MODIFICATION OF NaY BY La3+ FOR THE DEHYDRATION

OF LACTIC ACID: THE EFFECT OF PREPARATION PROTOCOL

ON CATALYST MICROSTRUCTURE AND CATALYTIC
PERFORMANCE
Dinghua Yu, Peng Sun, Zhenchen Tang, Zhixian Li and He Huang*
State Key Laboratory of Materials-Oriented Chemical Engineering, College of Biotechnology and Pharmaceutical Engineering,
Nanjing University of Technology, Nanjing 210009, Jiangsu Province, China

La-modified NaY zeolites have been prepared through impregnation and in situ synthesis methods. The surface structure of the obtained
zeolites was then characterised by XRD, UV–Vis DRS, FT-Far-IR, Raman spectra, H2 -TPR, N2 adsorption, and NH3 -TPD. The results of the catalytic
dehydration reaction of lactic acid showed that the La/NaY catalyst prepared by impregnation method exhibited higher selectivity to acrylic
acid than the La–NaY prepared by the in situ synthesis. The characterisation results indicated that the enhanced catalytic performance could be
attributed to the difference of La3+ ion location caused by the different preparation protocols, which would influence the electric field distribution
of zeolites cages, the reactant adsorption, chemical activation, and the reaction path.

Les zéolithes NaY modifiées avec du lanthane (La) ont été préparées grâce à des méthodes d’imprégnation et de synthèse in situ. La structure de la
surface des zéolithes ainsi obtenues a été ensuite caractérisée par DRX, spectrophotomètre UV–VIS DR, FT-Far-IR, spectroscopie Raman, réduction
thermo-programmée de H2, adsorption de N2 et désorption thermo-programmée de NH3. Les résultats de la réaction de déshydratation catalytique
de l’acide lactique montrent que le catalyseur La/NAY préparé grâce à la méthode d’imprégnation a fait preuve d’une plus grande sélectivité à
l’acide acrylique que le catalyseur La/NAY préparé grâce à la synthèse in situ. Les résultats de caractérisation indiquent que le meilleur rendement
catalytique peut être dû aux différences d’emplacement de l’ion La3+ causées par les différents protocoles de préparation, qui peuvent influer sur
la distribution du champ électrique des cages de zéolithes, l’adsorption du réactif, l’activation chimique et le chemin réactionnel.

Keywords: zeolite, location, selectivity, lactic acid, dehydration

INTRODUCTION the chemical transformation processes of biorenewable feedstock

mainly include dehydration (Chai et al., 2007; Roman-Leshkov et

M
olecular sieves with various pore dimensions and sur-
al., 2007), deoxygenation (Maris and Davis, 2007), hydrogenoly-
face acid-base are catalytic materials of great importance
sis, hydrogenation (Zhang et al., 2001; Gallezot and Perrard, 2002;
because of their industrial applications in petroleum
Murzin and Simakova, 2008), etc.
refining (Corma, 1995; Busca, 2007), petrochemical industry
Lactic acid, a bulk fermentation product, can be transformed
(Arandes et al., 2009; Nawaz and Wei, 2009), fine chemical pro-
into high-value derivates such as acrylic acid (Smith et al., 1942),
duction (Armor, 2001; Jaimes and Lasa, 2009), etc. Researchers
1,2-propanediol (Cortright et al., 2002), 2,3-pentanedione (Gunter
have made a lot of efforts on the preparation and modification of
molecular sieves in order to improve the selectivity to the desired
products (Xue et al., 2007; Chao et al., 2008). With the depletion of ∗ Author to whom correspondence may be addressed.
non-renewable fossil resources, nowadays people are shifting the E-mail address: biotech@njut.edu.cn
research focus on the catalytic conversion of biorenewable feed- Can. J. Chem. Eng. 89:484–490, 2011
stock, not only for energy supply, but also for synthetic chemicals. © 2010 Canadian Society for Chemical Engineering
DOI 10.1002/cjce.20424
In comparison with petrochemicals, the biorenewable feedstock Published online 9 November 2010 in Wiley Online Library
have excessive functional group containing oxygen; therefore, (wileyonlinelibrary.com).

