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High-performance SS-fiber@HZSM-5 core-shell catalyst for methanol-to-

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DOI: 10.1016/j.micromeso.2015.09.039

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 Microporous and Mesoporous Materials 221 (2016) 187e196

Contents lists available at ScienceDirect

Microporous and Mesoporous Materials

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

High-performance SS-fiber@HZSM-5 coreeshell catalyst for

methanol-to-propylene: A kinetic and modeling study
Ming Wen, Jia Ding, Chunzheng Wang, Yakun Li, Guofeng Zhao, Ye Liu, Yong Lu*
Shanghai Key Laboratory of Green Chemistry and Chemical Processes, School of Chemistry and Molecular Engineering, East China Normal University,
Shanghai 200062, China

a r t i c l e i n f o a b s t r a c t

Article history: For the methanol-to-propylene process, a lumped kinetic model was developed on the basis of dual-cycle
Received 18 August 2015 reaction mechanism, which attempted to reflect the main reaction paths with a combination to show the
Accepted 22 September 2015 evolution of mole fraction of individual light olefins (C2 ] , C3 ] and C4 ] ) with space time. The experi-
Available online 9 October 2015
ments were performed in a continuous flow fixed-bed reactor at 0.1 MPa as well as varied reaction
temperature from 400 to 480
C and space time from 0.3 to 32.0 gcatalyst h mol1, and the experimental
Keywords:
data obtained on the structured SS-fiber@HZSM-5 and powdered HZSM-5 catalysts were fitted by
Methanol-to-propylene
MATLAB software based on the established model. The fitted results show that the lumped kinetic model
Kinetics
Modeling study
well describes the product distribution and is identified to be suitable by model identification. Compared
Structured catalyst to the powdered HZSM-5, the SS-fiber@HZSM-5 shows higher diffusion efficiency and narrower resi-
ZSM-5 zeolite dence time distribution, not only promoting the propylene formation but also improving the utilization
efficiency of the structured HZSM-5.
© 2015 Elsevier Inc. All rights reserved.

1. Introduction namely MTH) in some acidic zeolite catalysts (e.g., HZSM-5 and
HSAPO-34) under appropriate reaction conditions [7]. Depending
Propylene is one of the most important raw materials in on the desired product, MTH process is classified into the following
chemical industry and widely used for the production of poly- types: methanol-to-gasoline (MTG, mainly producing gasoline)
propylene, acrylonitrile, and propylene oxide, as well as the syn- [8,9], methanol-to-aromatics (MTA, mainly aromatics) [10,11],
thesis of plastics, rubber and many other daily necessities [1,2]. In methanol-to-olefins (MTO, mainly ethylene and propylene) [12,13]
recent years, with the ever-increasing dilemma between the and methanol-to-propylene (MTP, mainly propylene) [14e16]. The
continuous consumption of the finite petroleum reserves and the global demand for propylene is growing faster than ethylene [6],
sharply increased demands for propylene and its derivatives, the and it is thus particularly desirable to develop catalysts preferable
traditional petroleum-based production (such as steam thermal to MTP process.
cracking of naphtha and refinery fluid catalytic cracking (FCC)) is Since the first discovery on MTH process by Mobil researchers in
difficult to meet the requirement of propylene. Therefore, it be- 1976 [17], its mechanism has become one of the most controversial
comes urgent to develop economical and energy-efficient pro- topics in heterogeneous catalysis [2]. In the early 1990s, Dahl and
cesses to replace the petroleum-based production of propylene Kolboe proposed the “hydrocarbon pool” mechanism over HSAPO-
[1,2]. 34 [18e20]. Subsequently, Svelle et al. investigated the MTH
Natural gas [3] and some gasifiable carbon-rich materials such pathway over HZSM-5 by 13C labeling strategy, which revealed that
13
as coal [4] and biomass [5] can be firstly transformed into syngas C is divided into two groups in the products: one group of C3eC6
(mixture of H2 and CO) and subsequently converted into methanol olefins and the other group of ethylene and aromatics [21].
through the well-established technologies [6]. Methanol can be Accordingly, dual-cycle mechanism consisting of aromatic-based
transformed into hydrocarbons (methanol-to-hydrocarbons, cycle (main products of ethylene and aromatics) and olefin-based
cycle (main products of C3eC6 olefins) were proposed and widely
accepted as the dominant reaction mechanism of MTH process on
HZSM-5 [22]. Notably, the general process of olefin-based cycle is
* Corresponding author. Tel./fax: þ86 21 62233424. methylating light olefins to higher olefins and higher olefins
E-mail address: [email protected] (Y. Lu).

http://dx.doi.org/10.1016/j.micromeso.2015.09.039
1387-1811/© 2015 Elsevier Inc. All rights reserved.
188 M. Wen et al. / Microporous and Mesoporous Materials 221 (2016) 187e196

