Bi2O3 modification of HZSM-5 for methanol-to-propylene conversion: evidence of olefin-based cycle

Article abstract of DOI:10.1039/c6ra27849c

Bi₂O₃-modified HZSM-5 catalysts were prepared via a traditional wetness impregnation approach, and used for the methanol-to-propylene conversion reaction. The selectivity for propylene increases significantly with bismuth loading, while that for ethylene shows the opposite trend. However, the Bi₂O₃/HZSM-5 catalysts have significantly lower capacities for methanol conversion than the parent HZSM-5. The underlying causes are the reduced acid site strength, narrower pore openings, and reduced pore width in Bi₂O₃/HZSM-5. This work provides insights into the olefin-based cycle operation for methanol-to-olefin reactions using modified HZSM-5 catalysts.

Full text of DOI:10.1039/c6ra27849c

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PAPER
Bi O modification of HZSM-5 for methanol-to-
2
3
propylene conversion: evidence of olefin-based
Cite this: RSC Adv., 2017, 7, 16602
cycle
a
a
a
a
a
Hairong Zhang, Zhangxuan Ning, Hongyan Liu,* Jianpeng Shang, Shenghua Han,
a
b
a
Dingding Jiang, Yu Jiang and Yong Guo*
Bi
for the methanol-to-propylene conversion reaction. The selectivity for propylene increases significantly
with bismuth loading, while that for ethylene shows the opposite trend. However, the Bi /HZSM-5
2 3
O -modified HZSM-5 catalysts were prepared via a traditional wetness impregnation approach, and used
2 3
O
Received 6th December 2016
Accepted 3rd March 2017
catalysts have significantly lower capacities for methanol conversion than the parent HZSM-5. The
underlying causes are the reduced acid site strength, narrower pore openings, and reduced pore width
DOI: 10.1039/c6ra27849c
in Bi
2 3
O /HZSM-5. This work provides insights into the olefin-based cycle operation for methanol-to-
rsc.li/rsc-advances
olefin reactions using modified HZSM-5 catalysts.
3
5–37
be achieved via either reducing the particle size
ducing an additional mesoporous transport network.
(3) Modifying the reaction conditions, such as diluting
or intro-
Introduction
20,21,23,38–50
Because methanol can be produced from natural gas, coal,
1
3,13,51
biomass, or CO2 hydrogenation, the methanol-to-propylene methanol with an inert gas or co-feeding water,
and
(
MTP) process is an alternative route to produce propylene with changing the temperature. It is generally known that the addi-
high yield and high propylene/ethylene ratio (P/E). This process tion of water stabilises of the catalyst during the MTO reaction,
was rst developed by the Lurgi company based on a xed bed and that the product distribution may change according to the
3
,4,28
reactor with a high-silica nanosized HZSM-5 zeolite catalyst, and partial pressure of methanol.
Reducing the partial pressure
2
the process was commercialised in China in 2010. During the and weight hourly space velocity (WHSV) of methanol could
past four decades, many attempts have been made to selectively possibly suppress the inuence of hydrogen transfer reactions
3
52
produce propylene from methanol, not only on medium-pore over H–T zeolite. Water competes with light olens for the
zeolites (ZSM-5, EU-2) but also on small-pore (HFU-1, SAPO-34, Brønsted and Lewis acid sites, and accelerates the desorption of
3,4
Sigma-1, and ZSM-58 (ref. 4)) and large-pore zeolites (modied the olens. Therefore, the adsorption of water on these acid
5
Y zeolites, Mn/ZSM-12, Ba/dealuminated mordenite, and CON ). centres reduces their strength and concentration, as well as
There are four general strategies to improve propylene selectivity their probability of interaction with hydrocarbons. As a conse-
in the methanol-to-olen (MTO) reaction:
1) Reducing the Brønsted acidity (in terms of both site into oligomers, aromatics, and coke is lowered. However, while
quence, the initial conversion of light olens (mainly propylene)
3
(
6
,7
density and strength) of zeolite catalysts in order to limit/ a high P/E ratio can be achieved with a low methanol partial
inhibit the side reactions. The approaches include: adjusting pressure, a very low value of the latter is not economical for
8–10
11–16
37
the Si/Al ratio of the zeolite,
and isomorphous substitution of heteroatoms for zeolite.
post-synthesis modication,
practical operations. (4) Changing the reactor conguration.
