M. Escola, E. Garagorri, J.M. Rodrguez, L. Morselli, G.
Palazzi, R. Orsi, Appl. Catal. 49 (2004) 257265.
A. Marcilla, A. Gomez-Siurana, D. Berenguer, Appl. Catal. A: Gene. 301 (2) (2006)
222231.
A. Marcilla, M. Beltran, J.A. Conesa, Anal. Appl. Pyrol. 5859 (2001) 117226.
A. Marcilla, A. Gomez, S. Menargues, J. Anal. Appl. Pyrol. 6869 (2003) 507526.
A. Marcilla, A. Gomez-Siurana, J.C. Garca Quesada, D. Berenguer, Polym. Degradat.
Stab. 92 (10) (2007) 18671872.
D.P. Serrano, J. Aguado, J.M. Escola, Micropor. Mesopor. Mater. 34 (2000) 4354.
A. Marcilla, A. Gomez-Siurana, D. Berenguer, J. Anal. Appl. Pyrol. 7 (12) (2007)
443449.
A. Marcilla, M. Beltran, J.A. Conesa, J. Anal. Appl. Pyrol. 5859 (2001) 117126.
A. Marcilla, A. Gomez-Siurana, A.O. Odjo, R. Navarro, D. Berenguer, Polym.
Degradat. Stab. 93 (3) (2008) 723730.

Please cite this article in press as: A. Marcilla, et al., J. Anal. Appl. Pyrol. (2008), doi:10.1016/j.jaap.2008.08.010

Publicacin V: Characterization of vacuum gas oillow density polyethylene

blends by thermogravimetric analysis, A. Marcilla, A. Gmez-Siurana, A.O. Odjo,
R. Navarro and D. Berenguer, Polymer Degradation and Stability, Volume 93, Issue
3, (2008), Pages 723-730

Con el objetivo de estudiar el reciclado de residuos plsticos mediante el proceso

de pirlisis cataltica, se consider la posibilidad de llevar a cabo el proceso utilizando
unidades similares a las de craqueo cataltico en lecho fluidizado (FCC) de las
refineras, y disolviendo el material plstico en un gasleo de vaco similar al que se
suele usar como alimento para obtener productos dentro del rango de las gasolinas. Con
el fin de evaluar esta posibilidad, se prepararon muestras con diferentes relaciones
VGO/Polietileno, y se realizaron estudios en termobalanza del comportamiento de las
mezclas frente a diferentes catalizadores, utilizando tanto los sintetizados en el
laboratorio (Publicacin I) como con otros slidos cidos comerciales, as como
tambin un catalizador de FCC de equilibrio. Para este estudio se trabajo con diferentes
relaciones muestra:catalizador y se determin mediante termogravimetria en atmsfera
oxidante la cantidad de coque depositado sobre cada catalizador.

Los resultados obtenidos en este estudio permiten cubrir los siguientes

objetivos especficos:

o Estudio de la viabilidad de utilizar la descomposicin cataltica de mezclas

de fuel y residuos plsticos en presencia de distintos catalizadores como va
de reciclado qumico de dichos residuos.

Available online at www.sciencedirect.com

Polymer Degradation and Stability 93 (2008) 723e730

www.elsevier.com/locate/polydegstab

Characterization of vacuum gas oilelow density polyethylene

blends by thermogravimetric analysis
A. Marcilla*, A. Gomez-Siurana, A.O. Odjo, R. Navarro, D. Berenguer
Departamento de Ingeniera Qumica, Universidad de Alicante, Apdo. 99, 03080 Alicante, Spain
Received 2 October 2007; received in revised form 20 November 2007; accepted 12 December 2007
Available online 27 December 2007

Abstract
The study of the catalytic pyrolysis of mixtures of fuel and polymers is interesting in order to explore the possibility of using commercial
fluid catalytic cracking (FCC) units or similar processes for recycling plastic wastes. In this work, different samples of vacuum gas oil (VGO),
polyethylene (PE) and vacuum gas oilepolyethylene blends (VGOePE) have been studied by thermogravimetric analysis. Vacuum gas oile
polyethylene blends with 1, 2.5, 5, 7.5 and 10% w/w of PE were prepared by continuously stirring for 120 min, at 60 rpm at 120  C, and
afterwards, the effect of different catalysts (HZSM-5, HUSY, HBeta zeolites, FCC catalysts and Al-MCM-41) on the decomposition of these
mixtures was studied. Moreover, the deposition of coke over each catalyst was studied by thermogravimetric analysis in an oxidant atmosphere.
The catalytic pyrolysis behaviour of the VGOePE mixtures indicates a two-step process, the degradation of the VGO and the PE fraction being
almost independent. The degradation or evaporation of the VGO fraction is only slightly affected by the presence of the catalyst, whereas the
PE fraction showed similar behaviour as that already described in the literature for the pure polymer. The results show that the HBeta zeolite is
the most active catalyst for the decomposition of the mixtures, and that the ZSM-5 zeolite is the catalyst with the lowest amount of coke
formation. These results are in very good agreement with the structural characteristics of the different catalysts studied, i.e., with their pore
size and acidity.
2008 Elsevier Ltd. All rights reserved.
Keywords: Vacuum gas oil (VGO); LDPE; Blends; TGA; Coke; Catalytic pyrolysis

1. Introduction
Since 1970, the production and consumption of plastics
have increased drastically with an increase of 98.1 kg per capita consumption of virgin plastics in 2003 [1]. This noticeable
increase in the use of these materials has caused an important
environmental problem due to the accumulation of plastics in
municipal solid waste (MSW).
Different alternatives are currently beginning to be considered for reducing the environmental impact of plastic wastes.
Primary or mechanical recycling consists of grinding the plastics and producing new goods with the resulting recycled material, however, the quality of the recovered material is lower

* Corresponding author. Tel.: 34 96 590 2953; fax: 34 96 590 3826.

E-mail address: antonio.marcilla@ua.es (A. Marcilla).
0141-3910/$ - see front matter 2008 Elsevier Ltd. All rights reserved.
doi:10.1016/j.polymdegradstab.2007.12.010

than that of fresh materials [2]. In the secondary recycling, incineration, calorific energy is generated. The calorific value of
plastics is comparable to that of fuels, around 46 MJ/kg [3],
but uncontrolled incineration can produce different pollutants
which are toxic at very low concentration. Finally, pyrolysis is
a tertiary recycling process, where the polymer sample is
heated in an inert atmosphere causing the cracking of the polymer backbone to convert these wastes into gas and liquid
hydrocarbons [4e6]. Moreover, the addition of catalysts improves the thermal process [7] because it permits more valuable products to be obtained at lower temperatures and at
lower reaction time.
An alternative approach, of the tertiary recycling, that is receiving increasingly more attention, is based on the fact that it
is possible to mix olefinic (polyethylene, polypropylene) and
styrenic polymers (polystyrene, polystyreneepolybutadiene)
in the usual feed of the process of catalytic cracking of

724

A. Marcilla et al. / Polymer Degradation and Stability 93 (2008) 723e730

hydrocarbons (FCC) in the refineries, i.e., in the vacuum gas

oils (VGO), and to turn them into products in the range of gasoline [8]. This approach would be feasible in the present units
of FCC since it does not involve important changes in the facilities given its versatility [9]. In this way, Ng [8] studied the
conversion of polyethylene (PE) dissolved in a commercial
VGO, and observed that for a certain relation of catalyst/
feed it was possible to significantly increase the production
of gasoline.
Zeolites and mesoporous materials are the most important
materials used as catalysts in the pyrolysis of plastics
[10e12], due to their porous structure and acid properties
[13]. An important application of these materials is in the fluid
catalytic cracking of hydrocarbons process (FCC), that is one
of the key processes in refineries, aimed at the conversion of
heavy feedstocks into lighter, more valuable products such
as light olefins, liquefied petroleum gas (LPG), gasoline and
diesel fuel [14].
The catalyst used in a commercial FCC unit (FCC catalyst)
is a very complex composite, where the main active component, the zeolite, is deposited on a matrix. Moreover, binders
and various additives are also present [15]. Matrices are of different types and they can be classified according to different
criteria: the chemical composition, the origin of their components (synthetic, semi-synthetic or natural), or the catalytic
role they play (inactive, or with low, medium or high activity).
Most commercial catalysts have semi-synthetic matrices,
consisting of a synthetic compound, usually amorphous silica,
alumina or silica/alumina, and a natural component, usually
clay [16].
The effects of several zeolites and other catalysts on the decomposition of different polymers have been extensively studied using thermogravimetric analysis (TGA) in dynamic
conditions [10,17e19]. Moreover, some authors used TGA
analysis to develop kinetic models for polymer decomposition
and to study the deactivation of the catalysts by coke deposition [12,20,21]. As an example, Manos et al. [12] studied the
catalytic decomposition of three polymers, LLDPE, PP and
LDPE, using several catalysts such as USY, HZSM-5, FCC
and a clay catalyst in thermobalance equipment. In this study,
the authors conclude that the USY catalyst was the most active
but produced the highest amount of coke, due to its strong
acidity.
In this work, different samples of vacuum gas oil (VGO),
polyethylene (PE) and vacuum gas oilepolyethylene blends
(VGOePE) have been characterized using thermogravimetric
analysis to study their behaviour in the thermal and catalytic
pyrolysis process, and to analyze the possibility of recycling
plastics by mixing them with the vacuum gas oil in refineries.
Thus, different catalysts were used, three commercial zeolites,
HZSM-5, HBeta and HUSY, a commercial equilibrium FCC
catalyst, and a mesoporous material, Al-MCM-41. Moreover,
considering that the deposition of coke is one of the principal
factors in the deactivation of catalysts, thermogravimetric
analysis of the coked zeolites in an oxidant atmosphere was
performed to estimate the proportion of coke over each
catalyst.