| 484 | THE CANADIAN JOURNAL OF CHEMICAL ENGINEERING | | VOLUME 89, JUNE 2011 |
et al., 1994; Langford et al., 1995), poly-(lactic acid) (Nijenhuis
et al., 1992), and propylene glycol (Zhang et al., 2002), through
relative mature traditional chemical catalysis process. The dehy-
dration of lactic acid is a hot topic for two reasons. Firstly, acrylic
acid is a higher value product than lactic acid. Secondly, lactic acid
is the simplest hydroxyl carboxylic acid, therefore, the research
of catalytic dehydration of lactic acid has significant contribu-
tion to the development of effective catalysts for multi-functional
biorenewable transformation.
Recently, we have proved that potassium modified NaY (KNaY)
is a durable selective catalyst for the dehydration of lactic acid
to acrylic acid (Shi et al., 2007; Sun et al., 2009). Moreover, the
catalytic dehydration performance on NaY-based catalysts modi-
fied by lanthanide has been significantly improved and the results
showed that the optimum metal is lanthanum with the content of
2 wt% (Wang et al., 2008). Our research results have indicated
that the location of cations in zeolites has large effects on cat-
alytic performance, agreed with the results reported by Breck et
al. (1956).
In this research, we are interested in the influence of La3+
ion location on catalytic dehydration performance and surface
microstructure. La-modified NaY zeolites with different lan-
thanum ion locations were controllably synthesised through
delicate protocols. The catalytic dehydration of lactic acid to
acrylic acid was used as probe reaction to compare the differences
on catalytic performance of samples with different lanthanum ion
locations. The surface microstructure of those catalysts was char-
acterised by X-ray diffraction (XRD), nitrogen adsorption, UV–Vis
diffuse reflectance spectra (UV–Vis DRS) and chemical adsorption
methods such as hydrogen temperature-programmed reduction
(H2 -TPR) and NH3 temperature-programmed desorption (NH3 -
TPD).
EXPERIMENTAL
Catalysts Preparation
The La/NaY catalyst was prepared by the impregnation method.
The powder NaY (Si/Al = 4.5) was impregnated in an aqueous
solution of 2.2 wt% La(NO3 )3 ·6H2 O (obtained from Sinopharm
Chemical Reagent Co., Ltd, Shanghai, China) at 353 K for 4 h
to obtain 2 wt% La, then dried at 393 K for 4 h, and calcined at
823 K over a period of 5 h. Finally, the sample was cooled to room
temperature under ambient conditions.
The La–NaY catalyst was prepared by the in situ synthesis. The
synthesis mixture of molar composition (10 Na2 O:1.0 Al2 O3 :15
SiO2 :300 H2 O:0.05 La2 O3 ) was stirring at room temperature for
4 h. After 24 h of aging, the gel was then transferred into Teflon-
lined steel autoclave. Crystallisation was achieved at 448 K under
autogenous pressure for 24 h. The product was then cooled and
separated from the mother liquor by centrifugation. At last, the
sample was obtained after drying and calcinations at 823 K to
remove the templates.
Catalysts Characterisation
XRD analysis was carried out using a Bruker D8 ADVANCE X
diffractometer with a Cu K˛ monochromatised radiation source,
operated at 40 kV, 30 mA, and a scanning speed of 5◦ min−1 .
The acidity of the catalyst was measured by temperature-
programmed desorption of ammonia (NH3 -TPD). It was per-
formed with an automated BEL-CAT-B-82 system equipped with a
thermal conductivity detector (TCD). 0.12 g of sample in a quartz
tube was heated in a flow of helium to 873 K at a rate of 20 K min−1
| VOLUME 89, JUNE 2011 | |
and maintained at this temperature for 30 min. The adsorption of
NH3 was performed at 373 K in an NH3 –He (10 vol% NH3 ) mix-
ture for 0.5 h, and then the physically adsorbed NH3 was purged
by high purity He at 373 K. TPD of ammonia was performed at a
helium flow of 30 mL min−1 and a heating rate of 10 K min−1 from
373 to 873 K. The acid amount was determined by integrating the
TPD curve in the temperature range from 373 to 873 K.
Temperature-programmed reduction with H2 (H2 -TPR) was
measured with the same apparatus as that of NH3 -TPD. Prior to
the TPR experiments, the catalysts were dried in flowing O2 at
573 K for 3 h followed by purging with pure N2 . An H2 –Ar mix-
ture (5 vol% H2 ) was used as the reducing gas at a flow rate of
30 mL min−1 . The temperature in the TPR experiment was raised
up to 973 K at rate of 10 K min−1 .
Raman spectra were recorded with a Renishaw Invia System.
A laser at 514.5 nm was used as the excitation source, of which
output power was set at 20 mW, and the maximum incident power
at the sample was approximately 6 mW in each measurement. Far-
infrared spectra were acquired with a BioRad FTS-40 instrument
equipped with a DTGS polyethylene detector. The samples were
mixed with paraffin.
UV–Vis DRS were collected with a UV-2401PC spectrometer.
The UV–Vis spectra of La/NaY and La–NaY samples were col-
lected at room temperature in air in the range of 190–600 nm with
a resolution of 2 nm and NaY powder was used as a reference.
The La content after doping and calcinations was determined by
X-ray fluorescence on a PW1400 Philips instrument.BET surface
area was determined from nitrogen isotherms and pore volume
was estimated by means of t-plot. These measurements were
carried out using an ASAP 2020 instrument from Micromeritics
Instrument Corporation, Norcross (Atlanta), GA. Before the mea-
surements, the catalysts were vacuumed for 10 h at 573 K and 4 h
at 623 K, respectively, in order to remove any adsorbed water.
Catalytic Reaction
The dehydration of lactic acid to acrylic acid over different cat-
alysts was tested in a quartz fixed-bed reactor of 8 mm inner
diameter. The catalyst with a constant mass of 1.5 g was charged
in the middle section of the reactor, with quartz wool packed in
both ends. Before catalytic evaluation, the catalyst was pretreated
at required reaction temperature (623 K) for 0.5 h under high
purity N2 (0.1 MPa, 30 mL min−1 ). Then the feedstock (38 wt%
solution of lactic acid) was pumped into the preheating zone first
(LHSV = 3 h−1 ) and then the vapour was driven through the cata-
lyst bed by nitrogen. The products were condensed and analysed
using a GC (Agilent 6890 N) equipped with an FFAP capillary
column and FID detector. Lactic acid conversion and product
selectivity were calculated according to the following equations:
Moles of lactic acid reacted
Conversion (mol%) = × 100 (1)
Moles of lactic acid in the feed
Moles of carbon in a product defined
Selectivity (mol%) = × 100
Moles of carbon in lactic acid racted
(2)
The reaction tail gas was analysed by GC–MS (Thermo finnigan
trace GC2000 DSQ) equipped with a DB-225 capillary column and
MS detector.
THE CANADIAN JOURNAL OF CHEMICAL ENGINEERING | 485 |
Figure 1. UV–Vis diffuse reflectance spectra of NaY-based catalysts
modified by lanthanum.
Figure 2. H2 -TPR profile of NaY-based catalysts modified by lanthanum.