5
,17–21
It is known that in the reactions of toluene disproportion-
(
2) Modifying the porosity of the zeolite and thereby inu- ation, methylation of toluene, and xylene isomerisation, post-
encing the transition state shape selectivity, such as by using synthesis modication of HZSM-5 with oxides not only
2
2–30
zeolites with different topologies
or tailoring their pore size by decreased the Brønsted acidity (density and strength) of the
Moreover, a shorter diffusion zeolite catalyst, but also narrowed/blocked the pore openings
3
1–33
post-synthesis modication.
length in zeolites enhances the molecular diffusion, which may and reduced the pore size. This may affect the transition state
34
53
27
dramatically inuence the product shape selectivity. This could shape selectivity and enhance the para-selectivity for toluene
disproportionation. In the case of MTO reaction, it is well
accepted that the zeolite performance is controlled by its
framework structure, pore architecture, and acidity. The
product distribution in methanol to hydrocarbon conversion
a
College of Chemistry and Chemical Engineering, Institute of Applied Chemistry,
Shanxi Datong University, Datong 037009, P. R. China. E-mail: liuhongyan@tyut.
over ZSM-5 can be rationalised in terms of the relative propa-
edu.cn; liuhongyan9629@163.com; ybsy_guo@163.com
b
50
gation rates of the aromatic- and olen-based cycles. If we
Datong Coal Mine Group Co., LTD, Datong 037003, P. R. China
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separate these two cycles by sterically suppressing the forma- Catalytic tests
tion of the larger aromatic molecules and only allowing product
The MTP reaction was carried out at atmospheric pressure in
a xed-bed stainless steel reactor (i.d.: 15 mm, length: 550 mm).
The catalyst powder was compressed to form wafers, then
crushed and sieved to obtain 40–60 mesh particles. In all the
formation via the C3+ alkenes, ethylene formation might be
23
avoided in the MTP application. However, few experimental
studies have been conducted using such steric constraints to
25,51,54
suppress the aromatic-based cycles.
experiments, 0.5 g of the catalyst was placed in the middle of the
In this study, bismuth oxide-modied HZSM-5 catalysts were
prepared by a wetness impregnation method. The catalysts were
characterised by X-ray powder diffraction (XRD), Brunauer–
Emmett–Teller (BET) adsorption, and NH3 temperature pro-
grammed desorption (TPD) analyses. Their catalytic activities
for MTP conversion were tested. Our main goal was to under-
stand the inuence of the acidic properties and microporous
structure of HZSM-5 on its catalytic performance. We are
especially interested in their effects as well as those of the
methanol WHSV on the dual cycles.
ꢀ
reactor and activated in situ at 550 C for 3 h under an N
3
2
ow of
ꢁ1
0 mL min . The total products were analysed online with
a gas chromatograph (GC-950) equipped with a ame ionisation
detector and an HP-Plot Q capillary column (30 m, 0.53 mm i.d.,
stationary phase thickness 40 mm). Both methanol and dime-
thylether(DME) were regarded as reactants in the calculations.
Results and discussion
Effect of Bi O on the structure and acidity of HZSM-5
2 3
In Fig. 1, the similar XRD patterns of all zeolite samples indicate
that the framework of HZSM-5 was preserved aer the modi-
cation. However, the relative intensities changed slightly,
meaning that the crystallinity of the catalysts is inuenced by
the amount of Bi O used for modication. Compared to the
Experimental
Catalyst preparation
2
3
The ZSM-5 zeolite was hydrothermally synthesised according to
HZSM-5 sample and using the intensities of the typical MFI
55
our previous work. The parent HZSM-5 was prepared by ion
56
peaks of 501, 051, 151, 303, and 133, the relative crystallinities
ꢀ
ꢀ
exchange of ZSM-5 three times in 1 M NH NO solution at 90 C
for 4 h each time. Aer ltration, the residue was dried at 100 C
for 12 h, and further calcined at 550 C in air for 6 h.
4
3
of a and b were estimated as 89.8% and 78.1%, respectively. The
crystalline phases of Bi
zeolites with up to 5 wt% Bi
Bi was dispersed on the external surface of zeolite in the
form of nanosized crystal particles,
2
O
3
were not detected in the modied
ꢀ
2 3
O . This suggests that some of the
2 3
The HZSM-5 catalyst was modied by Bi O using a wetness
2 3
O
impregnation method. The bare HZSM-5 was mixed with
a solution containing the desired amount of bismuth nitrate in
deionised water. Thereaer, the solution was transferred into
a vacuum evaporator to eliminate the water. The residue was
57,58
which is one reason for
the reduced crystallinity aer the modication. Moreover,
compared with HZSM-5, the intensities of XRD peaks with 2q <
ꢀ
1
0 in a and b decreased evidently. This observation implies
ꢀ
ꢀ
dried at 100 C for 12 h, and further calcined at 550 C in air for
2 3
that Bi O entered the zeolite channels, since the low-angle XRD
6
h. The catalysts with 3 or 5 wt% Bi O in HZSM-5 were denoted
2 3
intensities for ZSM-5 are known to be sensitive to the presence
a and b, respectively.