cracking into light olefins, and therefore the generation and con- kinetic models suffer either from severe complexity or from over-
sumption of propylene can be approximately regarded as a simplification. For example, Park [60,61] formulated detailed ki-
consecutive reaction. netic models at the elementary step level, including 726
Compared with other MTO catalysts such as SAPO-34, ZSM-5 elementary steps, 142 olefins and 83 carbenium ions, which is so
favors competing formation of the propylene with relatively slow complex that it is difficult to apply; while, in contrast, Aguayo [62]
coke-induced deactivation, making it possible to use fixed bed established a very simple kinetic model, only containing seven
reactor with excess catalysts [23]. In this context, most attention lumps (oxygenates, n-butane, C2eC4 olefins, C2eC4 paraffins
has focused on tuning the acidity (strength and density) [24e27], (without n-butane), C5eC10 fraction and methane), with regarding
size- and/or morphology-controllable synthesis [28e31] and hier- the C2eC4 olefins as a lump, being unable to meet the requirements
archical design of the pore structure [32,33] of the ZSM-5 zeolite. In of separately describing ethylene and propylene formation. It is
a case of ZSM-5 synthesized via the fluoride route [28], its low thus necessary to further improve the model to study MTP reaction
density of strong acid sites in combination with the long diffusion kinetics. Xiao [63,64] proposed a lumped kinetic model consisting
pathway and few crystal defects delivers a good propylene to of 17 reactions among 15 species, in which light olefins are
ethylene ratio of ~5 with 66% selectivity toward C2eC4 olefins and described separately, which could be applied to describe their
complete methanol conversion at 350
C. Moreover, very high monolith reactor behavior of MTP.
propylene to ethylene ratio of above 10 is also reported to be In the present work, we established a reaction network based on
obtainable over the ZSM-5 zeolite catalysts with additives (ZrO2 the dual-cycle mechanism (olefin-based cycle and aromatic-based
and H3PO4) by using dimethyl ether (DME) and N2 as feedstock cycle). This network not only simply described the rapid equilib-
(DME to N2 mole ratio of 1:5) due to the depression of ethylene rium, olefin-based cycle, aromatic-based cycle, methanation, and
formation rather than promotion of the propylene selectivity [34]. the generation of other alkanes and high-carbon hydrocarbons, but
In spite of these promising results, their practical application in also particularly described the individual formations of C2 ] , C3 ]
a fixed bed reactor is still significantly challenging, as macroscopic and C4 ] . Accordingly, a kinetic model (consisting of 19 reactions
shape of microgranules or extruded pellets a few millimeters in size involving 10 lumps: methanol, dimethyl ether, ethylene, propylene,
are required in the real-world forms rather than as-made powders. butene, pentene, hexene, methane, C2eC6 alkane and C7þ) was
Therefore, some problems emerge in these cases of mass/heat developed. The experimental kinetic data obtained from our
transfer limitations, high pressure drop, non-regular flow pattern structured and powdered catalysts were fitted in our kinetic model
and adverse effects of the used binders, which will reduce the by MATLAB software, and the pre-exponential factors and activa-
intrinsic catalyst selectivity and activity. Recently, microfibrous tion energies were obtained, indicating that the active center uti-
structured catalysts and reactors (MSCRs), as one primary kind of lization efficiency and hexene cracking into propylene apparent
structured catalysts or catalytic reactors (SCRs), have been devel- reaction rate of the structured catalyst are higher than of the
oped and applied in order to achieve the aim of process intensifi- powdered one. Therefore, the structured SS-fiber@HZSM-5 cor-
cation in chemical industry, because MSCRs and other SCRs can be eeshell catalyst exhibited longer lifetime and higher propylene
precisely designed in full detail up to the local surroundings of the selectivity [16,58].
catalyst, and the exact shape and size of all column internals are
determined by pre-design and calculation rather than trial and 2. Experimental
error [35,36]. Therefore, these MSCRs exhibit great flexibility with
respect to different length scales (e.g., diffusion lengths and voi- 2.1. Synthesis of the structured SS-fiber@HZSM-5 coreeshell
dage) and allow exceptionally large rates and selectivities [36,37], catalyst
and have many significant functional advantages over the con-
ventional catalysts and reactors, providing broad prospects in The structured SS-fiber@HZSM-5 coreeshell catalyst was syn-
desulfuration [38,39], air filtration [40,41], H2 fuel generation and thesized, as described elsewhere [58], by direct growth of ZSM-5
cleanup [42e45], selective oxidation [46e52] and other fields crystals on macroscopic thin-sheet sinter-locked microfiber of
[53e56], especially providing a new way of designing efficient stainless steel 316-L fibers consisting of 15 vol% SS-fiber and 85 vol%
catalysts and reactors for mass and/or heat transfer limited re- voidage (SS-fiber, 20 mm in dia., purchased from Western Metal
actions [57]. In our previous studies [16,58], a new standing-free Material Co. Ltd., China). Firstly, circular chips (16.1 mm in dia.) of
microfibrous-structured ZSM-5 zeolite catalyst was developed, SS-fiber substrate were soaked in HCl (1 wt%) aqueous solution for
being obtainable in a macroscopic scale by direct growth of the 0.5 h, sonicated in acetone for 5 min, thoroughly washed using
ZSM-5 zeolite crystals onto a three-dimensional (3D) porous deionized water, and then dried at 80
C in air. Secondly, the SS-
network of sinter-locked metal microfibers. Thanks to the above fiber substrate chips were seeded with the ZSM-5 nanocrystals
beneficial properties, our structured SS-fiber@HZSM-5 coreeshell using dip-coating method. The dip-coating suspension was pre-
catalyst demonstrated visible promotion on the selectivity to C2eC4 pared by adding 1 wt% ZSM-5 seeds (SiO2/Al2O3 ratio ¼ 180; crystal
olefins especially to propylene with obviously prolonged lifetime in size: 100e200 nm) into a silica solegel (1 wt% SiO2) and its pH was
stream, compared to the corresponding pure powdered HZSM-5 adjusted to 2.3 using HCl (1 wt%) aqueous solution prior to the dip
catalyst. However, deep insight into such selectivity/stability pro- coating. Seeding of the ZSM-5 was performed by slowly dipping the
moting effect of the microfibrous-structured design is particularly SS-fiber substrates into the above suspension for 10 s, followed by
desirable to further improve the catalyst performance or design drying at 25
C for 14 h and calcining at 450
C for 2 h in air. Thirdly,
next-generation catalyst with more advanced performance. This the seeded SS-fiber circular chips (3 g) were placed in a Teflon-lined
work attempts to carry out kinetic and modeling study of MTP steel autoclave (100 mL) filled with 70 mL synthesis gel consisting
reaction over our structured SS-fiber@HZSM-5 catalyst as well as of tetraethylorthosilicate (TEOS, A.R.)/tetrapropylammonium
powdered HZSM-5 catalyst for contrastive study, because it is a (TPAOH)/NaOH (C.P.)/NaAlO2 (C.P.)/H2O with a mole ratio of 1/0.25/
useful and helpful tool for us to accomplish this goal. 0.4/0.010/250 (corresponding to the gel SiO2/Al2O3 mole ratio of
Due to the early rudimentary understanding of the complexity 200), followed by gel-aging at room temperature for 4 h. After
of reaction mechanism, rigorous kinetic treatments may neither be hydrothermal synthesis at 180
C for 48 h, the resulting samples
practicable nor have much practical justification [59]. Subse- were washed thoroughly, dried at 100
C overnight, and directly
quently, some progress has been made in kinetic studies, but the calcined in air at 550
C for 5 h to remove the organic template.
 M. Wen et al. / Microporous and Mesoporous Materials 221 (2016) 187e196 189