RESULTS AND DISCUSSION

La3+ Ion Location
UV–Vis DRS could be used to study the metal–oxygen environ-
ment and identify the status of transition metal ions in solid
samples. The UV–Vis DRS spectra of Lanthanum modified NaY
catalysts synthesised by different methods are shown in Figure
1, which shows the differences of the two samples, indicating
the differences of La3+ locations. Two percent La/NaY catalyst
has a strong absorption at about 210–250 nm in the UV–Vis DRS,
which could be attributed to the absorption of four- or sixfold
lanthanum ion (Kannan et al., 2006). In contrast, 2% La–NaY
catalyst synthesised by in situ process shows weak absorption
between 190 and 210 nm instead of obvious absorption above
200 nm region, which is generally attributed to low coordination
number of La3+ ion. Therefore, the UV–Vis DRS results indicate Figure 3. Far IR spectra of the typical catalyst samples.
that La3+ ion location could be controlled in NaY catalysts by
different synthesis protocols. Precisely speaking, the La3+ ions
114, 157 and 188 cm−1 are assigned to cations located at sites
mainly stayed in extra-framework with high coordination num-
III, I , I, and II, respectively. However, the absorption peaks at
ber if prepared by impregnation method, otherwise they mainly
258 cm−1 is attributed to the oxygen framework mode. Compared
located in framework with low coordination number if prepared
with unmodified NaY zeolites, NaY catalysts modified by lan-
by in situ synthesis process.
thanum showed that the 88 cm−1 band red shifted to ∼84 cm−1 ,
H2 temperature-programmed reduction (H2 -TPR) was often
the 157 cm−1 band blue shifted to 164 cm−1 , and the 204 cm−1
used to study the reducibility of metal oxide and it could sen-
band blue shifted to ∼210 cm−1 . Moreover, the 258 cm−1 band
sitively characterise chemical environment of metal cations.
attributed to oxygen framework mode blue shifted to 261 and
Figure 2 shows the H2 -TPR results of the two samples. Two per-
271 cm−1 , respectively, indicating the different lanthanum ion
cent La/NaY sample showed a reduction peak in the range of
locations induced by different preparation protocols.
750–900 K, which is the reduction of La3+ ion. The quantita-
Based on the characterisation results shown above, we come
tive calculation results indicated that this peak corresponded to
to the conclusion that the locations of La3+ species in the
the reduction of La from the oxidation number of three (3+) to
two samples were different and the La3+ in La/NaY catalyst
zero (0). Moreover, with respect to the reduction temperature of
could be reduced much easier than that in La–NaY counterpart.
La2 O3 , the reduction peak of La/NaY shifted to higher tempera-
Impregnation method resulted in the extra-framework location of
ture, indicating the stronger interaction between La3+ species and
lanthanum ion in the NaY zeolites and in situ synthesis process
NaY zeolites. However, 2% La–NaY sample did not show obvi-
could locate lanthanum ion into the framework of NaY zeolites.
ous reduction peak in the tested temperature range, which could
reflected the nature of framework lanthanum ion, in agreement
with UV–Vis DRS results. Catalysts Structure and Crystal Lattice Parameters
Far-infrared spectroscopy is able to directly probe the cations The structures of NaY unmodified and modified samples were
immobilised in zeolites via their characteristic site vibration characterised by XRD as shown in Figure 4. Compared with NaY
modes. Figure 3 shows the Far-IR spectra of NaY unmodified and unmodified zeolites, the modified NaY zeolites retained most of
modified samples. According to the results reported by Ozin et the characteristic peaks but showed poorer crystallinity. The rela-
al. (1985); and Baker et al. (1985), the absorption peaks at 90, tive crystalline degree of 2% La–NaY and La/NaY was about 56%

