Thermal Treatment of Catalysts

Modern Methods in Heterogeneous Catalysis Research

Friederike C. Jentoft, October 31, 2003

Outline
1. Terminology (calcination) 2. Sample vs. oven set temperature 3. Self-generated atmosphere & self-steaming of zeolites 4. Combustion 5. Glow phenomenon & zirconia catalysts 6. Crystallization 7. Loss of surface area 8. Effect of additives 9. Solid-solid wetting 10.Reductive treatments & SMSI

Steps of Catalyst Preparation

v IUPAC defines 3 steps of catalyst preparation 1. Preparation of primary solid, associating all the useful compounds 2. Processing of that primary solid to obtain the catalyst precursor for example by heat treatment 3. Activation of the precursor to give the active catalyst (reduction to metal, formation of sulfides, deammoniation of zeolites)

Heat Treatment of Intermediate Solids or Precursors

v drying v thermal decomposition of salts (nitrates, ammonium salts) v calcination v product is a "reasonably inert solid" which can be stored easily

Annealing

v in a general meaning: a heating of a material over a long time span; strain and cracks in a crystalline solid can be removed

Origin of the Term "Calcination"

v latin "calx" = playstone limestone, (greek chlix) v burning of calcium carbonate (limestone) to calcium oxide (quicklime) CaCO3 CaO + CO2 H(900C)=3010 kJ mol-1

v used to construct Giza pyramids (ca. 2800 A.C.), burning of limestone ("Kalkbrennen") mentioned by Cato 184 A.C. v performed in kilns (ovens) at 900C v addition of air to sustain combustion + cool product

Examples for Kilns for Calcination

v Schematic of a vertical shaft kiln. a) Preheating zone; b) Calcining zone; c) Cooling zone

v Schematic of a rotary kiln a) Burner; b) Combustion air; c) Pre-heater; d) Kiln; e) Cooler

General Definition of "Calcination"

v decomposition of a substance through heating, transformation in lime-like substance Duden v to heat (as inorganic materials) to a high temperature but without fusing in order to drive off volatile matter or to effect changes (as oxidation or pulverization) Websters v heating (burning) of solids to a certain degree of decomposition, whereby with e.g. soda, gypsum the crystal water is completely or partially removed Rmpp's Chemielexikon v the heating of a solid to a high temperature, below its melting point, to create a condition of thermal decomposition or phase transition other than melting or fusing Hsing, Synthesis of Inorganic Materials

Definition of "Calcination" in Catalysis Research

v thermal treatment (of a catalyst) in oxidizing atmosphere. The calcination temperature is usually slightly higher than that of the catalyst operating temperature Ullmann's Encyclopedia of Industrial Chemistry v a heat treatment of catalyst precursor in an oxidizing atmosphere for a couple of hours - Catalysis from A to Z, Eds. Cornil et al. v heating in air or oxygen; the term is most likely to be applied to a in the preparation ofto a catalyst - IUPAC v step often, with respect catalysts, an Compendium oxidizing of Chemical Terminology

treatment is meant

v however, you will find statements such as "calcined in inert atmosphere" v sample-generated atmosphere may be oxidative (nitrate decomposition)

Example from Patent Literature

v extremely vague! unimportant? v no, there is a secret to it! v often only temperature + holding time given
E.J. Hollstein, J.T. Wei, C.-Y. Hsu, US Patent 4,918,041

Calcination Procedure: Temperature Program

900 800 Temperature / K 700 600 500 400 300 0 100 200 300 400 500 Time / min

v heating rate, holding time, cooling rate v cooling usually uncontrolled below certain T, slower

Actual Temperature Program

v oven may not be able to perform selected program (lack in power): temperature lag of actual temperature behind set temperature v poorly tuned controller may give temperature oscillations v heat needs to be transferred from oven to sample, needs a gradient: temperature lag of sample temperature vs. oven temperature