2. Experimental procedure
2.1. Materials
A low density polyethylene (LDPE) (200e500 mm particle
size) supplied by Dow Chemicals, with a density of 0.918 g/
cm3 (ASTM D 792) and melt flow index of 7.7 g/min (ISO
1133) has been used in this work. The vacuum gas oil
(VGO) and the commercial equilibrium FCC catalyst were
supplied by Repsol YPF (Spain). The VGO has a boiling range
of 240e560  C and a density of 0.920 g/cm3. The physicochemical and structural characteristics of the equilibrium
FCC catalyst are shown in Table 1.
A HUSY zeolite and a HZSM-5 zeolite were supplied by
Grace Davison, and a HBeta zeolite was supplied by SudChemie Inc. (HBeta 25). Al-MCM-41 was prepared according
to the method reported in literature [22]. All the catalysts were
characterized by X-ray diffraction (XRD), X-ray fluorescence
(XRF), N2 adsorption isotherms at 77 K, using the equipment
and experimental conditions described elsewhere [23] and
temperature-programmed desorption (TPD) of ammonia. Temperature-programmed desorption (TPD) of ammonia was performed in a Netzsch TG 209 thermobalance. The samples
were previously outgassed in a N2 flow of 45 ml/min by heating to 500  C with a rate of 10  C/min, retaining at this temperature for 30 min. After cooling to 100  C, the acid sites
were saturated by treatment with an ammonia flow of 35 ml/
min for 30 min. The physisorbed ammonia was removed by
passing a N2 flow of 45 ml/min for 60 min at 100  C. Finally,
the TPD measurements were carried out by heating the sample
in the N2 flow at a rate of 10  C/min up to 900  C. The acidity
of the materials was calculated using the weight loss observed
in the thermobalance at each TPD stage.

Table 1
Characteristics of the catalysts studied in this work
Property

FCC

ZSM-5

Pore size (nm)

0.51  0.55 0.74

BET area (m2/g)b

External surface
area (m2/g)c
Pore volume
(cm3/g)d
Si/Al ratioe
Acidity/weak
acid (mmol/g)f
Acidity/strong
acid (mmol/g)f
Total acidity
(mmol/g)f
T desorption
NH3 ( C)f

268
77

341
38

614
28

0.66  0.67 1.75

0.56  0.56
510
956
183
126

0.18

0.18

0.35

0.17

1.00

0.97
0.13

22
1.2

4.8
2.1

25
1.1

7
1.4

0.06

0.8

1.0

0.7

0.19

2.0

2.1

2.1

2.1

154

190e370

155e550

a
b
c
d
e
f

156e632 166e466

USY HBeta

BJH.
N2 adsorption isotherms; BET method.
N2 adsorption isotherms; t method.
N2 adsorption isotherms; measured at P/P0 0.995.
XRF.
TPD of NH3.

Al-MCM-41

A. Marcilla et al. / Polymer Degradation and Stability 93 (2008) 723e730

2.2. Experimental equipment

Thermogravimetric runs were performed in a Netzsch TG
209 thermobalance. The sample temperature was measured
with a thermocouple directly at the crucible, i.e., very close
to the sample. A temperature calibration procedure was performed, in accordance with the equipment recommendations,
and the different samples were pyrolyzed in dynamic conditions from 30 to 550  C at 10  C/min under a nitrogen flow
of 30 ml/min (STP). Samples of around 4 mg were pyrolyzed
in the thermogravimetric analysis (TGA) equipment. For the
catalysteLDPE, catalysteVGO and catalysteVGOePE mixtures, the sample of LDPE, VGO or VGOePE mixture, respectively, were thoroughly mixed with around 20% of
powdered catalysts (i.e., 3.2 mg of the sample with 0.8 mg
of the catalyst).
For estimating the amount of coke formed over each catalyst, thermogravimetric runs in oxidizing atmosphere, with
a ratio helium/oxygen of 80:20, were performed in a Mettler
Toledo thermobalance, TGA/SDTA851e/LF/1600 model, calibrated in accordance with the equipment recommendations,
from 25 to 850  C at 10  C/min.

behaviour for decomposition of polymers. Later, a 7:1 ratio

of catalyst/sample was used, which is a typical ratio used in
the refineries in the fluidized catalytic cracking processes.
Fig. 1 shows the weight loss curves (TGA) and the derivatives of the weight loss curves (DTG) obtained in the thermal
decomposition of the different samples of vacuum gas oil,
polyethylene, and the different blends of vacuum gas oilePE.
Table 2 shows the temperatures of maximum decomposition
rate corresponding to each reaction step, i.e., the temperatures
of each DTG peak. As it is possible to see, the comparison between the curves corresponding to VGO, pure PE and their
blends show the existence of a single decomposition step in
the cases of VGO and PE, but two decomposition steps in
the case of the blends. As can be seen in Table 2, the temperature of the first peak of the blends is very close to that of
the VGO peak, whereas the temperature of the second peak
of the blends is very close to that of the PE. Therefore, the first
stage can be clearly associated with the decomposition of the
vacuum gas oil, although the weight loss associated with
VGO may also be related to the evaporation of the different
components of VGO, whereas the second one can be related
to the PE decomposition. Moreover, both stages seem to proceed independently, despite the fact that some shift towards
higher temperatures of the peak associated to the VGO, when
the proportion of PE in the mixture increases, can be observed.
This increase seems to relate to the addition of the first 2.5% of

a 100
90
80
70
60

%w

The first peak of the TGA derivative curve (DTG) identifies

the temperature of desorption from weak acid sites and the
second peak of desorption identifies strong acid sites. Table 1
shows the physicochemical and structural characteristics of the
different catalysts studied in this work.
The VGOePE blends were prepared using a Jankel & Kunkel IKAVISC MR-F12 mixer by continuously stirring for
120 min, at 60 rpm and at temperatures of 120  C, mixtures
of the base components (LDPE and VGO) with different
weight fractions (1, 2.5, 5, 7.5 and 10%) of the polymer.
This temperature was selected for the sample preparation because at 120  C the LDPE is completely melted, thus permitting a good mixing degree with the VGO.

50
40
30
20

3. Result and discussion

VGO
PE
VGO-PE10
VGO-PE7.5
VGO-PE5
VGO-PE2.5
VGO-PE1

10
0
100

3.1. Study of the decomposition of VGOeLDPE blends in

the presence of an equilibrium FCC catalyst

200

300

400

500

400

500

T (C)

DTG

A mother blend of vacuum gas oil (VGO) and low density

polyethylene (PE) with 10% w/w of polyethylene was prepared as described in the previous section. From this mother
blend, other mixtures, lowering the percentage of polyethylene, were prepared, with 1% (VGOePE1), 2.5% (VGOe
PE2.5), 5% (VGOePE5), 7.5% (VGOePE7.5) and 10%
(VGOePE10) of PE, respectively.
The study of the behaviour of the samples during the pyrolysis process was carried out by TGA, considering the thermal
degradation of the mixtures, as well as the catalytic process in
the presence of an equilibrium FCC catalyst (FCC). For the
catalytic study, two types of experiments have been developed
modifying the proportion of catalyst. Firstly, a concentration
of catalyst of 20% w/w has been used, which is widely used
by other authors in the study by TGA of the catalytic

725

30
25

VGO
PE

20

VGO-PE10
VGO-PE7.5
VGO-PE5
VGO-PE2.5
VGO-PE1

15
10
5
0
100

200

300

T (C)
Fig. 1. (a) TGA and (b) DTG curves obtained for the thermal pyrolysis of different VGOePE blends.

A. Marcilla et al. / Polymer Degradation and Stability 93 (2008) 723e730

Table 2
Temperature of maximum decomposition rate for each reaction step of the
thermal and equilibrium FCC catalyst-catalytic pyrolysis of VGOePE
mixtures
Sample
Thermal pyrolysis
VGOePE10
VGOePE7.5
VGOePE5
VGOePE2.5
VGOePE1
PE
VGO

T ( C) VGO peak
320.3
324.9
322.2
320.1
301.4

T ( C) PE peak
478.1
477.6
477.5
472.4
466.4
475.2

0.7
0.6
0.5
0.4
0.3
0.2
0.1

VGO
PE
VGO-PE10
VGO-PE7.5
VGO-PE5
VGO-PE2.5
VGO-PE1

0
100

291.1

200

300

400

500

T (C)
462.1
454.4
444.8
444.1
438.1
439.9

0.02
0.018

VGO

0.016

PE

0.014

DNTG

Catalytic pyrolysis (20% of FCC catalyst)

VGOePE10
313.1
VGOePE7.5
306.4
VGOePE5
315.7
VGOePE2.5
299.9
VGOePE1
295.6
PE
VGO
282.7

1
0.9
0.8

(w-wc)/(wo-wc)

726

0.012
0.01
0.008

VGO-PE10
VGO-PE7.5
VGO-PE5
VGO-PE2.5
VGO-PE1

0.006

PE and further addition does not cause any additional increase.

The peak related to the decomposition of the PE fraction always appears at very close temperatures, except in the case
of the blend with 1% of PE, that approaches the pure PE temperature. Therefore, it seems that when the percentage of VGO
is high enough (<2.5% of PE in the blend) some tendency of
the peak associated to the PE to approach to the peak of
VGO can be observed.
Fig. 2 shows the normalized weight loss curves (NTGA)
and the corresponding normalized derivatives of weight curves
(DNTG) for the catalytic pyrolysis in the presence of the FCC
equilibrium catalyst with a relation of 20% in weight. The
NTGA curves show (w  wc)/(w0  wc) versus the temperature, where w weight of sample at time t, w0 weight of
sample at t 0, and wc weight of catalyst, obtained in the
thermobalance as the weight of the residue at the final temperature. As can be seen, as in the case of the thermal process, the
VGOePE blends decompose through two decomposition
steps, the first related to the degradation or evaporation of
the vacuum gas oil, and the second related to the PE decomposition. As in the previous case, when the proportion of PE
diminishes, the temperature of maximum decomposition rate
of the process associated with the pyrolysis of the VGO fraction tends to be closer to that of the VGO (Table 2), whereas
the temperature of maximum reaction rate associated with the
PE decomposition step increases when the proportion of PE
increases, so this temperature, in all the cases, is higher than
the pure PE peak temperature (Fig. 2b). On the other hand,
the effect due to the presence of the catalyst can also be
observed. In fact, both decomposition steps occur at a lower
temperature than that observed in the thermal process
(Table 2), despite the fact that in the presence of VGO, the catalytic pyrolysis of the PE fraction occurs at slightly higher
temperatures than those corresponding to the catalytic pyrolysis of the pure PE. For the case of the VGO peak, the catalytic

0.004
0.002
0
100

200

300

400

500

T (C)
Fig. 2. (a) NTGA and (b) DNTG curves obtained for the catalytic pyrolysis in
the presence of 20% w/w of equilibrium FCC catalyst for different VGOePE
blends.