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Figure 4. XRD patterns of NaY-based catalysts modified by lanthanum.
and 93%, respectively, which indicated that in situ synthesis pro-
cess could insert lanthanum ion into framework of zeolites and
cause serious crystal cell distortion and decrease of crystallinity.
In order to study the effect of amount of lanthanum ion on zeolites
structure, a series of NaY zeolites modified by different amount of
lanthanum were prepared by using the in situ process. The results
showed that the crystallinity decreased with the increase of lan-
thanum content. Five percent La–NaY catalyst showed complete
collapse of the zeolites structure, which confirmed the location of
La3+ ions in the framework of La–NaY sample. In addition, differ-
ent from the NaY unmodified zeolites, the diffraction peaks of two
modified samples shifted to lower angle, indicating the expansion
of crystal cell because of the introduce of lanthanum, the crystal
cell expansion of La–NaY sample was more obvious than that of
La/NaY catalyst, which is probably because of the isomorphous
replacement of lanthanum ion.
Figure 5 shows the Raman spectra of the NaY zeolites before
and after the lanthanum modification. In the case of using excita-
tion laser with the wavelength of 514.5 nm, La2 O3 shows typical
peak at 104, 191, and 408 cm−1 (Scheithauer et al., 1998). With
the absence of those peaks, our samples showed no existence
of bulk La2 O3 in NaY zeolites before and after the modification
of lanthanum, consistent with the XRD characterisation results.
Compared with pure NaY unmodified sample, La–NaY showed
the similar peaks, and no characteristic Raman scattering peak
of lanthanum species was detected. However, for the La/NaY cat-
alyst, a strong new peak at 1051 cm−1 could be assigned to the
Figure 5. Raman spectra NaY-based catalysts modified by lanthanum.
| VOLUME 89, JUNE 2011 | |
Table 1. The surface area, pore structure, and lanthanum content of
modified NaY zeolites
Laa (%)
BET surface Pore volume
Zeolites area (m2 g−1 ) (cm3 g −1 ) As-prepared Calcined
NaY 495 0.31 — —
2% La–NaY 547 0.33 2.05 1.97
2% La/NaY 537 0.33 1.95 1.94
a
The content was calculated based on XRF results.
non-framework oxygen atoms bonded to the lanthanum and the
existence of La–O–Al bond formed during calcinations (Carva-
jal et al., 1990). Moreover, the peak at 1051 cm−1 appeared in all
La/NaY samples with different lanthanum contents (not shown).
These results indicated that synthesis protocol had really affected
the lanthanum ion location.
Surface Acidity and Pore Structure
Table 1 shows the surface area and pore volume of NaY before and
after the modification. The modification increased the surface area
of NaY slightly. The reason could be that the modification process
including both the impregnation and in situ synthesis broke the
crystal particles and resulted in the increase of surface area. Com-
pared with NaY unmodified sample, the pore volume of modified
samples also showed slight increase, indicating the expansion of
the crystal cell upon the addition of lanthanum.
Figure 6 shows the pore size distribution curves of those sam-
ples. We can see that the pore size of La/NaY increased, while
the pore size of La–NaY decreased. This pore size change could
imply the different coordination status of La3+ ion in NaY zeo-
lites. According to the data reported by Ahmed et al. (2005), the
dynamic radius of La3+ ion is 1.12 Å. Comparing with the pore
diameter of NaY zeolites (5.2 Å), La ion is smaller and could move
into the pores of the NaY zeolites. Moreover, some literatures have
studied the metal ion location in modified NaY zeolites by impreg-
nation method, and the reported results showed that the La3+
ions partially stripped off their hydration shell and migrated from
cation positions in the supercage of position to SI in the sodalite
cage (Klein et al., 1995) during the calcination process, which
might enlarge the pore size of NaY zeolites. By comparison, the
Figure 6. Pore size distribution curves of NaY-based catalysts modified
by lanthanum.
THE CANADIAN JOURNAL OF CHEMICAL ENGINEERING | 487 |
 Table 2. Acid properties of different zeolites studied by NH3 -TPD