Role of Sample

v strongly endo- or exothermic events may interfere with the heating program v endothermic events: solvent evaporation v exothermic events: combustion of organics, crystallization

Evaporation of Water: Thermal Effects

v example: a 10 g sample containing 18 % water (0.1 mol) v Hevap(H2O, 373 K) = 41 kJ mol-1 v to evaporate in 1 minute: 70 Watt

Example: Calcination of Zirconium Hydroxide

700

Sample bed temperature / K

10 K min

-1

600 500 400 300 0.0 0.5 1.0 1.5 Time / h 2.0

3 K min

-1

1 K min

-1

2.5

3.0

v with a 10 g sample, deviations can occur already at moderate heating rates

Evaporation of Water: Gas Formation

v example: a 10 g sample containing 18 % water (0.1 mol) v at 400 K: corresponds to 3.3 l of water vapor v depending on the - form of the bed - the type of furnace (tubular / muffle) - static / dynamic atmosphere (no flow / flow) the sample will be exposed to vapor for minutes!

Zeolite Y as a Cracking Catalyst

v zeolite Y is used as a cracking catalyst (FCC)

Faujasite structure

v first synthesize NaY, then exchange Na+ by NH4+ (liquid phase) v obtain active HY through thermal decomposition of NH4Y v regular HY not very stable

Ultrastable Y zeolite

v McDaniel and Maher 1967 report new ultra-stable form of faujasite v worked with 100 g of zeolite, first exchange then heat treatment
900 800

Temperature / K

700 600 500 400 300 0 100 200 300 400 500 Time / min

v keeping the elapsed time between the exchange step and the heating step at 815C to a minimum is quite critical
C.V. McDaniel, P.K. Maher in Molecular Sieves, Soc. Chem. Ind. London, 1968, p. 186

Ultrastable Y Zeolite

v Kerr 1967: treatment of HY at 700-800C in inert static atmosphere v any technique keeping this water in the system during the heating process will result in a stable product v published comparison of heating in deep bed or shallow bed: deep bed produces stable product v ascribes success of McDaniel & Maher to the large amount that they used

G.T. Kerr, J. Phys. Chem. 1967, 71, 4155 and J. Catal. 1969, 15, 200.

Influence of Packing
MS analysis m/e = 18 (H2O)

v Packing of a solid influences evolution of gas (water vapor)

Evaporation Autogeneous Pressure

5.8 mg H2O, sealed explosion 2.09 mg H2O, 50 m hole in lid onset

6.2 mg H2O no lid

v boiling point of water is determined properly only in crucible with lid + hole in lid!

Stabilization Through Dealumination

v water vapor removes aluminum from zeolite framework (extra-framework aluminum) v leads to stabilization v today, ultrastable Y or USY is obtained through steaming, treatment of NH4-Y 600-800C in rotary kilns v USY is used in fluid catalytic cracking and hydrocracking and hydroprocessing v steaming is a general method for dealumination of zeolites

Exothermic Reactions: Combustion

v organic matter may be present, e.g. from sol-gel process, surfactant-assisted synthesis v will combust upon thermal treatment in oxygencontaining environment v look at thermochemical data
CRC Handbook of Thermophysical and Thermochemical Data Eds. David R. Lide, Henry V. Kehiaian, CRC Press Boca Raton New York 1994 FHI library 50 E 55 D'Ans Lax, Taschenbuch fr Chemiker und Physiker Ed. C. Synowietz, Springer Verlag 1983, FHI library 50 E 54

Example: Pentane Combustion

C5H12 (g) + 8 O2 (g) 5 CO2 (g) + 6 H2O (g)

r H

= i f Hi
i =1

r H = 5 f H CO2 + 6 f H H 2O 1 f H C5 H12
r H = 5 ( 393.51 kJmol 1 ) + 6 ( 241.82 kJmol 1 ) 1 (146.44 kJmol 1 ) r H = 3272.0 kJmol 1

v combustion is strongly exothermic! v oxygenates have higher enthalpies of formation, i.e. enthalpy of combustion becomes smaller