process occurs in a wider range of temperature than the thermal process. When the proportion of polymer diminishes,
the VGO and PE peaks tend to shift to lower temperatures.
This behaviour can be observed in the 0e5% PE range for
the VGO peak, and in the overall range of composition studied
for the PE peak. In good agreement with the bibliography [24],
when increasing the catalyst:polymer relation, the difference
between the temperatures corresponding to the thermal and
catalytic process increases. In this case, the relation catalyst:PE increases when the percentage of PE in the mixture diminishes, whereas the relation catalyst:VGO increases when
increasing the percentage of PE in the mixture. Therefore,
the PE peak shows the expected behaviour, shifting towards
lower temperatures when the catalyst:PE ratio increases. However, in the case of the VGO peak, the effect of the catalyst is
less important, and is only noticeable from 1 to 5% of PE.
In order to clearly assess the effect of the concentration of
the catalyst on the behaviour of the blends, Fig. 3 shows the
DNTG for the catalytic pyrolysis using a 7:1 catalyst:VGOe
PE blend ratio. This ratio is very often used in the commercial
units of FCC. In this case, for all the samples, and independently of the proportion of polymer, three peaks in the
DNTG curve are observed. The first step has been associated
to the elimination of the water contained in the catalyst which,
considering the high proportion of catalyst used, represents

A. Marcilla et al. / Polymer Degradation and Stability 93 (2008) 723e730

1

VGO
PE
VGO-PE10
VGO-PE7.5
VGO-PE5
VGO-PE2.5
VGO-PE1

0.9

(w-wc)/(wo-wc)

0.8
0.7
0.6
0.5
0.4
0.3
0.2
0.1
0

25

125

225

325

425

525

T (C)

0.02
VGO
PE
VGO-PE10
VGO-PE7.5
VGO-PE5
VGO-PE2.5
VGO-PE1

0.018
0.016

DNTG

0.014
0.012
0.01
0.008
0.006
0.004
0.002
0

25

125

225

325

425

525

T (C)
Fig. 3. (a) NTGA and (b) DNTG curves obtained for the catalytic pyrolysis in
the presence of a 7:1 ratio of equilibrium FCC catalyst:VGOePE blends.

a considerable percentage of the mixture. The second step is

related to the decomposition or evaporation of the VGO fraction and the third to the degradation of the PE fraction. Moreover, both, the second peak of decomposition (VGO) and the
third peak of decomposition (PE), appear at approximately
the same temperature for all the samples, independently of
the amount of polymer in the blend. This behaviour seems
to indicate that the catalyst, which is in a clear excess with
respect to the sample, has developed the maximum catalytic
effect for both decomposition steps. As can be seen in
Fig. 3b, the VGO fraction decomposes in a very wide range
of temperatures, starting at around 120  C, and extends up to
around 390  C. It can be seen that the PE peak area increases
as the PE amount in the blend increases.

corresponding peak temperatures. As can be seen, two decomposition peaks are observed in the presence of all the catalysts
studied, associated to the decomposition of the VGO and the
PE fractions, respectively. In the case of the peak associated
to the decomposition or evaporation of the VGO fraction,
the effect of all the catalysts is similar. The observed peak
temperatures are in the range of 299e306  C. This is slightly
lower than that corresponding to the process in the presence of
the FCC equilibrium catalyst (320  C). This behaviour is in
good agreement with the chemical nature of the FCC, with
only a small part formed by the active component, the zeolite.
Moreover, we use an equilibrium catalyst, which has lost part
of its activity with respect to the fresh catalyst. Accordingly,
with respect to the peak of the PE, the catalytic activity of
the four materials considered is higher than that of the FCC
catalyst. An estimation of the catalytic activity of a material
can be obtained from the decrease of temperature that it causes
with respect to the thermal process [20,25]. Therefore, in
accordance with the results shown in Fig. 4 and in Table 3,
in this case the order of activity is: HBeta > Al-MCM41 > HUSY > HZSM-5 > FCC. This behaviour can be explained considering the physicochemical properties of the
catalysts (Table 1). In accordance with the bibliography
[23,26], the catalytic activity increases when the pore size,
the surface area and the external surface area, and the acidity
of the material increase. In this way, the most active catalyst is
the HBeta zeolite that, in comparison with the rest of

1
0.9

HBeta
FCC
Al-MCM-41
HUSY
HZSM-5

0.8

(w-wc)/(w0-wc)

727

0.7
0.6
0.5
0.4
0.3
0.2
0.1
0

50

150

250

350

HBeta
FCC
Al-MCM-41
HUSY
HZSM-5

0.007

DNTG

In this section, the effect of other catalysts different to the

FCC catalyst on the process of degradation of VGOePE
blends is studied. In this case we have related the VGOePE
blend with 10% (w/w) of PE, and the effect of three commercial zeolites (HZSM-5, HUSY and HBeta) and a mesoporous
material (Al-MCM-41), has been studied. The pyrolysis experiments have been carried out in a thermobalance, using a proportion of catalyst of 20% in weight. Fig. 4 shows the NTGA
and DNTG curves obtained and Table 3 shows the

550

0.01
0.009
0.008

3.2. Study of the decomposition of VGOeLDPE blends in

the presence of different catalysts

450

T (C)

0.006
0.005
0.004
0.003
0.002
0.001
0

25

125

225

325

425

525

T (C)
Fig. 4. (a) NTGA and (b) DNTG curves obtained in the catalytic pyrolysis of
VGOePE mixtures in the presence of 20% (w/w) of different acid solids.

A. Marcilla et al. / Polymer Degradation and Stability 93 (2008) 723e730

728

Table 3
Temperature of maximum decomposition rate for each reaction step of the
thermal and catalytic pyrolysis of VGOePE mixtures using different acid
solids
Sample

T ( C) VGO peak

T ( C) PE peak

HBeta
FCC
Al-MCM-41
HUSY
HZSM-5

310.4
313.0
310.9
313.0
313.0

376.3
462.2
411.7
416.8
459.6

materials, presents the larger acidity associated with strong

acid sites and the larger external surface area. The following
material in order of decreasing activity is Al-MCM-41, with
the higher pore size, which confers the higher BET area, and
also presents a noticeable acidity. The HUSY zeolite presents
a relatively high BET area and also a relatively large pore size,
but the external surface area is relatively small and, despite
presenting high acidity, it is related exclusively to the presence
of weak acid sites, and exhibits lower activity than the previous material. Finally, the zeolite HZSM-5 presents a noticeable
acidity, comparable with the acidity of the most active materials, but it exhibits the more unfavourable physicochemical
parameters, showing a relatively small external surface area,
and the lower pore size, and BET area. Therefore, HZSM-5
is the less active material.
3.3. Study of the deactivation of catalyst by coke
deposition
As has been previously mentioned, the deposition of coke
over the acid solid catalysts is an important factor in the deactivation processes of these materials. The degradation of
organic compounds over zeolitic materials generates a carbonaceous residue, which remains retained inside the pores, in
the surface of the material or in both zones. The deactivation
of zeolites for coke deposition is very important. When the
amount of coke in the surface and in the pores increases, the
number of available acid sites and the local diffusion possibilities decreases, thus decreasing the activity of the catalyst.
In this work, the amount of coke formed in the presence of
the five catalysts studied has been determined by TGA as has
been described in Section 2, from the weight loss associated to
the oxidation of the residue generated after the catalytic pyrolysis process. Table 4 shows the values obtained for the temperature of higher reaction rate of coke oxidation obtained in each
case, and Table 5 shows the amount of coke obtained,
Table 4
Temperature of oxidation of coke obtained from different samples over different catalysts
Catalyst

VGO

PE

VGOePE10

Beta
ZSM-5
USY
FCC
Al-MCM-41

580
578
551
560
552

552
575
550
562
552

580
577
546
561
552

calculated as a percentage of deactivated catalyst obtained after the VGOePE catalytic pyrolysis process, and where the
amount of coke has been considered to be equal to the mass
loss in the coke oxidation experiment.
The interpretation of the results corresponding to the temperature of the coke oxidation is complex, because there are
different influencing factors. Firstly, it depends on the composition of the coke, which changes for each catalyst and for
each pyrolyzed mixture. In addition, the location of the coke
in the zeolite framework and the possible diffusion effects,
which can make the access of the oxygen difficult to the molecules of coke, also affects the oxidation temperature. On the
other hand, the amount of coke formed also depends on the
same factors, and the zeolite and the type of pyrolyzed mixture
determine the nature, the amount and the location of the
carbonaceous residues formed in each case. According to the
literature [27], in general, the carbonaceous deposits can be
classified into two types; hard coke, which derives from aromatic hydrocarbon and usually forms at high temperatures,
and soft coke, which tends to form at low temperatures.
When the pore size of the zeolites is small, the reactions
between voluminous aromatic compounds with important steric hindrances are restricted, and the coke formation tends to
be very low. When the pore size is intermediate, the reactions
of cyclization and dehydrogenation to give aromatic simple
compounds and cycloparafines are possible, and could favour
the formation of soft coke. In the zeolites of great pore size,
the aromatic compounds can react to give more complex compounds that favour the formation of hard coke.
As Table 4 reflects, the temperature of oxidation of the coke
is between 546 and 580  C, depending on the system considered. In general, the lowest temperatures correspond to the
coke formed on the HUSY zeolite and MCM-41 material,
whereas the higher temperatures of oxidation correspond to
the coke formed on the FCC, HZSM-5 and HBeta catalysts.
Despite the fact that there are generally no noticeable differences in the temperature of oxidation depending on the considered samples (VGO, VGOePE, PE), in the case of the HBeta
zeolite, slightly different behaviour is observed when the pyrolyzed blend is VGO or VGOePE, which presents a higher
temperature of coke oxidation, than when PE is pyrolyzed,
with a relatively low temperature of oxidation. This change
of behaviour must be due, necessarily, to differences in the
composition of the coke formed in each case, which must be
less polyaromatic and/or less heavy when it comes from PE
than when it comes from VGO or VGOePE. The behaviour
of the VGOePE blend is clearly dominated by the greater
abundance of VGO. On the other hand, despite the fact that
the coke composition should be different in each case, the

Table 5
Percentage of coke obtained from different samples over different catalysts
%wt