Finally, the SS-fiber@ZSM-5 products were all converted to the H- acts as the raw material for all the following reactions, the meth-
form by the ion-exchanging with an aqueous NH4Cl (1 mol L1) anol conversion (C) and product selectivity (Sj) are calculated by
solution at 80
C and calcining at 550
C for 5 h in air, the HZSM-5 treating DME as reactant based on carbon number and expressed as
zeolite content loaded on the catalyst was 19 wt%. the following equations:

2.2. Synthesis of the powdered HZSM-5 catalyst xCH3 OH þ 2xDME

C ¼1 PN (1)
j¼1 nj xj
As previously noted, when using the synthesis gel with SiO2/
Al2O3 mole ratio of 200, the SiO2/Al2O3 mole ratio of HZSM-5 nj xj
zeolite shell for the as-prepared structured SS-fiber@HZSM-5 is Sj ¼ PN (2)
j¼1 nj xj  xCH3 OH  2xDME
147 [58], while the SiO2/Al2O3 mole ratio of the HZSM-5 collected at
autoclave is consistent with that in the synthesis gel. Therefore, in
order to assure the comparative study of the structured and where N is the number of components, xj is the mole fraction of
powdered HZSM-5 catalysts at equivalent SiO2/Al2O3 mole ratio, component j in the reaction effluent, xCH3 OH and xDME are respec-
the powdered HZSM-5 catalyst was hydrothermally synthesized tively the mole fractions of methanol and DME in the reaction
using a synthesis gel of TEOS/TPAOH/NaOH/NaAlO2/H2O ¼ 1/0.25/ effluent, nj is the carbon number of component j.
0.4/0.014/250 (corresponding to the gel SiO2/Al2O3 mole
ratio ¼ 147) with other conditions unchanged. The real SiO2/Al2O3 3. Results and discussion
mole ratio for such obtained ZSM-5 zeolite was determined to be
155 by means of inductively coupled plasma atomic emission 3.1. Kinetic experimental data for our structured and powdered
spectrometry (ICP-AES; Thermo IRIS Intrepid II XSP ICP spectrom- HZSM-5 catalysts
eter, USA). After ion-exchanging and calcining, the resulting HZSM-
5 was pressed and then crushed and sieved to 100e300 mm as the Fig. 1 shows the space time dependent reactant conversion
powdered catalyst. (reactant includes methanol and DME, see previous definition of
reactant conversion in the section of “Experimental”) in MTP pro-
2.3. MTP reaction kinetic measurement cess using the structured SS-fiber@HZSM-5 and powdered HZSM-5
catalysts. Clearly, the structured SS-fiber@HZSM-5 catalyst is able
MTP kinetic experiment of the catalysts was conducted in a to deliver 100% conversion over a much wider range of space time,
continuous flow fixed bed reactor, using a quartz tube reactor (i.d. compared to the powdered HZSM-5 catalyst. Complete conversion
16 mm, length 765 mm) vertically placed in a tubular electric is maintained over the SS-fiber@HZSM-5 along with the space time
furnace. Methanol (A.R., Sinopharm Chemical Reagent Co., Ltd.) was until to 3.2 gcatalyst h/molCH3 OH while until to 16.0 gcatalyst h/
fed continuously using a high-performance liquid chromatography molCH3 OH over the powdered HZSM-5 only. We believe that the
(HPLC) pump. Electrical heating tape was wrapped around the micro-structured design is paramount to the enhanced conversion
entrance of the reactor to control the temperature of 130
C, pre- at very short contacting time rather than the zeolite acidity because
heating the liquid methanol to vapor in the highly purified N2 flow of the equivalent SiO2/Al2O3 ratio of the powdered HZSM-5 to
to obtain a gaseous mixture feed with methanol concentration of HZSM-5 shell over the structured catalyst (structured, 147;
30 vol%. Each catalyst was packed into the reactor with a constant powdered, 155). The possible explanation is that the SS-
HZSM-5 zeolite content of 0.2 g. Note that circular chips (16.1 mm fiber@HZSM-5 catalyst bed presents much higher acid site utiliza-
diameter) of the SS-fiber@HZSM-5 catalyst were packed layer-up- tion efficiency than the powdered HZSM-5 catalyst bed. For the SS-
layer into the tube reactor, the diameter of 0.1 mm larger than fiber@HZSM-5 catalyst, zeolite crystals are directly grown on the
the i.d. of the tubular reactor was retained deliberately to avoid the cylindrical fiber core surface to form a uniform density membrane
appearance of the gap between the reactor wall and the edges of shell as thick as ~5 mm. For the powdered HZSM-5 catalyst, the
catalyst chips thereby preventing the gas bypassing. The powdered powders are nearly spherical with a diameter of 100e300 mm,
HZSM-5 catalyst was diluted using 100e300 mm quartz sand to which is much larger than zeolite shell thickness of ~5 mm for the
assure an equivalent bed volume as to the microfibrous structured
bed. The effluent gas was quantitatively analyzed by an on-line gas
chromatography-flame ionization detector (GC-FID, Shimadzu
2014C) with a 30-m HP-PLOT/Q capillary column.
At the beginning of the experiment, the reactor tube was heated
in the highly purified N2 flow (heating rate of 10
C/min), after the
temperature of the catalyst bed reached to the set value and was
stable, turn on the pump to input methanol, regulate the flow of
methanol and nitrogen according to the space time value ¼ 32.0
gcatalyst h/mol, corresponding to the methanol weight hourly space
velocity (WHSV, to ZSM-5 zeolite mass) of 1 h1. Then the space
time was gradually reduced (i.e., the WHSV was gradually
increased) at intervals of 1 h by adjusting the flow rate of N2 and
methanol. The product distribution was measured at different
space time, until the space time and the catalysts' conversion of
methanol were reduced to very low.

