Modeling and Analysis of the Lurgi-Type Methanol to

Propylene Process: Optimization of Olefin Recycle

Xun Huang, Hu Li, Hui Li, and Wen-De Xiao
School of Chemistry and Chemical Engineering, Shanghai Jiao Tong University, Shanghai 200240, China
DOI 10.1002/aic.15565
Published online November 17, 2016 in Wiley Online Library (wileyonlinelibrary.com)

This work proposed a strategy to improve the yield of light olefins of industrial methanol to propylene process by reducing the olefins recycled back into the main reactor and appending an olefin cracking reactor. The heterogeneous fixedbed model was employed to simulate the reactors with a robust mathematical procedure developed to determine the
reactor configuration and the recycle flow rates of the olefins. Two methods were proposed for the modulation: the recycle ratio and species of the olefins, respectively. Results show that the yield of C2C3 olefins can be improved up to
70% from the basement of about 60% when the ratio is reduced from 100% to less than 23% or when only butene apart
from pentene and hexene is recycled back into the main reactor, and the latter method is more effective as its catalyst
C 2016 American Institute of Chemrequirement is seven times less than the formers in the appended cracking reactor. V
ical Engineers AIChE J, 63: 306313, 2017
Keywords: methanol to propylene, process optimization, reactor modeling, propylene

Introduction
Light olefins, i.e., ethylene and propylene, are the key
carbon-based building blocks in the main industrial sectors,
and the majority of them are traditionally produced by thermal
or catalytic cracking of petroleum-based feedstock, i.e., naphtha, gas oil, condensates, and light alkanes. However, because
of the expanding market and the periodic oil crisis, diversification of light olefin feedstock is urgently appealed to reduce the
oil dependence and meet the demand increase.1,2
Methanol to propylene (MTP)3,4 is a famous non-oil route
to produce on-purpose propylene over ZSM-5 zeolite from
coal, natural gas and biomass via methanol as intermediate.
The first industrial MTP process was developed by Lurgi company and has been commercialized in China since 2010 with a
design capacity of 1.5 Mt methanol per year.5 In this process,
the raw material methanol was first converted into an equilibrium mixture of methanol, dimethyl ether (DME) and water in
a pre-reactor to remove partial reaction heat. Then the MTP
reactions were carried out in a three parallel six-stage adiabatic fixed-bed reactors, with two performing MTP reactions
while the rest regenerating catalyst or standing by after the
5
5
regeneration. The olefins including C5
2 and C4 C6 are
recycled back into the reactor and react with the oxygenates
(methanol and/or DME) to achieve the highest yield of propylene, which unfortunately turned out to be only 61.62%, lower
than the expected figure 65% and much lower than the total
yield of ethylene and propylene from a MTO process (over
80%)6,7 using SAPO-34 zeolite catalyst and fluidized reactor.

Correspondence concerning this article should be addressed to W.-D. Xiao at

wdxiao@sjtu.edu.cn.
C 2016 American Institute of Chemical Engineers
V

306

Paraffins and aromatics account for the byproducts, which

are irreversibly produced from olefins through hydrogen transfer mechanism over the acidic sites of the zeolite catalyst. In
our previous work,8 we have modeled and analyzed the industrial six-stage MTP reactor, and found the overlong contact
time in the six stages is one of the main reason for the low propylene yield. Therefore, an immediate way one may conceive
to improve propylene selectivity is to suppress the hydrogen
transfer reactions by decreasing the contact time of olefins over
the acid catalyst. Nevertheless, in the industrial MTP process,
the unwanted C4C6 olefins are recycled back into the reactor,
which dramatically increases the contact time between the reactants and the catalyst. Moreover, the MTP reactors consists of
six stage with parallel methanol and DME introduction but cascade flow of the recycled olefins, making the contact time longer and the yield even worse. A possible way to reduce the
contact time is to pack less catalyst in the reaction zone, but it
will lead to shorter life time of the catalyst and more frequent
regeneration, which is not favorable for industrial operation
with large capacity. Consequently, reducing the amount of olefins recycled into the main reactor becomes a potential strategy
to decrease byproduct and improve propylene yield.
Conversely, feeding olefins into the first stage is probably
indispensable. When methanol is fed alone, an autocatalysis
phenomenon has been observed,9 i.e., the methanol conversion
is very slow at low space time but increases rapidly at longer
space time. When methanol is co-fed with olefin, however, the
methanol conversion is remarkably accelerated and high reaction rate can be obtained even at very small space time, as the
C5C bond already exists in the feed.1012 Faster rate leads to
shorter contact time and thus less byproduct generation. Furthermore, catalyst deactivation can also be significantly
slowed down by co-feeding olefins.13,14

January 2017 Vol. 63, No. 1

AIChE Journal

Mathematical simulation is a convenient way to investigate

the chemical reactors as long as a reliable kinetic model is
established.15 Several kinetic studies1620 on methanol to olefins reactions over HZSM-5 catalyst have been published so
far, but these models were developed mainly based on the condition where methanol was fed alone. However, as revealed by
the recent works,9,21 the dominant pathway of methanol and
olefin is different when methanol is co-fed with olefins. In our
previous work,22,23 we developed a comprehensive kinetic
model for MTP process under the industrial operation process
based on the olefin methylation-cracking mechanism,1012,24,25
which gives excellent agreement with the experimental data
under various reaction conditions. Moreover, a kinetic model
on the generation of byproducts paraffin and aromatics was
recently published as well.26
In this work, we tried to optimize the industrial MTP reactor
by modulating the recycling of the unwanted C4C6 olefins
into the main reactor and appending a subsidiary olefin cracking reactor. A heterogeneous mathematical model was established for the main and the cracking reactors, which were
solved by combining Comsol with Matlab. The effect of
design parameters of the cracking reactor was also analyzed.