HBeta

HZSM-5

HUSY

FCC 7:1

Al-MCM-41

VGO
PE
VGOePE

9.8
9.4
10.6

4.6
5.1
4.7

14.4
16.3
15.9

5.6
4.9
5.8

11.0
13.9
11.0

A. Marcilla et al. / Polymer Degradation and Stability 93 (2008) 723e730

lower temperature of coke oxidation obtained when using

HUSY zeolite and Al-MCM-41 could be related to the high
BET area and the relatively high pore size of both materials
that can favour the diffusion of the oxygen and facilitate the
oxidation [28].
With respect to the amount of coke formed in each case
(Table 5), the smaller amounts are obtained on the HZSM-5
zeolite and on the FCC catalyst. Despite the deactivation of
the catalyst not only depends on the amount of coke, but
also depends on its nature and location, a first approximation
to the resistance of deactivation can be assessed from the
amount of coke [20,29], and this fact indicates that these are
the most resistant materials to the deactivation by coke formation. Nevertheless, these catalysts also presented the lower activity (Table 4). The HUSY zeolite, with an intermediate
activity, presents the higher coke amount, and is the material
that favours the coke deposition more among the five catalysts
studied, possibly due to the high acidity associated to weak
acid sites (Table 1). The high tendency of the HUSY zeolite
to the deactivation by coke in the PE pyrolysis has also been
pointed out by other authors [20]. Finally, Al-MCM-41 and
the HBeta zeolite present a relatively high formation of
coke, but lower than in the case of the HUSY zeolite. Therefore, both materials show a tendency to the deactivation by
coke deposition similar to each other, and intermediate between HZSM-5 and the FCC catalyst. Both materials also
present a high catalytic activity, but the temperature of oxidation of the coke obtained on the Al-MCM-41 is lower than that
corresponding to the coke obtained for the HUSY zeolite.
Therefore, the conditions of regeneration will be more favourable for Al-MCM-41. Thus, excluding any other type of economic considerations, stability of the material or commercial
interest of pyrolysis products, the Al-MCM-41 can be considered a good choice to carry out the recycling of plastic residue
process by means of fluidized catalytic cracking of VGOePE
blends.
4. Conclusions
The results obtained in this work indicate that the thermal
and the catalytic pyrolysis of VGOePE blends proceeds
through two decomposition steps, the first related to the degradation or evaporation of the VGO fraction and the second
related to the decomposition of PE fraction. When the PE content of the mixture increases, the temperature of maximum
reaction rate for the first step increases and the NDTG peak
associated with the VGO decomposition approaches the PE
peak. As the VGO content increases, the PE peak tends to approach the VGO peak. This behaviour is less significant for the
VGO peak.
Both degradation steps are affected by the presence of the
catalyst, being displaced towards lower temperatures. The
effect of the catalyst is more noticeable for the decomposition
of the PE fraction than for the degradation or evaporation of
the VGO fraction. For a ratio 7:1, the equilibrium FCC catalyst used in this work has developed its maximum catalytic
activity.

729

The study of the decomposition of VGOePE blends in the

presence of different catalysts indicates that the effect of these
materials on the decomposition of the VGO fraction is very
similar for all the catalysts studied in this work, whereas in
the case of the decomposition of the PE fraction, the catalytic
effect of each material depends strongly on the physicochemical and structural characteristics of the catalysts, and the activity increases with the acidity, the BET area, the external
surface area and the pore size.
The composition of the coke formed as a consequence of
the pyrolysis process depends on the type of pyrolyzed mixture and the catalyst. Among the materials studied in this
work, the catalysts showing the lower tendency to coke formation are HZSM-5 and FCC, next are the HBeta zeolite and AlMCM-41 and the material that most favours coke formation is
the HUSY zeolite. On the other hand, the coke formed on the
HUSY and MCM-41 materials presents a lower temperature of
oxidation, whereas that formed on FCC and ZSM-5 displays
higher temperatures of oxidation. In the case of the coke
formed on HBeta, the temperature of oxidation clearly depends on the composition of the pyrolyzed material.
As a conclusion, the results obtained in this work indicate
the feasibility of the treatment of the VGOePE blends in
a conventional FCC process as an alternative way for plastic
recycling. Moreover, considering a criterion based exclusively
on the catalytic activity and the expectable deactivation behaviour, the material showing the best characteristics for the
pyrolysis of VGOePE blends in a FCC conventional process
is the Al-MCM-41, because this presents high catalytic activity, a low tendency to the formation of coke deposits and low
temperature of regeneration by oxidation of the coke.
Acknowledgements
Financial support for this investigation has been provided by
the Spanish Comision de Investigacion Cientfica y Tecnologica de la Secretara de Estado de Educacion, Universidades, Investigacion y Desarrollo and the European Community (FEDER
refunds) (CICYT PPQ2004-02187) and by the Generalitat
Valenciana (ACOMP06/162 and ACOMP/2007/094).
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[6] Kaminsky W, Schmidt H, Simon CM. Recycling of mixed plastics by
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[7] Aguado J, Serrano DP. Feedstock recycling of plastic wastes. Cambridge:

Royal Society of Chemistry; 1999.
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[11] Serrano DP, Aguado J, Escola JM, Rodrguez JM, Morselli L, Orsi R.
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[12] Manos G, Garfoth A, Dwyer J. Catalytic degradation of high-density
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[16] Scherzer J. Designing FCC catalysts with high-silica Y zeolites. Applied
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[17] Gobin K, Manos G. Thermogravimetric study of polymer catalytic
degradation over microporous materials. Polymer Degradation and
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[18] Fernandes GJT, Fernandes VJ, Araujo AS. Catalytic degradation of
polyethylene over SAPO-37 molecular sieve. Catalysis Today 2002;75:
233e8.

[19] Garca RA, Serrano DP, Otero D. Catalytic cracking of HDPE over
hybrid zeolitic-mesoporous materials. Journal of Analytical and Applied
Pyrolysis 2005;74:379e86.
[20] Marcilla A, Beltran MI, Hernandez F, Navarro R. HZSM-5 and HUSY
deactivation during the catalytic pyrolysis of polyethylene. Applied
Catalysis A General 2004;278(1):37e43.
[21] Marcilla A, Gomez-Siurana A, Valdes F. Catalytic cracking of lowdensity polyethylene over H-Beta and HZSM-5 zeolites: influence of
the external surface. Kinetic model. Polymer Degradation and Stability
2007;92(2):197e204.
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Microporous and Mesoporous Materials 2000;34:43e54.
[23] Marcilla A, Gomez-Siurana A, Berenguer D. Study of the influence of
the characteristics of different acid solids in the catalytic pyrolysis of
different polymers. Applied Catalysis A General 2006;301(2):222e31.
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pyrolysis: thermogravimetric study. Journal of Analytical and Applied
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[28] Magnoux P, Guisnet M. Comparison of rates of coke oxidation of HX, HMordernite and HZSM-5. Applied Catalysis 1988;38:341e52.
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Publicacin VI: Study of the decomposition of Vacuum Gas Oils-Low Density

Polyethylene blends: evolution of the gases, A. Marcilla, A. Gmez-Siurana, D.
Berenguer, Polymer Degradation and Stability, Available online 24 July 2008.

Al igual que en la Publicacin V, con el objetivo de estudiar el reciclado de

residuos plsticos mediante el proceso de pirlisis cataltica, disolviendo el material
plstico en un gasleo de vaco similar al que se suele usar como alimento de las
unidades de craqueo cataltico en las refineras, se estudi en un reactor de lecho fijo la
evolucin con la temperatura de la composicin de los productos obtenidos en la
pirlisis de VGO, PE y de una mezcla VGO/PE al 10% en presencia del catalizador de
FCC de equilibrio con una relacin catalizador:polmero de 7:1. Durante el proceso de
descomposicin, los gases generados fueron recogidos en bolsas de Tedlar y fueron
posteriormente analizadas mediante CG/MS, lo que permiti identificar los diferentes
compuestos generados y analizar la evolucin de stos con la temperatura.

Los resultados obtenidos en este estudio permiten cubrir los siguientes

objetivos especficos:

o Estudio de la viabilidad de utilizar la descomposicin cataltica de mezclas

de fuel y residuos plsticos en presencia de distintos catalizadores como va
de reciclado qumico de dichos residuos.

VI

ARTICLE IN PRESS
Polymer Degradation and Stability xxx (2008) 110

Contents lists available at ScienceDirect

Polymer Degradation and Stability

journal homepage: www.elsevier.com/locate/polydegstab

Study of the decomposition of low density polyethylene blends with

vacuum gas oils: Evolution of the gases
A. Marcilla*, A. Gomez-Siurana, D. Berenguer
Departamento de Ingeniera Qumica, Universidad de Alicante, Apdo. 99, 03080 Alicante, Spain

a r t i c l e i n f o

a b s t r a c t

Article history:
Received 19 May 2008
Accepted 8 July 2008
Available online xxx

Previous studies focused on the behaviour of different samples of vacuum gas oil (VGO), polyethylene
(PE) and vacuum gas oilpolyethylene blends (VGOPE) in thermal and catalytic pyrolysis, showed that
the pyrolysis of the blends goes through two decomposition steps, where the rst is related to the
elimination of the VGO fraction, and the second to the pyrolysis of PE. Moreover, the presence of catalyst
mainly affects the PE decomposition. In this work, the evolution of the composition of the gases evolved
in the thermal and catalytic pyrolysis decomposition of VGO, PE and VGOPE blend with temperature (or
time) has been studied by GC/MS. The results agree with the previous studies and allow the behaviour of
such systems to be better understood, yielding valuable information for designing processes of plastic
recycling by mixing with VGO and the mixture being treated in a unit similar to the industrial uid
catalytic cracking unit.
2008 Elsevier Ltd. All rights reserved.