56,59–62
of any species inside the channels.
We made two interesting discoveries. First, the main XRD
peak shis to a lower angle upon the incorporation of more
1
3,14,56,63–70
bismuth. Most modied HZSM-5 zeolite catalysts
ZSM-5 zeolite with increased Si/Al ratio
and
display this
Catalyst characterisation
8,30,71,72
The XRD patterns were acquired on a Shimadzu XRD-6000
diffractometer operated at 40 kV and 40 mA with Cu Ka irra-
diation and nickel lter (l ¼ 0.15406 nm). The diffraction
ꢀ
patterns were recorded in the angle range of 2q ¼ 5–35 with
ꢀ
ꢁ1
a scan speed of 8.0 min . The specic surface areas, pore size
distributions, and total pore volumes of the catalysts were ob-
ꢀ
tained via N adsorption/desorption at ꢁ196 C using a Micro-
2
meritics ASAP 2010 apparatus, aer rst outgassing the sample
at 300 C for 4 h under vacuum. Specic surface areas were
ꢀ
3
calculated according to the BET method. NH -TPD analysis was
performed in a quartz xed-bed micro-reactor equipped with
a thermal conductivity detector. Prior to the experiment, 100 mg
of the catalyst was pre-treated in a He stream (99.99%, 20 mL
ꢁ
1
ꢀ
ꢀ
min ) at 400 C for 0.5 h. Aer cooling down to 100 C, the
catalyst was exposed to a ow of 20 vol% NH /N mixture (30 mL
3
2
ꢁ
1
min ) for 30 min, and then treated in an N ow for 40 min in
2
order to remove any physically adsorbed molecules. Finally, the
2
desorption experiment was carried out in an N ow (99.99%, 20
Fig. 1 XRD patterns for the samples. Bottom to top: HZSM-5, (a) 3 wt%
Bi /HZSM-5, (b) 5 wt% Bi /HZSM-5, and Bi
ꢁ
1
ꢀ
ꢀ
ꢁ1
mL min ) from 100–600 C at a heating rate of 10 C min
.
O
2 3
O
2 3
2 3
O .
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Acidity is one of the most important characteristics of
aluminosilicate zeolites, because the amount and strength of
the acid sites are key for the catalytic performance. The
NH -TPD measurements were used to determine these charac-
3
teristics. In Fig. 3, all three catalysts showed two distinct
desorption peaks in the TPD proles, in accordance with the
21
Fig. 2 Proposed interactions between Bi
2
O
3
and Brønsted acidity.
reported data for MFI materials. In general, the desorption
temperature represents the strength of acid sites: the peak at
the lower (higher) temperature is associated with the weak
behaviour. Second, the framework tetrahedral Al is preserved (strong) acid sites. Aer 3% Bi
O
loading, the number of strong
2
3
2
7
and the framework Al shis slightly downeld (in Al MAS acid sites decreased sharply and the ammonium desorption
2
7
NMR spectra) compared to modied HZSM-5 zeolite. The Al temperature was slightly lower than that of HZSM-5, while those
MAS NMR spectra of HZSM-5 is known to contain two signals: of the weak acid sites showed the opposite trend. When the
an intense peak centred at 55 ppm (the framework tetrahedral Bi
2 3
O loading was increased to 5%, the acidity trend remained
Al), and a weak signal centred at 0 ppm (extra-framework similar to that for a, hence the amount of acid sites remained
3
2,37,73
64
Al).
spectrum shows that all the Al exists as framework tetrahedral and strength of the strong acid sites in the bismuth-containing
Al, and the peak corresponding to framework Al shis slightly HZSM-5 catalysts decrease with increasing Bi content, while
downeld (from 53.3 to 56.5 ppm) aer phosphate treatment. In those of weak acid sites increase, in agreement with other
In phosphorous-modied ZSM-5 zeolite, the NMR approximately the same. We conclude that the concentration
O
2 3
70
11
Mo-modied ZSM-5 zeolite, the peak corresponding to modied HZSM-5 catalysts.
framework tetrahedral Al was shied to higher elds by
ꢁ
2.5 ppm. Based on these reports, we speculate that the Effect of Bi O on catalytic performance in the MTP reaction
2 3
introduced Bi
ZSM-5 zeolite, but also formed defects in the ZSM-5 structure
Fig. 2). These structural defects in the HZSM-5 structure are
another reason for the lower crystallinity in the modied
zeolites.