Example: Surfactant-Assisted Synthesis Mesoporous Zirconia

v surfactants (hexadecyl-trimethyl-ammonium bromide) form micelles v inorganic matter forms around micelles

Example: TG/DTA Analysis of ZrO2-Precursor

80

H2O loss
exo

60 50 40

70

TG (mg)

60

endo

30 20 10 0 -10

50

SO42- decomposition
40 200 400 600 800 1000 1200

Temperature (K)

v ZrO2/CTAB composite synthesized with Zr(O-nPr)4 in the presence of sulfate ions at Zr:S:CTAB = 2:2:1, measured with 10 K/min in an air stream

DTA (mV)

combustion of organics

Other Exothermic Reactions

v Example: calcination of X-ray amorphous zirconium hydroxide v "ZrO2 * 2.5 H2O"

Heating of Zirconium Hydroxide

Heating time / min 115 120 125 130 135 140 145 150 155

Sample bed temperature / K

950 900 850 800 750 700 650 600 550 640

17.1 ml boat 8.4 ml boat

2.2 ml 8.4 ml 17.1 ml

2.2 ml boat

660 680 700 720 Oven temperature / K

740

760

v strong influence of batch size / heat transfer v rapid overheating (up to 40-50 K/s) v overshoot of up to 300 K

History of Glow
v Overheating is so violent, it is accompanied by emission of visible light ("glow")
Berzelius 1812 (antimonates, antimonites)

The Glow Phenomenon

Oxides Showing a Glow

Origin of Glow

v combustion of organic contaminants v heat of crystallization v loss of surface energy through sintering

Effect of Combustion?
Heating time /min 165 170 175
Oxygen Argon Air

Sample bed temperature / K

900 880 860 840 820 800 780 760 780

180

790

800 810 820 Oven temperature / K

830

840

v atmosphere little influence on overheating effect v heat not caused by combustion of organic contaminants

Origin of Glow

v combustion of organic contaminants v heat of crystallization v loss of surface energy through formation of larger particles

Heat of Crystallization of ZrO2 (kJ mol-1)

?-ZrO2 any ZrO2 t- or m-ZrO2 t- or m-ZrO2 t-ZrO2 t-ZrO2 t-ZrO2 t-ZrO2 t-ZrO2 m-ZrO2 28.7 23.2 4.3 to 22.5 12.9 29.3 to 33.4 19.6 d n : a 2 30.1 rO 0.8 .3 Z 4 t n e of 53 e n o tw i t e 13 a b iz l l re 58.6 3.3 a u t t rys era Keshavaraja Srinivasan Chuah -1 Tatsumi l o m J Livage k 6 . -53 Mercera Haberko Molodetsky Xie Molodetsky Molodetsky Molodetsky Xie Coughlin

c lit f o o t t in surface a g energy upon a-ZrO2 t-ZrO2 e Change n i h rd o 2 -1 c (assumed ac ABET = 100 m g ): +14.6
Transition t-ZrO2 to m-ZrO2: 5 6 6

Estimation of Temperature Rise through Crystallization

v assume a medium heat of 25 kJ mol-1 v process assumed quasi-adiabatic (Q = 0) v molar heat of precursor / intermediate assumed similar to that of ZrO2: 82.3 J mol-1 K-1
H T = 300 K cp

v corresponds approximately to observation

Does Crystallization Happen During Glow?

v use method that allows structure-determination and good time resolution v X-ray absorption spectroscopy at Zr K edge at ESRF (1 spectrum per s; 10 K min-1 heating rate) v allows observation of local environment around Zr4+ ions

In situ X-ray Absorption Spectroscopy

v use large pellet to create a sufficiently large glow effect v put small pellet inside that is transparent for X-rays

5 mm 5mm

XAS Spectra

Norm. absorption

1.0

0.75

0.5 200 0.25 50 0.0 18 18.25 18.5 18.75 19 150 100

m Ti

e ,s

d on

Photon energy [keV]