2.4. Definition of reactant conversion and product selectivity

Fig. 1. The reactant conversion against the space time for the MTP reaction over the
Given that the very fast transformation of methanol-to-DME structured SS-fiber@HZSM-5 catalyst (denoted as SS) and powdered HZSM-5 catalyst
initially takes place, and more particularly, DME subsequently (denoted as Powder, hereinafter inclusive).
190 M. Wen et al. / Microporous and Mesoporous Materials 221 (2016) 187e196

SS-fiber@HZSM-5 (Supporting Fig. S1). As a result, the structured independent on the reaction temperature of both catalysts. This
SS-fiber@HZSM-5 catalyst significantly improves the mass transfer observation is most likely due to that the reaction is wholly gov-
by nature. Actually, it can be estimated from the evolution of con- erned by diffusion limitation in the whole temperature range
version with space time that the SS-fiber@HZSM-5 catalyst offers studied.
the maximum utilization efficiency of acid site (it can be reflected Unlike the ethylene formation, the structured catalyst shows a
by the space time corresponding to the conversion beginning to fall space time dependent propylene formation evolution quite
from 100%) much higher than the powdered HZSM-5 catalyst different from the powdered catalyst (Fig. 2B). Over the structured
(Fig. 1). The structured design of HZSM-5 crystals provides a very SS-fiber@HZSM-5 catalyst, the propylene selectivity increases
low turning space time of 3.2, being 1/5 lower than that of 16.0 over sharply and reaches the climax along with the space time from 0.3
the powdered HZSM-5 catalyst, meaning that the acid site utiliza- increased to ~1.1 gcatalyst h/molCH3 OH , and then decreases gradually
tion efficiency of the structured SS-fiber@HZSM-5 catalyst is 4-fold with further increasing the space time. Over the powdered HZSM-5
higher than of the powdered HZSM-5 catalyst. catalyst, such peaking feature of propylene selectivity against space
Besides improving the zeolite utilization efficiency, our struc- time is not observed, instead of a monotonously decreasing ten-
tured design of HZSM-5 zeolite provides ability to promote the dency. At 400
C, the propylene selectivity of these two catalysts is
propylene formation. Fig. 2 shows the selectivity evolution of basically identical. At 420
C and 450
C, propylene selectivity of the
ethylene and propylene in the MTP reaction along with the space structured catalyst is higher than that of the powdered catalyst
time over the two catalysts, and both of them show similar ethylene when the space time is low (<10.7 gcatalyst h/molCH3 OH at 420
C and
selectivity evolution against space time (Fig. 2A). Whereas the <~19.0 gcatalyst h/molCH3 OH at 450
C), and much higher with the
ethylene selectivity is increased with the space time below ~5 gca- decrease of the space time. Most notably, at 480
C, our structured
talyst h/molCH3OH and then remains almost unchanged with further HZSM-5 catalyst always delivers much higher propylene selectivity
increasing the space time, the powdered HZSM-5 catalyst always compared to the powdered HZSM-5 catalyst. We believe that our
delivers higher ethylene selectivity than the structured one in the structured design of the HZSM-5 is paramount to the improved
whole space time range studied. As previously noted, our struc- propylene selectivity. A possible explanation is that the micro-
tured design shows ability, to some extent, to suppress the structured catalytic bed provides a narrow resistance time distri-
aromatic-based reaction cycle that is favorable for the ethylene bution, being essential for the enhanced formation of propylene
formation [16,58]. In addition, at the space time below ~5 gcatalyst h/ that is the intermediate of the serial methylation/cracking (namely
molCH3 OH , it is observed that the ethylene selectivity almost seems olefin-based cycle) pathway in the MTP mechanism [22,65].
Clearly, the above results of the ethylene and propylene for-
mation evolution against the space time confirms their separated-
generation mechanism while the structured design of HZSM-5
shows an ability for promoting the methylation/cracking pathway
and inhibit the aromatic-based cycle. Therefore, aromatic-based
cycle and olefin-based cycle, which are favorable to form ethylene
and propylene respectively, should be taken into account to the
MTP reaction network establishment for distinguishing the pro-
duction of ethylene and propylene.