Keywords:
Catalytic pyrolysis
Dynamic pyrolysis
GC/MS
VGO
PE
VGOPE blends

1. Introduction
Plastics consumption, and consequently its disposal, has exponentially increased over the last 30 years [1]. This has resulted in
a huge quantity of plastic waste, most of which is landlled. Among
the different methods to treat plastic waste, recycling is being
encouraged by different administrations.
Mechanical recycling (primary recycling) consists of grinding
the plastics and producing new goods with the resulting recycled
material; however, the quality of the recovered material is lower
than that of fresh materials [2]. In the secondary recycling, incineration, caloric energy is generated. The caloric value of plastics
is comparable to that of fuels, around 46 MJ/kg [3], but the principal
disadvantage is that this method can produce toxic gaseous
compounds. Finally, pyrolysis is a tertiary recycling process, where
the polymer sample is heated in an inert atmosphere causing the
cracking of the polymer backbone to convert these wastes into gas
and liquid hydrocarbons [46]; Moreover, the addition of catalysts
improves the thermal process [7] because it permits more valuable
products to be obtained at lower temperatures and at lower reaction time.
An alternative approach to tertiary recycling, which is receiving
increasingly more attention, is based on the fact that it is possible to
mix olenic (polyethylene, polypropylene) and styrenic (polystyrene, polystyrenepolybutadiene) polymers in the usual feed of
* Corresponding author. Tel.: 34 96 590 2953; fax: 34 96 590 3826.
E-mail address: antonio.marcilla@ua.es (A. Marcilla).

the catalytic cracking of hydrocarbons (FCC) in reneries, i.e., in the

vacuum gas oils (VGO), and to turn them into products in the range
of gasoline [8]. This approach would be feasible in renery FCC
units because it does not involve important changes in the facilities
given its versatility [9]. In this way, Ng et al. [8] studied the
conversion of polyethylene (PE) dissolved in a commercial VGO,
and observed that for a certain relation of catalyst/feed it was
possible to signicantly increase the production of gasoline.
Zeolites and mesoporous materials are the most important
materials used as catalysts in the pyrolysis of plastics [1012], due
to their porous structure and acid properties [13]. The FCC catalyst
used in commercial FCC units is a very complex composite, where
the main active component is a zeolite which is deposited on
a matrix. Matrices are of different types and can be classied
according to different criteria: the chemical composition, the origin
of their components (synthetic, semi-synthetic or natural), or the
catalytic role they play (inactive, or with low, medium or high
activity). Moreover, binders and others additives are also present
[14]. Most commercial catalysts have semi-synthetic matrices,
consisting of a synthetic compound, usually amorphous silica,
alumina or silica/alumina, and a natural component, usually clay
[15]. The fact that the active component in the FCC catalyst is
a zeolite, justies the possibility of the FCC catalyst acting as
a catalyst for plastics [16].
In previous work [17], different samples of vacuum gas oil
(VGO), polyethylene (PE) and vacuum gas oilpolyethylene blends
(VGOPE) with different percentages of PE (1, 2.5, 5, 7.5 and 10%)
were studied by thermogravimetric analysis, in the presence of

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different catalysts (HZSM5, HUSY, HBeta zeolites, FCC catalyst and

Al-MCM-41). The results obtained showed, considering a criterion
based exclusively on the catalytic activity and the deactivation
behaviour, that the material with the best characteristics for the
pyrolysis of VGOPE blends in a FCC conventional process was AlMCM-41, because it presents high catalytic activity, low tendency to
the formation of coke deposits and low temperature of regeneration by oxidation of the coke. Moreover, the results indicated that
the thermal and the catalytic pyrolysis of VGOPE blends goes
through two decomposition steps, the rst related to the degradation of the VGO fraction and the second related to the decomposition of PE fraction. Both degradation steps seem to be affected
by the presence of the catalyst, being displaced towards lower
temperatures, and the effect of the catalyst is more noticeable for
the decomposition of the PE fraction than for the degradation of the
VGO fraction.
In this work, dynamic pyrolysis of different samples of vacuum
gas oil (VGO), polyethylene (PE) and vacuum gas oilpolyethylene
blend with 10% PE (VGOPE) has been performed in a vertical
reactor in order to study the thermal and the catalytic pyrolysis
using an equilibrium FCC catalyst. In contrast to most studies of the
composition of the products evolved in the pyrolysis process, which
analyze the overall gaseous or liquid product collected through the
complete degradation of a given polymer [1820], in this case, the
evolution with the temperature (or the time) of the composition of
the gases evolved has been studied by GC/MS. The results obtained
permit the nature of the processes involved in each step of
decomposition to be better understood and to analyze the possibility of recycling plastics by mixing them with the vacuum gas oil
in reneries.
2. Experimental
2.1. Materials
A low density polyethylene (LDPE) (200500 mm particle size)
supplied by Dow Chemicals, with a density of 0.918 g/cm3 (ASTM D
792) and melt ow index of 7.7 g/min (ISO 1133) was used. The
vacuum gas oil (VGO) and the commercial equilibrium FCC catalyst
were supplied by Repsol YPF (Spain). The VGO has a boiling range of
240560  C and a density of 0.920 g/cm3.
An FCC catalyst was characterized by X-ray uorescence (XRF),
N2 adsorption isotherms at 77 K, and temperature-programmed
desorption (TPD) of ammonia, using the equipment and experimental conditions described elsewhere [21]. Table 1 shows the
physicochemical and structural characteristics of the equilibrium
FCC catalyst.
The VGOPE blend was prepared using a Jankel and Kunkel
IKAVISC MR-F12 mixer by continuously stirring mixtures of the
base components (LDPE and VGO) with a weight fraction of 10% of
the polymer for 120 min, at 60 rpm and120  C. This temperature

Table 1
Characteristics of the catalyst
Property

FCC
2

BET area (m /g) 1

External surface area (m2/g)a2
Pore volume (cm3/g)a3
Si/Al ratiob
Acidity/weak acid (mmol/g)c
Acidity/strong acid (mmol/g)c
Total acidity (mmol/g)c
T desorption NH3 ( C)c
a
b
c

268
77
0.18
0.97
0.13
0.06
0.19
156632

N2 adsorption isotherms: 1BET method; 2t-method; 3measured at P/P0 0.995.

XRF.
TPD of NH3.

was selected for the sample preparation because at 120  C the LDPE
is completely melted, thus permitting a good mixing degree with
the VGO.
2.2. Experimental equipment
Thermogravimetric experiments were performed in a Netzsch
TG 209 thermobalance. The sample temperature was measured
with a thermocouple directly at the crucible, i.e., very close to the
sample. A temperature calibration procedure was performed, in
accordance with the equipment recommendations, and the
different samples were pyrolyzed in dynamic conditions from 30 to
550  C at 5  C/min under a nitrogen ow of 30 mL/min (STP).
A vertical batch reactor was used for the pyrolysis in order to
analyze the evolution of the composition of gases and condensed
products evolved. This disposition, as well as the carrier gas inlet
from the bottom of the reactor, facilitates the generated gas outlet
to the top. The reactor outlet was heated at 300  C to prevent
condensation of the less volatile compounds. The reactor was
heated by an electric furnace, which was connected to a programmable temperature controller. The sample was placed in a crucible
which was leaned against a rod in the middle of the reactor. A
thermocouple in direct contact with the sample was used in order
to monitor the actual temperature of the process (Fig. 1). In the
catalytic experiments, the ratio of catalyst:sample was 7:1, and
sample amounts of around 300 mg (VGO, PE or VGOPE) were
used. Prior to the experiment, the system was purged with
a nitrogen stream at room temperature for 30 min to ensure an
inert atmosphere. The nitrogen ow rate used was 150 mL/min
(STP). Experiments were carried out from 30 to 550  C at 5  C/min.
In each experiment, the non-condensed products (gas fraction)
and the condensed products (liquid fraction) were collected at
intervals of 50  C. The successive gas fractions evolved from the
reactor were collected every 10 min in different Tedlar bags of 2 L
capacity, and their composition was analyzed by gas chromatography in a gas chromatograph coupled to a mass spectrometer (GC/
MS) (Agilent 6890 N GC-MD 5973N), using a GS-GasPro column
(30 m  0.32 mm I.D.). The column program was: injector temperature, 200  C; initial column temperature, 35  C; initial time, 5 min;
heating rate, 5  C/min; nal temperature, 170  C; nal time,
20 min; run time, 52 min; carrier gas, He.
Glass traps with stainless steel Dixon rings were used to collect
the liquid fractions using a water/ice bath. The evolution of the
composition of the liquid fractions has not been studied in this
work.
2.3. Product analysis
The volatile compounds were analyzed by GC/MS in the
conditions specied in the previous section, and the compounds
generated were identied using the library Wiley 275, that comes
with the analysis program. Moreover, standard gaseous hydrocarbons (from Scott Speciality Gases) were used to identify and
quantify the volatile compounds.
3. Results and discussion
3.1. Study of the pyrolysis by TGA
In order to program suitably the sampling process in the vertical
reactor during the process of decomposition of the different
samples, thermogravimetric experiments were carried out at the
same heating rate as that selected for the experiments in the
reactor (5  C/min).
Fig. 2 shows the weight loss curves (TGA) and their derivatives
(DTG) obtained in the thermal decomposition of the VGO, PE and

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A. Marcilla et al. / Polymer Degradation and Stability xxx (2008) 110

Fig. 1. Diagram of the xed reactor system.

VGOPE samples. The thermal and catalytic pyrolysis of PE has

been widely studied [2123] and occurs in a single stage of
decomposition. In accordance with Fig. 2b, at the heating rate used
in this work, the degradation of pure PE shows a single decomposition step, which occurs in a relatively narrow interval (375
488  C), showing the temperature of maximum decomposition rate
at 463  C. Therefore, the interval of temperature selected for the
study of the degradation of PE was 350550  C.
In the case of the vacuum gas oil, the decomposition and/or
evaporation of the sample occurs in the range of 150350  C, and
goes through two decomposition steps, one at 243  C, a value that is

100
90
80
70

%w

60
50
40
30

VGO
VGO-PE10
PE

20
10
0

25

125

225

325

425

525

T (C)

3
VGO
VGO-PE10
PE

2,5

DTG

near to the initial boiling point of this VGO, and a shoulder that
appears at around 280  C. This shoulder was not observed in
previous work, where the heating rate used was 10  C/min [17].
Actually, the separation among the different stages of decomposition
of a complex process is improved as the heating rate decreases. In
accordance with these results, the interval of temperature selected
for the study of the decomposition of the VGO was 100550  C.
In the case of the VGOPE blend, two decomposition steps
appear. According to Fig. 2b, the comparison with the DTG curves
corresponding to the cases of PE and VGO clearly indicates that the
rst stage is associated with the decomposition or evaporation of
the vacuum gas oil, whereas the second one is related to the PE
decomposition. Moreover, both stages seem to proceed independently, despite the fact that both steps occur at high temperatures
as in the case of the pure samples, i.e. 290 and 465  C, respectively
(see Table 2). The differences between the behaviour observed for
the pure samples (i.e., PE and VGO) and the mixtures have been
discussed elsewhere [17]. According to these results, the interval of
temperatures selected to collect the gas samples in the case of
VGOPE was 100550  C.
Fig. 3 shows the normalized weight loss curves (NTGA) and their
corresponding normalized derivatives (DNTG) for the catalytic
pyrolysis in the presence of the equilibrium FCC catalyst, with
a ratio of catalyst:sample of 7:1. The NTGA curves show the
representation of (w  wc)/(w0  wc) versus the temperature,
where w weight of sample at time t, w0 weight of sample at
t 0, and wc weight of catalyst, obtained in the thermobalance as
the weight of the residue at the nal temperature. The assignment
of the different reaction steps was studied elsewhere [17], and as

Table 2
Temperature of maximum decomposition rate for each reaction step of the thermal
and catalytic pyrolysis of VGOPE mixtures

1,5

Sample

1
Thermal pyrolysis
VGOPE
PE
VGO

0,5
0

25

125

225

325

425

525

T (C)
Fig. 2. (a) TGA and (b) DTG curves obtained for the thermal pyrolysis of VGO, PE and
VGOPE blend.