Sample Temperature vs. Time

600 550 Temperature, C 500 450 400 350 110 112 114 116 118 120 122 124 126 128 130 Time, seconds

Heating rate 50 K s-1

Structural Evolution

6.0

2) FT( (k)*k

4.0

2.0

547 C 499 C 447 C 439 C 436 C

0 2 4 R [] 6 8

Origin of Glow

v combustion of organic contaminants v heat of crystallization - yes! v loss of surface energy through formation of larger particles

Sintering

v a heat treatment at 2/3 to 3/4 of the melting point to solidify shaped bodies from pressed metal powders, occurs in 3 steps v 1. increase of particle contacts through "sinter bridges" 2. formation of a contiguous backbone, original particles lose their identity, shrinkage, formation of new grain boundaries 3. rounding and elimination of pores, further shrinkage, closed pores

Tammann and Httig Temperature

v Tammann temperature temperature necessary for lattice (bulk) recrystallization for metal oxides TTammann 0.52 TF v Httig temperature temperature necessary for surface recrystallization for metal oxides THttig 0.26 TF with TF the absolute melting temperature

Influence of Particle Size

v decomposition of Al(OH)3, thermogravimetric analysis v smaller particles react at lower temperature

1 m 50-80 m 0.2 m

Influence of Particle Size on Melting Point of Au

v Melting point can decrease drastically with decreasing particle size!

Ph. Buffat, J. P. Borel, Phys. Rev. A 13 (1975) 2287-2298

Surface Energy

v loss of surface area through formation of larger crystals

v surface energy of t-ZrO2(101) 1.1 J m-2 v surface area shrinks from 250 to 150 m2 g-1 during calcination 110 J g-1 or 13.5 kJ mol-1 (ZrO2) v is not negligible in comparison to crystallization

Formation of a Crystalline Solid from Amorphous Precursor

H???

v nature of amorphous precursor usually not well-known v H depends on nature of precursor & product v if, through variation of the treatment conditions, for the same precursor different Hs are obtained, the products will be different

Effect of Additives
Time / min min Zeit /
Probentemperatur /K /K Sample bed temperature 120 1000 950 900 850 800 750 700 650 600 650 700
Rampe 3/min 17,1 ml-Schiffchen ZH SZH

130

140

150

160

170
FeSZH

180

190

MnSZH

750 800 850 /K/K OvenOfentemperatur set temperature

v additives shift glow to higher temperatures and reduce overshoot

Glow Phenomenon: MnSZ and FeSZ

165 Heating time / min 170 175 180
25 g 12 g 12 g 3g 3g
Temperature / K

185

190
1000 900 800 700 600 500 400 300 0 100 200 300 400 500 Time / min

Sample temperature / K

1000 950 900 850 800 750 780

25 g

2%MnSZH 2%MnSZ 2%FeSZH

800 820 840 Oven temperature / K

860

v max. calcination T may be exceeded v promoters influence calcination chemistry (systemic), Fe and Mn different v strong batch size dependence

Influence on Catalytic Activity?!

165 1000 Probentemperatur / K
25 g

170

Zeit / min 175 180

25 g 12 g

185

190

2%FeSZ

950 900 850 800 750 780

12 g 3g

3g

2%MnSZ
860

800 820 840 Ofentemperatur / K

16 Yield i-butane (%) 14 12 10 8 6 4 2 0 0 120 240

Yield i-butane (%)

17.1 ml boat 8.4 ml boat 2.2 ml boat

14 12 10 8 6 4 2 0

17.1 ml boat 8.4 ml boat 2.2 ml boat

360

480

120

240

360

480

Time on stream / min

Time on stream / min

samples calcined in larger batches are more active (1 vol% n-butane at 338 K) characterize catalysts

Surface Area & Calcination Batch Size

16

Yield i-butane (%)

14 12 10 8 6 4 2 0 0 120 240

Yield i-butane (%)