Acidity amount (␮mol g−1 )

Zeolites W (373–473 K) M (473–673 K) S (673–873 K) Total acid amount (␮mol g−1 ) Acidity density (␮mol m−2 )

NaY 837 664 34 1535 3.1

2% La/NaY 826 485 35 1346 2.5
2% La–NaY 711 471 25 1207 2.4
W, M, and S stand for weak (373–473 K), medium (473–673 K), and strong (673–873 K) acid sites.

pore size of La–NaY prepared by the in situ synthesis decreased
significantly could be the result of the entrance of La3+ ion into
the zeolite framework.
NH3 -TPD technique was used to characterise the surface acidity
of NaY zeolites before and after modification and the qualitative
calculation results are listed in Table 2. The amount of surface acid
decreased upon the modification, and the amount of weak acid
of La–NaY catalyst decreased more significantly. Moreover, the
calculated surface acidity density was used to correlate catalytic
performance with surface acidity nature. The surface acidity den-
sities of modified NaY zeolites obtained by different preparation
protocols were very close to each other.
The Catalytic Performance
The gas-phase dehydration reaction of lactic acid to acrylic
acid was use as the probe reaction to investigate the catalytic
performances of these zeolites and the results of catalytic activity
and selectivity are listed in Table 3. Compared with unmodified
NaY zeolites, catalysts after modification have both shown the
improvement of the catalytic dehydration performance and
higher selectivity to acrylic acid. The by-products have been
analysed through the combination of GC and GC–MS techniques
qualitatively (not shown), and the by-products comprise acrylic
acid, lactide, acetaldehyde, and COx. The quantity of by-product
is highest when lactic acid dehydration is performed upon NaY
zeolite, which indicates that unmodified NaY could accelerate
the side reaction such as decarboxylation, decarbonylation, or
polymerisation reaction of acrylic acid. Contrasting the quantity
of by-product acquired on modified NaY zeolites with lanthanum
ion through different preparation protocols, the 2% La/NaY
catalysts show the more advantages to diminish side reaction.
Moreover, primary contrast of the colour of reacted catalysts, the
coke-resistance of 2% La/NaY is the most obvious comparing
with other catalysts. As a result, it is reasonable to explain that
the existence of La3+ could notably improve the selectivity to
acrylic acid, simultaneously inhibiting the side reaction. There-
fore, the catalytic performance improvement could be attributed
Table 3. Catalytic performance of the NaY-based catalysts
Product distribution/mol%
Acrylic Propanoic
Catalyst Conversion/% acid Acetaldehyde acid Others
NaY 96.1 14.8 10.8 1.6 72.8
2% La–NaY 97.6 36.2 19.3 3.8 40.7
2% La/NaY 98.5 56.3 12.3 1.6 29.8
Reaction conditions: lactic acid feedstock: 38 wt%, lactic acid flow rate:
4.5 mL h−1 , N2 flow rate: 30 mL min−1 , catalysts: 1.5 g, TOS, 360 min.
to the specific catalysts surface structure produced by different
preparation protocols.
Our group (Wang et al., 2008) has shown that NaY zeolites
modified by rare earth metal improved the catalytic dehydration
performance of lactic acid to acrylic acid, and we speculated
the possible reasons. Based on some preliminary characterisation
results, we thought that the improvement was due to both the
physical structure factors (such as pore size, pore volume, and
surface area) and chemical factors (such as specific location of
rare metal ion, lower surface acidity density). This research was
also aimed to study the surface structure of catalysts and have
a deeper understanding about the relationship between surface
structure and catalytic performance.
Firstly, both catalysts modified by lanthanum in different ways
possess similar pore volume, specific surface area, and surface
acidity density, which indicate that these surface properties may
not cause the differences of the catalytic performance. Secondly,
the different preparation protocols lead to reverse change of the
pore size and also the change of pore volume of the two cat-
alysts. Based on literature results and above characterisation,
we propose a catalyst surface model as depicted in Figure 7.
Lanthanum ion could locate in the framework of zeolites for
La–NaY sample synthesised by in situ process. Since some of
the Al3+ ions were replaced by La3+ ion, the amount of surface
acidity of La–NaY decreased more than that of La/NaY sample
by impregnation process. However, La3+ ion in La/NaY had a
different environment according to literature and our research
results. Nery et al. (1997) have studied the position of La3+ and
Ce4+ ions in La/Ce–NaY zeolites through XRD technique and
Reitveld method of structure refinement. Their results showed
that both La3+ and Ce4+ migrated to SII sites that were located
inside the sodalite cage. The existence of tri-valence La3+ would
affect the electric field distribution of the sodalite cage severely,
especially for lanthanum ion located in exchangeable site. With
contrast, lanthanum ion located in framework, incorporated in
molecular framework through Si–O–La–O–Si bonds, would bring
minor effect on the electric field distribution of the sodalite cage.
The dehydration reaction of lactic acid to acrylic acid is mainly
acid/base catalysis process, so the microstructure and electric field
distribution of the reaction sites in the molecular sieve would have
significant influence on the reaction process, such as the chem-
ical adsorption of reactant molecular and reaction intermediate.
Miller and coworkers (Tam et al., 1997) showed that in the cat-
alytic dehydration process of lactic acid over sodium salt catalysts,
the sodium lactate, produced by lactic acid and sodium ion in cat-
alysts, was the real reactant and could be catalytic dehydration on
acidity or base sites. Therefore, we speculated that lactic acid was
firstly transformed to sodium lactate and the stronger electric field
action decreased the electron cloud density of hydroxyl group at
˛-site, which enhanced the selectivity to acrylic acid and inhibit
the side reaction such as decarboxylation or decarbonylation.