Catalytic pyrolysis
VGOPE
PE
VGO

T ( C)
VGO peak

PE peak

290

465
463

243

215

407
395

215

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9,E+06

100

8,E+06

DNTG

90
80

7,E+06

70

6,E+06

60

5,E+06

50

4,E+06

40
VGO
VGO-PE 10%
PE

20
10
0

500-550 C

3,E+06

30

25

125

450-500 C

2,E+06

400-450 C

1,E+06
225

325

425

525

0,E+00

350-400 C
0

10

20

T (C)

DNTG

Fig. 4. Chromatograms corresponding to the gases obtained at each interval of

temperature in the thermal pyrolysis of PE.

VGO
VGO-PE 10%
PE

1,2

indicating, in good agreement with previous work [17], the existence of some catalytic effect of the equilibrium FCC catalyst. In
accordance with the previous statements, the interval of temperatures selected for collecting the product samples is 50500  C in
the case of VGO and VGOPE blend, and 300500  C for the case of
PE. Table 2 shows the temperature of maximum reaction rate for
the different systems studied (i.e., the temperatures of the DTG and
NDTG peaks).

1
0,8
0,6
0,4
0,2
0

25

125

40

t (min)

1,6
1,4

30

225

325

425

525

T(C)
Fig. 3. (a) NTGA and (b) DNTG curves obtained for the catalytic pyrolysis of VGO, PE
and VGOPE blend.

can be seen, in the case of the VGO sample, two decomposition

steps appear, the rst being related to the loss of the water adsorbed over the catalyst, that, considering the high proportion of
catalyst used, represents a considerable percentage of the mixture.
The second step is related to the decomposition or evaporation of
the VGO. In the case of the PE sample, Fig. 3b indicates two
decomposition steps, the rst related to the loss of the adsorbed
water in the equilibrium FCC catalyst, and the second due to the
degradation of PE, that occurs in a narrow interval. Finally, in the
case of the VGOPE blend, three decomposition peaks in the DNTG
curve are observed. As in the previous cases, the rst peak has been
associated with the elimination of the adsorbed water contained in
the catalyst. The second step has been related to the decomposition
of the VGO fraction and the third step has been related to the
degradation of the PE fraction. As can be seen, in the VGOPE blend
decomposition, the temperature of the maximum reaction rate
associated with the VGO loss occurs at around 215  C, slightly lower
than the value observed in the absence of catalyst (see Table 2), and

Table 3
Yield of fraction distribution in thermal and catalytic pyrolysis (wt%)
VGO

PE

VGOPE 10%

Thermal pyrolysis
Gases
Condensables

0.0
98.0

18.7
80.6

3.0
97.2

Catalytic pyrolysis
Gases
Condensables
Cokea

41.4
66.4
5.6

71.9
31.7
4.9

34.9
65.1
5.8

a
Coke calculated with the TGA curves obtained in oxidation experiments at 10  C/
min.

3.2. Study of the effect of temperature in the composition of the

gases evolved in the degradation of VGOPE
The study of the effect of temperature in the composition of the
gases evolved in the thermal and catalytic pyrolysis of the VGO, PE,
and VGOPE samples was performed collecting the gases evolved
in intervals of 50  C, in the experiments carried out in the reactor,
and in the range of temperature selected according to the considerations pointed out in the previous section.
3.2.1. Thermal pyrolysis
The thermal pyrolysis of the VGO does not yield any gaseous
product, thus indicating that during the heating process, the VGO

Table 4
Composition of the non-condensed products (mg compound/g sample pyrolyzed) at
each interval of temperature in the thermal pyrolysis of the different samples
studied
NC

T ( C)
PE
350400

VGOPE 10%
400450

450500

500550

400450

450500

500550

Alkanes
C2 0.02
C3 0.04
C4 0.06
C5 0.03
C6 0.00
C7 0.04
C8 0.00
C9 0.00

0.16
0.44
0.61
0.37
0.25
0.44
0.11
0.00

1.96
3.62
3.89
3.33
3.06
3.04
1.02
0.18

0.54
0.43
0.30
0.34
0.40
0.48
0.54
0.13

0.08
0.12
0.13
0.13
0.19
0.11
0.00
0.00

0.36
0.48
0.53
0.34
0.34
0.37
0.09
0.00

0.05
0.02
0.02
0.00
0.00
0.02
0.20
0.00

Alkenes
C2 0.00
C3 0.04
C4 0.20
C5 0.08
C6 0.19
C7 0.00
C8 0.14
C9 0.00

0.14
0.72
2.05
1.22
1.89
0.99
0.67
0.00

4.83
15.71
20.38
21.59
31.93
15.69
4.27
0.55

2.35
4.67
4.92
6.57
9.75
6.32
2.45
0.78

0.08
0.33
0.42
0.22
0.43
0.00
0.00
0.00

1.08
2.58
3.49
3.17
3.93
1.73
0.87
0.00

0.25
0.41
0.36
0.38
0.67
0.33
0.00
0.00

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0,8
0,6

50

0,4
0,2

47
5

42
5

37
5

32
5

12
Alkanes PE
Alkenes PE
Aromatics PE

350
300

10
8

250
200

150

100

50

C
5

47

5
42

37

32

27

5
22

C
5

75

T (C)
140

100

6
5

5
47

5
42

5
37

5
32

5
27

75

20

40

60

80

Alkenes, Aromatics
mg comp/ g sample

Alkanes VGO-PE
Aromatics VGO-PE
Alkenes VGO-PE

120

22

27
5

400

Alkanes mg comp/ g sample

T (C)

Alkenes, Aromatics
mg comp/ g sample

was not degraded, but a process similar to fractional distillation

occurs. Therefore, the composition of the condensed product
obtained at the exit of the reactor must be equal to that corresponding to the original VGO, which is mainly evaporated as the
temperature increases, condensing in the cold trap placed at the
exit of the reactor. Table 3 shows the mass balance obtained for
the different cases studied in this work. As can be seen, in the case
of the thermal decomposition of VGO, 98.0% of liquids were
collected, and in the cases of the thermal decomposition of the PE
and the blend, the sum of gases and condensable products is very
close to the expected value of 100%.
In contrast to the case of the VGO, the thermal pyrolysis of PE
yields a gaseous fraction and a liquid fraction (see Table 3). Fig. 4
shows the chromatograms corresponding to the different samples
of the gases collected in the range of temperatures studied. As can
be seen, the chromatograms are very similar, and the main differences can be found in the relative abundance of each compound.
Table 4 shows the composition obtained at each temperature. The
different compounds have been grouped as alkanes or alkenes
(aromatics have not been detected) and by the number of carbon
atoms. Fig. 5a shows the evolution with the temperature of the
composition of the gases obtained in the thermal pyrolysis of PE. As
can be seen, the main generation of products has been obtained in
the 450500  C range. This result is in good agreement with the
data reported in Table 2. In all the studied intervals, alkenes are
the more abundant compounds. Moreover, in good agreement with
the literature [24], higher selectivity towards n-alkenes has been
observed. As Table 4 and Fig. 6 reect, the evolution of the yield of
alkenes with the temperature, indicates that at the lower

Alkanes mg comp/ g sample

Fig. 5. Changes with the temperature of the composition of alkanes and alkenes in the
gases obtained in the thermal pyrolysis of PE.

22
5

75

T (C)

52
5

47
5

42
5

37
5

32
5

27
5

22
5

17
5

12
5

0
C

0
C

20

1,4

100

40

17
5

1,6
1,2

17

60

1,8

150

17

200

80

2
Alkanes VGO
Alkenes VGO
Aromatics VGO

10

100

250

12
5

12

120

12

14

140

Alkenes, Aromatics
mg comp/ g sample

Alkanes VGO-PE
Alkenes VGO-PE
Alkanes PE
Alkenes PE

12

16

PE mg comp/ g pol

VGO-PE mg comp/ g pol

18

Alkanes mg comp/ g sample

A. Marcilla et al. / Polymer Degradation and Stability xxx (2008) 110

T (C)
Fig. 7. Changes with the temperature of the composition of alkanes and alkenes in the
gas generated in the catalytic pyrolysis of (a) VGO, (b) PE and (c) VGOPE.

mg comp/ g sample

35
C2
C3
C4
C5
C6
C7
C8
C9

30
25
20
15
10
5

C
5
52

C
5
47

C
5
42

C
37

C
5
32

C
5
27

C
5
22

C
5
17

12

T (C)
Fig. 6. Changes with the temperature in the composition of alkenes in the noncondensed products in the gases obtained in the thermal pyrolysis of PE (the
temperature axis indicates the middle of each interval).

temperatures (350450  C), the major compounds generated are

C4 and C6, being slightly higher the C4 yield (Table 4). Nevertheless
at higher temperatures (450550  C), although C4 compounds
continue to be abundant, the tendency changes, and C6 compounds
predominate and 1-hexene is the major compound generated in
the main interval of degradation. Moreover, a noticeable increase of
C5 alkenes can be also observed.
As indicated in the previous section, the pyrolysis of the VGOPE
blend shows two decomposition steps. The rst is associated with
the evaporation of the VGO and the second with the degradation of
the PE. The study of the evolution of the non-condensed products
indicates that, unlike the case of the pure VGO, gaseous compounds
were generated, but only in the range of temperatures corresponding to the PE decomposition. As in the case of PE, the range of
temperature showing the main generation of non-condensed
products is the 450500  C interval, where n-alkenes are the more