3.2. Reaction network and kinetic model for MTP process

We herein proposed a MTP reaction network based on the dual-

cycle mechanism (olefin-based cycle and aromatic-based cycle,
including 10 lumps: methanol, dimethyl ether, ethylene, propylene,
butene, pentene, hexene, methane, C2eC6 alkane and C7þ, Fig. 3),
with a notice of that the stoichiometric coefficients of all reactions
were omitted to write. In the reaction network, the main carbo-
naceous matters were taken into account, with ignoring hydrogen,
water and other trace matters (such as CO2, coke, etc.).
The reactions are classified into five categories (including the
rapid equilibrium (between methanol and DME), olefin-based cy-
cle, aromatic-based cycle, methanation, and generation of other
alkanes and high-carbon hydrocarbons, Table 1) with a total of 19
reactions. Initially, methanol molecules are quickly transformed
into DME, which could achieve a rapid equilibrium, and then the
following four kinds of reactions subsequently take place using
DME as reactant. Olefin-based cycle is divided into methylating
light olefins to higher olefins (C5 ] and C6 ] ) and higher olefins
cracking into light olefins (major C3 ] and C4 ] , and minor C2 ] ).
Methylation reactions include a small amount of propylene pro-
duced in the initial induction period reacting with DME to generate
butene, butene with DME to pentene, pentene with DME to hexene,
and hexene with DME to C7þ; cracking reactions include hexene
Fig. 2. The ethylene (A) and propylene (B) selectivities against the space time for the cracking into propylene, hexene into ethylene/butene, pentene into
MTP reaction over the structured SS-fiber@HZSM-5 and powdered HZSM-5 catalysts.
Note: the ethylene and propylene selectivities over the powdered HZSM-5 catalyst
ethylene/propylene, and two butene molecules polymerizing and
were not obtained at the space time of below 1.1 gcatalyst h/molCH3 OH , because of almost then cracking into propylene/pentene. There are many kinds of
undetectable methanol conversion. intermediate species which cannot be separated and detected
 M. Wen et al. / Microporous and Mesoporous Materials 221 (2016) 187e196 191

Fig. 3. The proposed reaction network for MTP process based on the dual-cycle mechanism.

Table 1
Classification and rate equation of each reaction of MTP process.

Category Reaction Rate equation

k1
Rapid equilibrium 2CH3 OH!CH3 OCH3 þ H2 O r1 ¼ k1 xCH3 OH
k2
CH3 OCH3 þ H2 O!2CH3 OH r2 ¼ k2 xDME
k3
Olefin-based cycle 2C3 H6 þ CH3 OCH3 !2C4 H8 þ H2 O r3 ¼ k3 xDME xC3 H6
k4
2C4 H8 þ CH3 OCH3 !2C5 H10 þ H2 O r4 ¼ k4 xDME xC4 H8
k5
2C5 H10 þ CH3 OCH3 !2C6 H12 þ H2 O r5 ¼ k5 xDME xC5 H10
k6
2C6 H12 þ CH3 OCH3 !2C7 þ r6 ¼ k6 xDME xC6 H12
k7
C6 H12 !2C3 H6 r7 ¼ k7 xC6 H12
k8
2C3 H6 !C6 H12 r8 ¼ k8 xC3 H6
k9
C6 H12 !C2 H4 þ C4 H8 r9 ¼ k9 xC6 H12
k10
C2 H4 þ C4 H8 !C6 H12 r10 ¼ k10 xC2 H4 xC4 H8
k11
C5 H10 !C2 H4 þ C3 H6 r11 ¼ k11 xC5 H10
k12
C2 H4 þ C3 H6 !C5 H10 r12 ¼ k12 xC2 H4 xC3 H6
k13
2C4 H8 !C3 H6 þ C5 H10 r13 ¼ k13 xC4 H8
k14
Aromatic-based cycle CH3 OCH!C2 H4 þ H2 O r14 ¼ k14 xDME
k15
Methanation CH3 OCH3 þ 2H2 !2CH4 þH2 O r15 ¼ k15 xDME
k16
C5 H10 þH2 !C4 H8 þCH4 r16 ¼ k16 xC5 H10
k17
Generation of other alkanes and high-carbon hydrocarbons C3 H6 !C2  C6 alkane r17 ¼ k17 xC3 H6
k18
CH3 OCH3 !C2  C6 alkane r18 ¼ k18 xDME
k19
C6 H12 !C7 þ r19 ¼ k19 xC6 H12