2 3
O not only reduced the Brønsted acid sites in
Catalyst conversion capacities. The conversion capacities of
the catalysts for MTP reaction were evaluated in a continuous
(
ꢀ

ow xed bed reactor under atmospheric pressure at 470 C,
using a mixture of 50 mol% methanol in water with methanol
ꢁ1
WHSV from 1 to 21 h . The catalyst conversion capacities were
Table 1 shows the BET specic surface area (t-micro-pore
and t-meso-pore), pore volume (t-micro-pore), and pore size of
estimated by using the methanol WHSV for complete methanol
conversion at a certain reaction time. In the results (Fig. 4A),
the catalysts calculated from the N
isotherms. All the parameters decreased in value aer 3 wt%
Bi loading: the total pore volume shrunk by 22.5%, the BET
surface area and microporous volume decreased respectively by
4.9% and 13.9%, and the pore size decreased by 22.9%
2
adsorption/desorption
ꢁ1
with WHSV from 1 to 2 h
at early time-on-stream, the
bismuth-containing HZSM-5 catalysts displayed higher meth-
anol conversion than the parent HZSM-5. During the MTO/MTP
processes, methanol molecules diffuse into the zeolite pores
and react at the active sites to produce light olens (e.g.,
ethylene, propylene, and butylenes). Then the rapid secondary
reactions could form paraffins, aromatics, and higher olens by
2 3
O
1
compared to the parent HZSM-5. These changes further imply
that some of the bismuth was dispersed on the surface and the
rest entered the channels of HZSM-5. Between 3 wt% and 5 wt%
3
hydrogen transfer, alkylation, and polycondensation. The
Bi
indicating that the deposition of Bi
pore openings and hence restricted further penetration of Bi
into the pores. In other words, a small amount of Bi O pene-
2
O
3
loading, the structural parameters only changed slightly,
2 3
O
partially blocked the
2 3
O
2
3
trated the pores of HZSM-5, while a larger fraction of Bi O was
2
3
located on the external surface of the HZSM-5 zeolite crystals.
This resulted in the narrowed pore openings and reduced
apparent pore size for the HZSM-5 zeolite channels.
Table 1 Textural and structural parameters of HZSM-5 catalysts
before and after bismuth modification
Specic surface area
m g
Pore volume
Pore size
nm
2
ꢁ1
ꢁ3 ꢁ1
cm
g
Catalysts
S
BET
S
mic
S
mes
Total
V
mic
BJH
HZSM-5
a
b
388
330
323
356.0
308.0
302.0
32.0
22.0
21.0
0.2422
0.1878
0.1804
0.1774
0.1527
0.1456
2.17
1.67
1.67
Fig. 3 NH -TPD profiles of the samples: HZSM-5, 3 wt% Bi O /HZSM-
3
2
3
5 (a), and 5 wt% Bi O /HZSM-5 (b).
2
3
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ꢁ
1
at 14 h . Similarly, the value for b was about 100% and 91.5%
ꢁ1
at WHSV ¼ 6 and 10 h , respectively. The conversion capacities
of bismuth-containing HZSM-5 catalysts were noticeably lower.
A similar phenomenon was described for the HZSM-5 zeolite co-
64
modied with P and Mn. The observations in this study can be
explained by the reduced concentration and strength of the
strong acid sites, narrowed pore openings, and reduced
apparent pore size of the channels of the bismuth-containing
HZSM-5 catalysts (a and b). It is known that the density and
strength of acid sites have profound effects on the activity and
76
lifetime of zeolite catalysts. Since the diffusion limitation
increases with the Bi O loading, the lower conversion capac-
2
3
ities aer the bismuth loading may also be partly due to the
higher diffusional resistance that reduces the overall reaction
rates.
Product selectivity. The selectivities for different hydrocar-
bons with varying methanol WHSV are shown in Fig. 4B–G. It
can be seen from Fig. 4B that the ethylene selectivity decreased
with increasing methanol WHSV, in close agreement with the
77
results by Dessau (which indicate that ethylene was only ob-
tained at low WHSV, i.e., long contact times). At identical
reaction conditions, a and b displayed lower ethylene selectivity
than the parent HZSM-5. Especially, the ethylene selectivity
decreases with decreasing pore volume and pore size of the
catalyst.