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abundant compounds (Table 4). These results indicate, as suggested

elsewhere [17] and in Section 3.1, that PE and VGO evolve in
practically independent steps. The chromatograms corresponding
to the gas fraction obtained in the four intervals where the generation of non-condensed products has been observed are very
similar to those shown in Fig. 4, and the change of the composition
of this fraction (Fig. 5b) is also very similar to that corresponding to
the pure PE (see Fig. 5a), where 1-hexene is also the major
compound in the range of temperatures corresponding to the
maximum decomposition rate. As can be expected, the yield of
gases is noticeably lower than in the case of pure PE, thus reecting
the fact that the sample only contains 10% PE.
3.2.2. Catalytic pyrolysis
In agreement with the literature [25], the yield of noncondensed products obtained in the pyrolysis carried out in the
presence of the catalyst increases noticeably with respect to the
thermal pyrolysis case (Table 3). Fig. 7a shows the evolution of
the gases generated during the catalytic decomposition of the
VGO sample. As it can be seen, unlike the thermal process, non-condensed products have been generated along the different
intervals of temperature considered (200500  C), where the
maximum yield is in the 250300  C interval. This behaviour
indicates that the catalyst interacts to some extent with the VGO
fraction, causing the degradation of a part of this fraction and the
corresponding generation of volatile compounds, despite the fact
that some delay of temperature (or time) with respect to the values
of maximum reaction rate observed in the TGA experiments can be
noted, related to the residence time of the products evolved in the
reaction system.
This catalytic activity in such a system is also reected in the
DNTG curves of Figs. 2 and 3, and in Table 2, which shows
a decrease of the temperature of maximum decomposition rate of
the VGO, as a consequence of the presence of the equilibrium FCC
catalyst. The generation of volatile products at temperatures higher
than that observed in TGA curves of Fig. 3 can be explained by the
delay between the time when the gases were produced and the

time where they were collected, but is also due to secondary

reactions undergone by the pyrolysis products inside the reactor,
favoured by the high temperature and the high time of residence of
these products inside the reactor.
Tables 5 and 6 show the composition of the non-condensed
fraction obtained in the catalytic pyrolysis of the different samples
studied in this work, and the evolution with the temperature of
alkanes and alkenes in the case of VGO is shown in Fig. 8. As can be
seen in Fig. 8a, for the VGO samples, the rst interval showing
generation of non-condensed compounds is between 200 and
250  C, where alkanes with seven carbon atoms are the favoured
compounds. The major compound of the C7 alkanes group was
iso-heptane. Nevertheless, as the temperature increases, the
selectivity changes towards compounds with a lower number of
carbon atoms. In this way, in the 250300  C interval, corresponding to the maximum non-condensed product generation,
the more abundant are C6 alkanes, although the major compound
collected in this interval is iso-pentane. In the 300450  C interval,
the favoured compounds are alkanes with four carbon atoms, isobutane being the major compound. Finally, at higher temperatures
(400450  C), the formation of C3 alkanes is favoured, iso-propane
being the major compound. According to Table 6 and Fig. 8b, in the
case of alkenes, the formation of C5 was favoured at low
temperatures (200250  C), 1-pentene being the major component of this group, whereas as the temperature increases (250
400  C), the selectivity changes towards C3 alkenes (i.e., propene).
Finally at higher temperatures (450500  C) ethylene is the
favoured alkene. With respect to the generation of aromatic
compounds, at low temperatures (200300  C) benzene is favoured, whereas at high temperatures (300500  C) toluene is
favoured.
Fig. 9a shows the evolution with the temperature of the yield of
alkanes, alkenes and aromatics in the non-condensed products
obtained in the catalytic pyrolysis of PE. As can be seen, alkanes are
the major compounds obtained in all the intervals of temperature
studied. This behaviour is similar to that observed in the decomposition of PE in the presence of FCC catalysts in a xed bed reactor,

Table 5
Composition (mg compound/g sample pyrolyzed) of alkanes present in the non-condensed products at each interval of temperature in the catalytic pyrolysis of the different
samples studied
T ( C)

Alkanes

NC

100150

150200

200250

250300

300350

350400

VGO

C2
C3
C4
C5
C6
C7
C8
C9

0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00

0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00

0.00
0.35
7.44
9.16
10.58
11.61
5.57
0.67

0.00
4.42
37.28
42.22
43.99
41.44
25.20
4.95

0.03
5.42
20.03
17.13
14.95
13.23
7.21
1.31

0.21
5.07
13.63
10.31
7.22
5.47
3.59
1.29

0.76
4.09
7.34
3.35
1.46
1.49
1.22
0.73

1.10
1.85
1.55
0.12
0.68
1.31
1.35
0.49

PE

C2
C3
C4
C5
C6
C7
C8
C9

0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00

0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00

0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00

0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00

0.02
4.29
32.04
19.61
8.41
1.25
0.00
0.00

0.24
11.18
72.14
44.89
19.41
3.31
0.17
0.00

2.82
30.46
156.48
110.93
52.05
10.65
1.31
0.00

0.32
0.48
0.82
0.59
0.40
0.19
0.02
0.00

VGOPE

C2
C3
C4
C5
C6
C7
C8
C9

0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00

0.00
0.00
0.03
0.00
0.02
0.00
0.00
0.00

0.00
0.34
4.46
0.46
5.90
6.13
3.76
0.85

0.00
2.97
22.77
25.03
24.87
23.20
14.57
3.48

0.08
5.29
21.11
17.98
15.00
10.64
4.87
0.01

0.22
5.10
17.26
12.59
8.02
4.55
1.67
1.16

0.72
5.20
14.02
7.90
3.61
1.70
0.89
4.06

1.12
2.11
2.36
0.91
0.74
0.95
0.81
0.67

400450

450500

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Table 6
Composition (mg compound/g sample pyrolyzed) of alkenes and aromatics present in the non-condensed products at each interval of temperature in the catalytic pyrolysis of
the different samples studied
Alkenes

T ( C)

NC

100150

150200

200250

250300

300350

350400

VGO

C2
C3
C4
C5

0.00
0.00
0.00
0.00

0.00
0.00
0.00
0.00

0.00
0.11
0.00
0.39

0.09
0.51
0.00
0.00

0.26
0.60
0.00
0.00

0.81
0.98
0.00
0.00

400450
1.19
0.51
0.05
0.00

0.71
0.35
0.50
0.00

450500

PE

C2
C3
C4
C5

0.00
0.00
0.00
0.00

0.00
0.00
0.00
0.00

0.00
0.00
0.00
0.00

0.00
0.00
0.00
0.00

0.23
1.08
0.69
0.00

1.16
6.00
7.58
1.78

6.81
22.38
12.88
9.85

0.30
0.23
0.07
0.00

VGOPE

C2
C3
C4
C5

0.00
0.00
0.00
0.00

0.00
0.00
0.00
0.00

0.00
0.08
0.00
0.00

0.08
0.39
0.00
0.00

0.36
0.90
0.00
0.00

1.10
1.84
2.07
0.00

1.63
2.44
2.04
0.37

1.08
0.71
0.34
0.10

VGO

C6
C7

0.00
0.00

0.00
0.00

0.21
0.10

0.56
0.14

0.30
0.69

0.33
1.06

0.40
1.46

0.28
0.71

PE

C6
C7

0.00
0.00

0.00
0.00

0.00
0.00

0.00
0.00

0.00
0.00

0.02
0.08

0.22
0.95

0.02
0.04

VGOPE

C6
C7

0.00
0.00

0.00
0.00

0.02
0.03

0.04
0.06

0.08
0.32

0.16
0.68

0.16
0.72

0.14
0.37

Aromatics

where mainly iso-alkanes, were obtained, whereas the formation of

n-alkenes in the thermal process is favoured [26]. This behaviour
can be related to the different mechanisms of reaction of the
thermal and catalytic pyrolysis (i.e., a free-radical mechanism in
50
45
40
35
30
25
20
15
10
5
0

C
47
5

C
5
42

C
37
5

32
5

5
27

5
22

5
17

5
12

75

mg comp/ g sample

C2
C3
C4
C5
C6
C7
C8
C9

mg comp/ g sample

T (C)
1,4
C2
C3
C4
C5

1,2
1
0,8
0,6
0,4
0,2

C
5
47

C
5
42

C
5
37

C
32

C
5
27

C
5
22

C
5
17

C
5
12

75

T (C)
Fig. 8. Changes with the temperature of (a) alkanes and (b) alkenes in the noncondensed products obtained in the catalytic pyrolysis of VGO (the temperature axis
indicates the middle of each interval).

the case of the thermal pyrolysis and a mechanism based on the

formation of carbonium ions on the catalyst surface in the case of
catalytic pyrolysis, where bond scissions, isomerisation and
hydrogen exchange reactions occur which favour the formation of
iso-compounds) [13].
As seen in Fig. 9b, the interval of maximum generation of
non-condensed products in the catalytic degradation of PE is 400
450  C. Catalytic pyrolysis yields a narrower distribution of products, due to the molecular sieve character of the catalyst [7].
According to Table 5 and Fig. 9, in all the intervals of temperature
studied the formation of C4 alkanes is favoured, and iso-butane is
the major compound in all the cases. In the case of the formation of
alkenes (Table 6), in the 350400  C interval the formation of C4 is
favoured, although the major component is propene. At higher
temperatures, the selectivity of alkenes changes towards C3, and
propene is also the major compound. Finally, in the 450500  C
range, the formation of ethene was favoured. The formation of
aromatics starts in the range of 300350  C, and the maximum
of aromatics appears at 400450  C, where toluene is the major
aromatic.
Once the evolution with the temperature of the composition of
the non-condensed products obtained in the thermal pyrolysis of
VGO, PE and VGOPE blend, and in the catalytic pyrolysis of pure
VGO and PE has been studied, the case of the catalytic pyrolysis of
the VGOPE blend, which is the main objective of this work, must
be considered, and compared with the previous results. In accordance with Fig. 3, in this case, two decomposition stages occur,
corresponding to the VGO and PE decomposition, respectively. In
agreement with the composition of the blend, the highest yield
must correspond to the rst decomposition step, i.e., to the VGO
evolution. Fig. 7c shows the yields obtained in this case. The
comparison with the results shown in Fig. 7a reects a higher
generation of products in the range of higher temperatures than in
the case of pure VGO, whereas the comparison with the results
shown in Fig. 7b indicates a higher generation of products in the
range of lower temperatures than in the case of pure PE. However,
despite some deviation, that can be observed related with the
overlapping of the processes, the composition of the gases obtained

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A. Marcilla et al. / Polymer Degradation and Stability xxx (2008) 110