17.1 ml boat 8.4 ml boat 2.2 ml boat

14 12 10 8 6 4 2 0 0 120 240

17.1 ml boat 8.4 ml boat 2.2 ml boat

120
360 480 Time on stream / min

115
2 -1

FeSZ MnSZ

360

480

Time on stream / min

Surface area / mg

2%FeSZ

110 105 100 95 90 85 80 0 2 4 6 8 10 12 14 16 18 20

2%MnSZ

Boat size / ml

v surface area increases with calcination batch size v differences in activity exceed differences in surface area

Activity and Bulk Structure

14

Yield i-butane (%)

Yield i-butane (%)

12 10 8 6 4 2 0 0 120 240

17.1 ml boat 8.4 ml boat 2.2 ml boat

16 14 12 10 8 6 4 2 0

17.1 ml boat 8.4 ml boat 2.2 ml boat

2%MnSZ
1.445 1.444 1.443 1.442 c/a 1.441 1.440 1.439 1.438 0 5 10

2%FeSZ
0 120 240 360 480 Time on stream / min

360

480

Time on stream / min

1.445 1.444 1.443 1.442 c/a 15 20 1.441 1.440 1.439 1.438 0 5 10 Boat size / ml 15 20

Boat size / ml

v lattice parameters of tetragonal ZrO2 change

Porosity of Iron-Promoted Sulfated Zirconia

70 60 50 40 30 20 10 0.0 0.2 0.4 p/p0 0.6 0.8 1.0

v large batch calcination: formation of mesopores, 1-4 nm

Adsorbed volume / cm*g

2.2 ml boat 8.4 ml boat 17.1 ml boat

-1

Effect of Calcination Batch Size

v samples from the same raw material (precursor) are converted into different products by variation of the batch size during calcination

Why Does Overheating Occur?

v heat is generated faster than transferred away v look at heat transfer

Heat Transfer Modes

v all of them play role during calcination v estimations can be made!

Heat Transfer by Convection

v free vs. forced convection makes a considerable difference

Thermal Conductivity
v data are for solids, conduction worse in loose powders v exact material during calcination unknown

ZrO2
Kingery 1955

Radiation

v conduction and convection are proportional to difference between the temperatures (T gradient , T) of the body of interest and the surrounding v radiation is proportional to the difference between the temperatures to the forth power

IUPAC Recommendations on Calcination

v all particles of catalyst should be subjected (..) to exactly the same (..) conditions only possible in moving beds (fluid beds, rotating furnaces, spray drying) v supply a sufficient quantity of gas or liquid to the reactor to ensure complete reaction (..); special consideration should be given to mass and heat transfer

J. Haber, J.H. Block, B. Delmon, Pure & Appl. Chem. 67 (1995) 1257-1306

Preparation of Supported Catalysts

v goal: disperse an active phase on an inexpensive and inert (?) support

increase surface area

support

Interaction Between Active Phase and Support

Spreading Mechanisms

v transport via gas phase also possible

Preparation of SCR Catalyst by Solid-Solid-Wetting

v MoO3/TiO2: typical catalyst for selective catalytic reduction (reaction of NOx with NH3 to give N2 and H2O)

720 K heating in O2, saturated with H2O

v start out with physical mixture: small particles, intimate mixture v evoke spreading through thermal treatment v analysis of surface composition!

Ion Scattering Spectroscopy

v topmost layer of surface is probed with ion beam (He+)
He+

Ekin (~kV) E'kin

He+

v also: LEIS = low energy ion scattering v kinetic energy after interaction depends on mass of scattering atom v highly surface sensitive, destructive

Spreading

v Spreading of MoO3 on TiO2 can be achieved by thermal treatment in O2/H2O

Supported Metal Catalysts: Metal-Support Interaction

Depth Profiling of Supported Noble Metal Catalyst

v Rh/TiO2: a system with strong metal support interaction (SMSI)

Conclusion

v Many things can happen during a thermal treatment!