easily by the gas chromatography in the aromatic-based cycle, equation of the components can be expressed by the linear com-
moreover some studies [63,66] show that aromatic-based cycle is bination of the 19 reaction rate equations, where W is the mass of
not dominant for HZSM-5 catalyst. Thus the process is simplified HZSM-5, F0 is the feed mole flow rate of methanol (equations
with DME to ethylene, and the specific steps are omitted. Metha- (3)e(12)). In order to fit more accurately, a few coefficients in front
nation reactions include DME-into-methane as well as pentene- of reaction rate constant in the kinetic equations are not in accor-
into-butane/methane. Moreover, C2eC6 alkane lump is assumed dance with the stoichiometric coefficients of the chemical equa-
to be derived from propylene and DME as well as C7þ lump directly tions in the reaction network, which may be due to the assumed
from hexene. reaction network simplifies the actual reaction mechanism, and
It should be noted that the reaction network is semi-empirical cannot accurately represent the true reaction pathway. Therefore,
and cannot fully express the real reaction process. As the elemen- some coefficients need to be modulated in order to make the dif-
tary reactions and intermediate species in MTP process are ference between the calculated and experimental values smaller.
numerous and difficult to measure completely and accurately by
experiment, so the reaction network simplifies the actual reaction
process and makes some assumptions on the premise of fitting to dxCH3 OH
rCH3 OH ¼ ¼ 2r1 þ 2r2 (3)
the experimental data very well. Although it does not represent the dðW=F0 Þ
reaction mechanism fully and accurately, the reaction network and
corresponding kinetic model can well predict the effects of reaction
conditions on product distribution. dxDME
rDME ¼ ¼ r1  r2  r3  r4  r5  r6  r14  r15  r18
According to the established reaction network, the rate equa- dðW=F0 Þ
tions of all reactions are written in Table 1, where k is the rate (4)
constant and x is the mole fraction of the component in the reaction
effluent. The reaction orders are firstly obtained by assuming each
reaction is elementary reaction, and they are repeated modulated dxC2 H4
to fit the experimental data and finally determined when the rC2 H4 ¼ ¼ r9  r10 þ r11  r12 þ r14 (5)
dðW=F0 Þ
calculated values and experimental values agree well. The rate
192 M. Wen et al. / Microporous and Mesoporous Materials 221 (2016) 187e196

where M is the number of experimental data sets, N is the number

dxC3 H6 of components, xij is the mole fraction of component j in the re-
rC3 H6 ¼ ¼ 2r3 þ 2r7  2r8 þ r11  r12 þ r13  r17
dðW=F0 Þ action effluent under the experimental condition i, while xijc rep-
(6) resents the calculated value corresponding to xij.
The purpose of parameter estimation is to minimize the objec-
dxC4 H8 tive function value by appropriate optimization method. The
rC4 H8 ¼ ¼ 2r3  2r4 þ r9  r10  2r13 þ r16 (7) termination condition of the optimization is that the relative
dðW=F0 Þ
objective function is changing by less than MATLAB default setting
value of 106:
dxC5 H10
rC5 H10 ¼ ¼ 3r4  2r5  r11 þ r12 þ r13  r16 (8)
dðW=F0 Þ OFn  OFn1
 106 (15)
OF
n
dxC6 H12
rC6H12 ¼ ¼ 3r5  2r6  r7 þ r8  r9 þ r10  r19 (9) where OFn is the objective function value of n-th optimization,
dðW=F0 Þ
OFn1 is the objective function value of (n1)-th optimization. If the
termination condition is satisfied, the assumed parameters are
dxCH4
rCH4 ¼ ¼ 2r15 þ r16 (10) regarded as the final fitted values, otherwise the MATLAB built-in
dðW=F0 Þ lsqnonlin program for solving the nonlinear least squares prob-
lems is used to generate new parameters by optimization compu-
dxC2 C6 tations, until the objective function meets the requirements.
rC2 C6 ¼ ¼ r17 þ r18 (11)
dðW=F0 Þ
3.4. Numerical simulation and promotion mechanism for catalytic
dxC7 þ performance improvement
rC7 þ ¼ ¼ 2r6 þ 2r19 (12)
dðW=F0 Þ
The experimental data (points) of the two catalysts at different
temperatures were fitted by the above-described numerical
method based on the proposed kinetic model, and the fitted curves
3.3. Numerical method for the kinetic study (lines) were shown in Figs. 4 and 5. Subsequently, we adopted two
important statistics parameters for the model identification: r2 and
The expression of the rate constant in Arrhenius equation is in F, and they are expressed as formulas (16) and (17), in which Ne is
the form of reference temperature (723 K, i.e., 450
C), that is the the number of experimental points, Np is the dimension of the
exponential term of reaction rate constant changes from the orig- model parameters, yei and yci are experimental value and calculated
inal ð1=TÞ to ðð1=TÞ  ð1=723ÞÞ, which can reduce the correlation value of the dependent variable for the i-th observation respec-
between the pre-exponential factors and activation energies. It is tively. The larger the two values, the more reliable the model to
expressed as the equation (13) [67], where ki is the reaction rate predict the experimental results. For simplicity, r2 is generally set to
constant of reaction i, k0i is the pre-exponential factor of reaction i, be >0.9 as well as F to be >10Fa (Np, NeeNp) (Fa value is obtained
k0i* is the pre-exponential factor of reaction i in the form of refer- from F-test table, significant level of a ¼ 5%, the Fa values of these
ence temperature, Ei is the activation energy of reaction i, R is the two catalysts are all less than 2) [68]. By calculating, for the
molar gas constant, and T is the reaction temperature. structured SS-fiber@HZSM-5 catalyst, r2 is 0.990 and F is 1250.9,
  while for the powdered HZSM-5 catalyst, r2 is 0.995 and F is 2161.9,
E
ki ¼ k0i exp  i which indicate all of the model identification parameters meet the
RT requirements well. Moreover, the calculated points on the fitted
     