180
160

C2
C3
C4
C5
C6
C7
C8

140
120
100
80
60

mg comp/ g sample

40
20

20
15
10
5

mg comp/ g sample

C2
C3
C4
C5
C6

15
10
5

C
47
5

C
42
5

C
37
5

C
32
5

C
27
5

C
22
5

17
5

12
5

25
20

75

C
47
5

C
42
5

C
37
5

32
5

27
5

22
5

C
17
5

C
12
5

C
75

T (C)

T (C)
3
C2
C3
C4
C5

2,5
2
1,5
1
0,5

Fig. 9. Changes with the temperature of (a) alkanes and (b) alkenes in the noncondensed products obtained in the catalytic pyrolysis of PE (the temperature axis
indicates the middle of each interval).

in each interval of temperature seems to be related to a linear

combination of the composition of the gases corresponding to pure
VGO and PE, according to their corresponding mass fraction.
Therefore, the results obtained suggest that both decomposition
steps occur in an independent way.
According to Table 5 and Fig. 10, at low temperatures (200
250  C) the more abundant alkanes are the C7s, as in the catalytic
decomposition of the VGO, whereas when the temperature
increases, the formation of C4 alkanes is favoured, iso-butane
being the major compound. Moreover, the amount of alkanes of
four carbon atoms generated between 150 and 500  C is higher
than in the case of VGO. This clear increase can be related to the
fact that, in this interval of temperature, the decomposition of PE
also occurs, favouring the formation of iso-butane in all the ranges
of temperature. The evolution of alkenes and aromatic compounds
(Table 6 and Fig. 10) generated in the degradation of the VGOPE
blend shows that in the interval of 200350  C, where the
decomposition of VGO occurs, the alkene favoured is propene,
whereas in the interval where the decomposition of PE occurs
(350500  C), the major compounds are C3 alkenes (propene),
although an important growth of C4 compounds has also been
observed, clearly due to the catalytic pyrolysis of PE. Finally,
toluene is the major aromatic compound in the whole interval of
decomposition.

3.3. Comparison of the non-condensed products generated during

the main interval of decomposition
Table 7 shows the composition of the non-condensed products
generated in the main interval of decomposition of the different

C
5
47

C
5
42

C
5

5
32

37

C
5
27

C
5
22

C
5
17

C
C
5
47

C
5
42

C
5

5
32

37

C
5
27

C
5
22

C
5
17

C
5
12

C
75

T (C)

75

mg comp / g sample

C2
C3
C4
C5
C6
C7
C8
C9

25

30

12

mg comp / g sample

T (C)
Fig. 10. Changes with the temperature of (a) alkanes and (b) alkenes in the noncondensed products obtained in the catalytic pyrolysis of VGOPE (the temperature
axis indicates the middle of each interval).

systems studied in this work: 450500  C for the thermal decomposition of PE and for the VGOPE blend, 250300  C for the
catalytic degradation of the pure VGO and for the rst step of the
catalytic decomposition of the VGOPE blend, and 400450  C for
the catalytic degradation of the pure PE and the second decomposition step of the VGOPE blend.
As can be seen and in good agreement with the results discussed
in the previous sections, in the thermal decomposition of PE, the
more abundant compounds are the n-alkenes. The major
compound is 1-hexene (14.58%), followed by propene (11.63%). 1butene and 1-pentene are in very similar proportions (10.54% and
10.20%, respectively). The VGOPE blend, only yields noncondensed products in the range of decomposition corresponding
to PE, and these products show a very similar distribution to that
corresponding to the case of pure PE: the major compound is 1hexene (14.68%) followed by propene (13.33%), and 1-butene and
1-pentene (11.46%, and 10.07%, respectively). As was indicated in
Section 3.2, this reveals that the behaviour of the decomposition of
the VGO and PE fractions in the blend is independent, and the noncondensed products obtained in the thermal pyrolysis have their
origin in the PE fraction pyrolysis.
The non-condensed products obtained in the catalytic pyrolysis
of the different samples (Table 7), show a change of selectivity
towards iso-alkanes. In the case of VGO, the major compound is isopentane (19.9%) followed by iso-butane (15.48%), and iso-hexane,
and iso-heptane (10.91% and 7.23%, respectively). The comparison
of these results with that corresponding to the decomposition of
the VGOPE blend in the range 250300  C (i.e., decomposition of
the VGO fraction) reects a very similar composition. On the other
hand, the catalytic decomposition of PE also yields iso-alkanes as
the major compounds, whereas, in this case, iso-butane is the main

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Table 7
Composition (mass percentage) of the non-condensed products generated in the main interval of decomposition of the different systems studied
Thermal

Ethane
Ethene
Propane
Propene
Iso-butane
Butane
1-Butene
1.3-Butadiene
Trans-2-butene
2-Methyl-propene
Iso-butene
Iso-pentane
Pentane
1-Penteno
Trans-2-pentene
Iso-hexane
Iso-pentene
1,3-Pentadiene
Hexane
1,3-Cyclopentadiene
1-Hexene
Iso-heptane
Heptane
1-Heptene
Octane
1-Octene
Nonane
1-Nonene
Benzene
Toluene
Remaining products

Catalytic

PE, 450500  C

VGOPE, 450500  C

VGO, 250300  C

PE, 400450  C

VGOPE, 250300  C

VGOPE, 400450  C

1.45
3.58
2.68
11.63
0.03
2.85
10.54
0.07
3.41
0.00
1.14
0.00
2.39
10.20
0.95
0.12
2.18
0.35
1.69
0.29
14.58
2.27
2.00
6.48
0.75
1.75
0.13
0.40
0.00
0.00
16.08

1.87
5.56
2.45
13.33
0.00
2.72
11.46
0.00
3.84
1.79
0.94
0.00
1.76
10.07
1.60
0.14
2.76
0.00
1.35
0.00
14.68
2.13
1.72
6.64
0.48
2.09
0.00
0.00
0.00
0.00
10.61

0.00
0.04
2.20
0.25
15.48
3.06
0.00
0.00
0.00
0.00
0.00
19.90
1.09
0.00
0.00
10.91
0.00
0.00
0.65
0.00
0.00
7.23
0.31
0.00
4.91
0.00
0.00
0.00
0.00
0.00
33.96

0.67
1.62
7.26
5.33
32.42
4.87
0.71
0.00
0.00
0.00
0.00
24.42
2.01
0.00
0.00
0.00
1.23
0.00
1.02
1.12
0.00
4.32
0.29
0.00
0.31
0.00
0.00
0.00
0.05
0.23
12.13

0.00
0.06
2.51
0.33
16.07
3.24
0.00
0.00
0.00
0.00
0.00
19.83
1.12
0.00
0.00
10.20
0.00
0.00
0.61
0.00
0.00
12.65
0.33
0.00
4.55
0.00
0.00
0.00
0.03
0.05
28.41

1.57
3.55
11.36
5.32
24.86
5.77
0.44
0.00
2.45
0.00
1.57
15.20
2.06
0.00
0.00
2.55
0.80
0.00
0.77
0.00
0.00
2.02
0.26
0.00
0.90
0.00
0.00
0.00
0.34
1.57
16.63

component of the mixture (32.42%) followed by iso-pentane

(24.42%), and in a lesser proportion appears propane at around
4.5%, and butane (at around 4.5%). The comparison with the
composition of the products obtained in the range of temperatures
where the pyrolysis of the PE fraction of the VGOPE blend occurs,
also shows a very similar behaviour (24.86% of iso-butane and
15.20% of iso-pentane), despite some differences related to the
overlapping with the products evolved in the VGO fraction pyrolysis and to the possibility of some interaction between the two
decomposition steps.
4. Conclusions
The results obtained in this work indicate that in the thermal
pyrolysis, VGO is not degraded, and only a fractional distillation
occurs. Nevertheless, during the thermal decomposition of polyethylene, gases are generated in the whole interval of temperature
studied, where n-alkenes are favoured. In the thermal decomposition of the VGOPE blend, non-condensed products were only
collected in the interval of decomposition associated with the
degradation of the PE, where n-alkenes were also the major
compounds.
The catalytic decomposition of the VGO yields non-condensed
products in the range of 200500  C, with a maximum in the 250
300  C range. This fact reveals the existence of some catalytic
activity of the FCC catalyst on the VGO decomposition. In this case,
the compounds favoured in the overall range of temperature are
the iso-alkanes. The catalytic pyrolysis of the PE reects a higher
yield of gases than in the thermal process, changing the selectivity
from n-alkenes towards iso-alkanes. Finally, the catalytic pyrolysis
of the VGOPE blend shows generation of non-condensed products
in the 150500  C range, where 250300  C is the main interval of
decomposition. As in the previous cases, selectivity exists towards

iso-alkanes. The behaviour of the VGOPE blend suggests that the

two processes involved in the catalytic pyrolysis process occur
mainly in independent ways.
The study of the composition of non-condensable products
obtained in the main interval of decomposition of the different
systems shows, that during the thermal decomposition of PE
the major non-condensed compound is 1-hexene, whereas in the
catalytic decomposition it is iso-butane. In case of the VGO, the
major non-condensed compound observed in the catalytic pyrolysis is iso-pentane. Finally, the behaviour of the blend indicates that
in the interval of temperature associated with the decomposition of
the VGO the major compound is iso-pentane, whereas in the
interval associated with the decomposition of PE, it is iso-butane.
Therefore, despite the fact that some interaction between both
reactions steps could be considered, the catalytic decomposition of
the VGO and PE fractions also seems to occur through independent
processes.
As a conclusion, the results obtained in this work indicate the
ability of the treatment of the VGOPE blends in a conventional FCC
process as an alternative way of plastic recycling, since the presence
of polyethylene does not signicantly affect the composition of the
gases with respect to the VGO, adding an additional decomposition
step at higher temperatures. Moreover, its presence favours the
formation of iso-butane, propane, and butane, which form part of
liqueed petroleum gas (LP).
Acknowledgement
Financial support for this investigation has been provided by the
Spanish Comision de Investigacion Cientca y Tecnologica de la
Secretara de Estado de Educacion, Universidades, Investigacion y
Desarrollo and the European Community (FEDER refunds) (CICYT
PPQ2004-02187), Generalitat Valenciana (ACOMP06/162 and

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ACOMP/2007/094), and University of de Alicante; Grupo de Procesado y Pirolisis de Polmeros (VIGROB099).

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Please cite this article in press as: Marcilla A et al., Study of the decomposition of low density polyethylene blends with vacuum gas oils:
Evolution of the gases, Polym Degrad Stab (2008), doi:10.1016/j.polymdegradstab.2008.07.019