| 488 | THE CANADIAN JOURNAL OF CHEMICAL ENGINEERING | | VOLUME 89, JUNE 2011 |
Figure 7. A possible lanthanum ion location diagram of NaY-based catalysts synthesised by different methods.
CONCLUSIONS
In summary, based on our previous work about the improvement
of catalytic dehydration performance on NaY zeolites modified by
rare earth metal, we prepared NaY zeolites modified by lanthanum
with controllable La3+ ion locations in different ways and studied
the influence of La3+ ion location on catalytic dehydration per-
formance and the surface microstructure. Characterisation results
from the Raman spectra, UV–Vis diffuse-reflectance, and H2 -TPR
suggested that La3+ ions were mainly located in the sodalite
cage in the La/NaY prepared by impregnation method, whereas
La3+ species were incorporated into the lattice of NaY in La–NaY
catalyst prepared by in situ method. N2 sorption experiment sug-
gested that pore size decreased in La–NaY catalyst, while the
pore size in La/NaY catalyst increased. Compared with the loca-
tion of La3+ ion in framework, La3+ located at the exchangeable
site of the sodalite cage affected the electric field distribution,
leading to the decrease of the electron cloud density of the
hydroxyl group at ˛-site, resulting the enhancement of the selec-
tivity to acrylic acid and the inhibition of the side reaction such
as decarboxylation or decarbonylation. This work is very impor-
tant for people to understand the catalytic mechanism of lactic
acid dehydration process and offers a guide to synthesise an effi-
cient catalyst for the catalytic transformation of biomass-derivate
feedstocks.
ACKNOWLEDGEMENTS
Authors thank the financial support from National Natural Sci-
ence Foundation of China (grant number 20906051) and Jiangsu
Province Fundamental Research Plan (grant number BK2009478),
hi-tech research and development program of China (grant num-
ber 2006AA020101) and the key discipline fund of Nanjing
University of Technology.
| VOLUME 89, JUNE 2011 | |
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