E 1 E 1 1 curves meet another requirement of that these points should be
¼ k0i exp  i exp  i 
R 723 R T 723 close to and evenly distributed on both sides of the diagonal in
   parity plots (Figs. S2 and S3 in Supporting information) [68]. All the
E 1 1
¼ k*0i exp  i  (13) above results indicate that the fitted curves for the evolution of
R T 723
mole fraction of each component in the reaction effluent with space
Kinetic model parameter estimation is fitting the unknown time wholly coincide well with the experimental data according to
parameters (the pre-exponential factors of each reaction rate con- our kinetic model, and consequently our proposed kinetic model
stant for the reference temperature and the activation energies) and calculated parameter values are reliable for the two catalysts.
with the experimental data based on rate equations of the com- PNe
ponents. In this work, we use MATLAB software to fit and estimate ðyei  yci Þ2
the parameters. The process is to assume a set of initial parameters,
r2 ¼ 1  i¼1
PNe 2 (16)
y
i¼1 ei
then use the fourth order and fifth order variable step RungeeKutta
method (i.e., MATLAB built-in ODE45 program) to solve the ordi- " #
nary differential equations of components' rate and calculate each PNe PNe
y2 
i¼1 ek i¼1
ðyei  yci Þ2 =Np
component's mole fraction in the reaction effluent corresponding
to different temperatures and different space time. The objective F¼ PNe   (17)
i¼1
ðyei  yci Þ2 = Ne  Np
function is the residual sum of squares of calculated and experi-
mental values: Table 2 lists the calculated kinetic parameters (pre-exponential
factors at a reference temperature of 450
C and activation en-
X
M X
N  2 ergies). It should be noted that, some calculated apparent activation
OF ¼ xijc  xij (14)
energies may be negative since the established reaction network is
i¼1 j¼1
the simplification of the actual reaction and each reaction is not
elementary reaction, which has also been reported in other
 M. Wen et al. / Microporous and Mesoporous Materials 221 (2016) 187e196 193

Fig. 4. Comparison of calculated (lines) and experimental (points) values for the evolution of mole fraction of each component in the reaction effluent with space time over the
structured SS-fiber@HZSM-5 catalyst. A & B, 400
C; C & D, 420
C; E & F, 450
C; G & H, 480
C.

literatures [69,70]. Since our study is based on the apparent ki- hence, with the increase of contacting time, propylene mole fraction
netics, the influence of diffusion has been contained in the kinetic rapidly increases at the beginning, and then gradually decreases
parameters. after reaches a maximum value, forming a turning point (Figs. 4E
Fig. 6 displays the main steps of the olefin-based cycle and the and 5E). Since the rate constant of hexene cracking into propylene
corresponding reaction rate constants of the two catalysts at 450
C, for the structured SS-fiber@HZSM-5 catalyst is much larger than
the generation and consumption of propylene can be approximately that for the powdered HZSM-5 catalyst and the residence time
regarded as a consecutive reaction. The generation rate of propylene distribution of structured SS-fiber@HZSM-5 catalyst is narrower,
from hexene cracking is much faster than its consumption rate, and the turning point for the structured SS-fiber@HZSM-5 catalyst is
194 M. Wen et al. / Microporous and Mesoporous Materials 221 (2016) 187e196

Fig. 5. Comparison of calculated (lines) and experimental (points) values for the evolution of mole fraction of each component in the reaction effluent with space time over the
powdered HZSM-5 catalyst. A & B, 400
C; C & D, 420
C; E & F, 450
C; G & H, 480
C.

more obvious and the corresponding mole fraction of propylene coupling process of flow, transfer and reaction. For both catalysts,
(~45%, as shown in Fig. 4E) is also much higher than that (~30%, as the impact of external diffusion on reaction is approximately same
shown in Fig. 5E) for the powdered HZSM-5 catalyst. at the same space time, and moreover, reactant concentration of
For the gasesolid heterogeneous catalysis, reactant molecules the gas phase and catalyst outer surface is basically consistent due
firstly pass through the laminar boundary layer outside the catalyst, to the large linear velocity in the reaction tube at low space time,
reach the outer surface of the catalyst (i.e., external diffusion), and and the influence of external diffusion to reaction can be ignored.
then diffuse along the internal hole of the catalyst to its inner Therefore, different internal diffusions of the two catalysts directly
surface (i.e., internal diffusion) [71], its apparent performance is a result in the different apparent catalytic performances.
 M. Wen et al. / Microporous and Mesoporous Materials 221 (2016) 187e196 195

Table 2 apparent reaction rate, and is also the ratio of the reaction rate
Kinetic parameters determined by fitting the kinetic model to the experimental constant, as shown in equation (19).
results.
robserved
Reaction k0i* Ei (kJ/mol) h¼ (18)
(molCH3 OH /h/ rintrinsic
gcatalyst)