From Fig. 4C and E, the selectivities for propylene and
butylenes rst increased and then decreased with increasing
methanol WHSV, whereas the opposite trend (Fig. 4F and G)
was observed for lower alkanes (C
1
–C
hydrocarbons or aromatics). The selectivity
toward propylene appears to be ordered as b > a > unmodied
Fig. 4 Methanol conversion and product selectivity vs. WHSV using HZSM-5. This may be due to the strong correlation among the
4
) and liquid heavy
+
hydrocarbons (C
5
different zeolite catalysts. Reaction conditions: P ¼ 0.1 MPa, and
pore volume, pore size, and number of acid sites. Increased
Bi O loading reduces the number of acidic sites, which can
n(MeOH)/n(H
2
O) ¼ 1/1.
2
3
successfully suppress the hydride transfer and propylene oli-
gomerisation reactions.
general consensus is that the intermediate in the dehydration
The ratio between the propylene and ethylene selectivities (P/
reaction of methanol to dimethyl ether over solid acid catalysts E ratio) as a function of methanol WHSV is shown in Fig. 4D.
is the surface methoxy group [SiO(CH )Al]. The highly reactive The P/E ratio was enhanced with increasing WHSV, albeit at the
3
surface methoxy species can contribute to the methylation of expense of the methanol conversion, in agreement with the
7
alkenes, alkanes, and aromatics, leading to the formation of report by Losch et al. Under identical reaction conditions, the
74,75
a hydrocarbon pool to start the MTO/MTG process.
The P/E ratios for a and b are higher than that of the parent HZSM-5.
narrowed pore openings of ZSM-5 in a and b limit the diffusion Especially, this ratio is increased while the pore volume and
of reactants and products within the catalysts. Therefore, the pore size of the catalyst are decreased. The research of Teketel
hydrocarbon pool species easily accumulate within the pores, et al. shows that even subtle changes in the pore size may
2
7
thereby enhancing the autocatalytic effect. From Fig. 4F and E, dramatically inuence the product shape selectivity.
+
a and b produced less C5 hydrocarbons than the parent HZSM- It is generally accepted that two catalytic cycles occur
, together with very low yields of C –C saturated hydrocar- simultaneously during the MTH (methanol to hydrocarbon)
5
1
4
bons. The results obviously show that the bismuth-containing reaction over HZSM-5 zeolite: the aromatic-based cycle (ethene
HZSM-5 catalysts could reduce the catalyst induction period formation from the lower methylbenzenes followed by reme-
and increase the rate of methanol conversion (Fig. 4A).
thylation), and the olen-based cycle (a methylation/cracking
78
With further increase in the methanol WHSV, the catalysts cycle involving only the C3+ alkenes). Narrowing the pore
exhibited nearly 100% methanol conversion. In the case of openings and reducing the apparent pore size of the HZSM-5
HZSM-5, the transformation of methanol remained approxi- channels are likely to suppress the aromatic-based cycle that
ꢁ1
mately 100% at WHSV ¼ 18 h and then declined to 95.5% at requires more space, and favour the alkene cracking and
ꢁ1
54
2
1 h . However, the methanol conversion for a remained at methylation. The ratio of ethene to (2-methylbutane + 2-
approximately 100% at WHSV ¼ 12 and then declined to 96.6% methyl-2-butene) yields (ethene/2 MB) can be used to describe
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the relative propagation of the aromatic- and olen-based cycles
in MTH catalysed by HZSM-5, where a high (low) ethene/2 MB
ratio indicates increased propagation of the aromatic-based
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1
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Bi O -modied HZSM-5 catalysts showed substantial propylene
5
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anol to propylene, compared with the parent HZSM-5 zeolite
catalyst. The enhanced catalytic performance can be attributed
to the narrowing of the pore openings, reduced the apparent
pore size of the HZSM-5 zeolite channels, together with the
lowered Brønsted acidity. Increasing the methanol WHSV also
enhanced the propylene selectivity and P/E ratio, although at
the expense of methanol conversion. These results contribute to
the fundamental understanding of selectivity control in the
MTP reaction. The approach discussed here can also be used for
the rational design of new catalysts for this process. In fact, we
have designed a high effective MTP catalyst by a direct synthetic
method.
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Datong Science and Technology Public Relations Project
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2
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(2015021), and the Doctoral Science Foundation of ShanXiDa-
Tong University (No. QD201049). We also thank Dian-Hua Song,
Yao-Ya Luo, Yi-Bo Gong, Jin-Yi Cao, and Bing-Xi Wang for their
assistance with the reaction experiments.
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