A B A B hmonolithic rmonolithic kmonolithic 2:14

 ¼ ¼ ¼ 5:9 (19)
k1
2CH3 OH!CH3 OCH3 þH2 O 2.14 0.36 13.46 1.77 hpowdered rpowdered kpowdered 0:36
k2
CH3 OCH3 þH2 O!2CH3 OH 3.70 0.64 13.46 1.77
Thus, the h of the structured SS-fiber@HZSM-5 catalyst is 4.9-
k3
2C3 H6 þCH3 OCH3 !2C4 H8 þH2 O 13.90 1.73 34.62 9.72
k4
2C4 H8 þCH3 OCH3 !2C5 H10 þH2 O 43.92 7.32 44.03 30.08 fold higher than that of the powdered HZSM-5 catalyst. This ex-
k5
2C5 H10 þCH3 OCH3 !2C6 H12 þH2 O 47.25 16.96 16.49 3.23
k6 plains the reason why the evolution of conversion with space time
2C6 H12 þCH3 OCH3 !2C7 þ 25.21 20.28 125.89 151.27
k7
C6 H12 !2C3 H6 123.31 82.27 109.08 0.22 of the two kinds of catalysts is very different in kinetic experiments.
k8
2C3 H6 !C6 H12 4.39 1.25 0.63 181.54 For traditional powdered catalyst, the utilization efficiency of the
k9
C6 H12 !C2 H4 þC4 H8 0.86 13.12 1.15 120.32 catalyst is reduced since the transfer and diffusion limitations
k10
C2 H4 þC4 H8 !C6 H12 0.27 1.57 103.56 48.92 hinder the contacting of reactants and catalyst active sites; while
k11
C5 H10 !C2 H4 þC3 H6 2.64 0.57 61.72 143.09
k12
C2 H4 þC3 H6 !C5 H10 3.05 0.50 123.64 200.00
the thin zeolite shell of the structured SS-fiber@HZSM-5 catalyst
k13
2C4 H8 !C3 H6 þC5 H10 0.03 0.01 235.91 283.90 possibly shorten the diffusion path, and therefore keeps a high
k14
CH3 OCH3 !C2 H4 þH2 O 0.33 0.02 94.96 133.90 utilization efficiency of the active sites. The structured SS-
k15
CH3 OCH3 þ2H2 !2CH4 þH2 O 0.10 0.03 141.02 99.48 fiber@HZSM-5 catalyst is still capable of transforming raw mate-
k16
C5 H10 þ H2 !C4 H8 þ CH4 0.01 0.01 63.90 5.62
k17 rials completely when the space time is very low, while only when
C3 H6 !C2  C6 alkane 0.01 0.01 46.72 43.38
k18
CH3 OCH3 !C2  C6 alkane 1.13 0.15 26.24 16.58 the space time is higher can the conversion of powdered HZSM-5
k19
C6 H12 !C7 þ 0.11 0.13 73.92 127.89 catalyst achieve 100%. In the previous kinetic experiment section
A: the structured SS-fiber@HZSM-5 catalyst; B: the powdered HZSM-5 catalyst.
we have revealed that the turning space time (corresponding to the
conversion beginning to fall from 100%, Fig. 1) of the structured SS-
fiber@HZSM-5 catalyst is 4-fold higher than that of the powdered
HZSM-5 catalyst, it is close to the reciprocal of their internal
diffusion effective factor ratio. It shows our kinetic model is reliable,
and the calculated kinetic parameters can well explain the exper-
imental phenomena.

4. Conclusions

A MTP reaction network and a corresponding lumped kinetic

model have been established based on the dual-cycle reaction
mechanism, and the model not only simplifies the complex reac-
tion mechanism but also shows each kind of light olefin's variation
with reaction conditions separately. Kinetic experimental data
were fitted and analyzed by MATLAB software, and the calculated
values agree well with the experimental ones, while the model
identification parameters also meet the requirements, indicating
Fig. 6. Comparison of the calculated reaction rate constants (beside arrows, the unit is that the established model is appropriate. The calculated macro-
molCH3 OH /h/gcatalyst) of the MTP olefin-based cycle main steps at 450
C for the scopic kinetic parameters of different catalysts show that the pro-
structured SS-fiber@HZSM-5 catalyst (upper numbers) and the powdered HZSM-5 pylene generation rate is much faster than its consumption rate.
catalyst (lower numbers).
Because the generation and consumption process of propylene are
consecutive reactions, and the narrower residence time distribu-
Internal diffusion and reaction occur simultaneously, and due to tion is more favorable to the formation of propylene, therefore,
overcoming the diffusion resistance and reaction consumption, the propylene selectivity of the structured SS-fiber@HZSM-5 catalyst is
reactant concentration gradually decreases with the internal higher than of the powdered HZSM-5 catalyst when the space time
diffusion, and the reaction rate is correspondingly reduced. Reac- is low especially at high temperatures. Moreover, the calculated
tion mostly proceeds in outer shell of the catalyst with a certain results also indicate a higher utilization efficiency of the structured-
thickness, while the inner part contributes little to the reaction due design HZSM-5 by a factor of ~5 than of the powdered HZSM-5. In
to the low concentration of reactants, so the inner surface of cata- conclusion, compared with the conventional powdered catalyst,
lyst has not been fully utilized [71]. The internal diffusion effective our structured SS-fiber@HZSM-5 catalyst has narrower residence
factor h is introduced to judge the influence degree of internal time distribution and higher diffusion efficiency, which could
diffusion on the reaction process in the chemical reaction engi- inhibit ethylene formation to promote propylene selectivity and
neering, which is equal to the ratio of apparent reaction rate and increase the utilization efficiency to enhance the catalytic activity.
intrinsic reaction rate (equation (18)) [71]. The h of 1 indicates that
the internal part of catalyst has been fully utilized, while h of 0.1 Acknowledgments
indicates only 10 vol% of catalyst has been efficiently used [72]. The
internal diffusion effective factor ratio (hstructured/hpowdered) of the This work was funded by the “973 program” (2011CB201403)
structured and powdered catalysts at 450
C can be obtained by from the MOST of China, and the NSF of China (21473057, 21273075,
substituting the kinetic parameters of methanol into equation (18). U146212, 21076083). We gratefully acknowledge the partial
Due to the intrinsic reaction rates of the two kinds of catalysts are financial support from the Science and Technology Commission of
the same, the ratio of the effective factor is equal to the ratio of the Shanghai Municipality.
196 M. Wen et al. / Microporous and Mesoporous Materials 221 (2016) 187e196

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