The Model Development

Process overview
Schematic flow sheet of the modified Lurgi-type MTP process is shown in Figure 1, which primarily includes catalytic
reaction, product separation, and olefin recycling. The main
reactor is packed with HZSM-5 zeolite catalyst for methanol
dehydration to olefins, and consists of six adiabatic fixed beds
in series, with the feedstock, a mixture of methanol, DME and
water from the pre-reactor packed with c-Al2O3 catalyst divided into six parts and introduced in between the beds and into
the reactor entrance where the recycled higher olefins are cofed as well. The pre-reactor helps alleviate the release of reaction heat in the main reactor for a rational adiabatic operation.
In the separation system, ethylene and propylene are drawn
out as the main products, while C1C4 paraffins and gasoline
containing heptene and aromatics as the byproducts. As this
work is a conceptual study and focuses on the performance of
reactors, the detail configuration of the overall separation process will not be discussed and it is assumed that the separation
system could feasibly separate the reactor output into the

desired light olefins, recycling olefins and the byproducts

which consists of the related distillates.
As a simplification, in all the cases the operation temperature of the pre-reactor was specified to be 3808C, the same
temperature as chosen by industrial process, and the product
distribution was methanol : DME : water 5 0.12:0.44:0.44,
calculated from the chemical equilibrium formula27:
ln K521:71

3320
T K

(1)

The main reactor consists of six stages packed with ZSM-5

extrudates with an equivalent pellet diameter of 3.6 mm. For
each stage, the temperature was specified as 4608C and the
inlet pressure of first stage as 1.5 atm, and the feed rate of
methanol and DME was determined by the specified temperature rise of 208C, as the main heat comes from the methylation
reactions.8 The feed composition at the stage inlet was then
calculated by the mixture of the flow from last stage or recycle
stream and the oxygenates from the DME reactor. The height
of catalyst bed was determined by meeting the specified methanol and DME conversion, i.e., 99.9%. As will be discussed
later, such a value of oxygenate conversion resulted in a comparable space velocity with the industrial performance, thus
the catalyst lifetime could be expected to be the same.
In this work, an improvement is proposed by modulating
the recycling of the higher olefins, butene, pentene, and hexene as well, with a subsidiary cracking reactor where the
higher olefins are able to crack into lighter ones and to further
enhance the yields of ethene and propylene, as depicted in Figure 1. The cracking reactor was a one-stage fixed bed reactor
packed with the same catalyst, so that the same kinetic model
could be used in the simulation. The inlet temperature and
pressure were 5008C and 1.5 atm, respectively. The height of
catalyst packed bed was also adjusted during the calculation
until the conversion met the specified value, such as 40%.
During the calculation, the methanol feed rate was set as
208 t/h, as same as the reported capacity of industrial MTP
process,28 and the other streams and the reactor configuration
were calculated through an iteration procedure. In practice,
C4C6 paraffins are not separated from the mixture but
recycled with the corresponding olefins, therefore butane with
the same flow rate as C4C6 olefins was added into F4 and F5
as the diluent. F4 was further diluted by 50% steam before

Figure 1. Flow sheet of the optimized MTP process.

AIChE Journal

January 2017 Vol. 63, No. 1

Published on behalf of the AIChE

DOI 10.1002/aic

307

entering the main reactor, which is helpful to prevent a fast

catalyst deactivation. As olefin cracking is thermodynamically
easier to occur under low partial pressure, F5 was also diluted
by steam to get an olefin fraction of 10%. The detail iteration
steps were as follows, which was coded in Matlab program:
1. An initial estimate of C4C6 olefin flow rates was
specified to F3.
2. The composition and flow rates of F4 and F5 were calculated from F3 and the dilution streams.
3. The design parameters (reactor height, feed methanol
rate, et al.) of the main reactor and the cracking reactor were
solved with the composition of F4 and F5, respectively,
through trial-and-error procedure.
4. The flow rate and composition of F2 was obtained by
mixing the two streams from the reactor outlets (F1 and F6).
5. If the flow rates of recycled olefins in F2 equaled their
value in F3 within a relative error less than 0.1%, the iteration process was regarded as to be converged; else the C4
C6 olefin flow rates in F2 were assigned to F3 and calculation repeated to step 2 for the next iteration loop.

Fix-bed reactor model

The classical heterogeneous and steady-state fixed-bed
model was used to simulate both the main and the cracking
reactors, in which the mass and heat balance of the reactor can
be described in one-dimensional form:


dCgi;j
5kg av Cgi;j 2Css
(2)
2ug
i;j
dz
g

2u

qg cgp

 g

dTig
5hg av Ti 2Tiss
dz

component in the catalyst pellet, which was calculated from

the combination of binary diffusivity and Knudsen diffusivity,
shown as follows:
!21
12yj
eP
1
X
1
(10)
De;j 5
s
yk =Djk DK;j
k

Djk 5

Ti 5Ti0 ;

The involved reaction network and the kinetic parameter

are summarized in Table 1, in which the reactions can be categorized into five groups: methanol dehydration (RM1), olefin
methylation (RMO1-RMO7), olefin interconversion (RO1RO10),
paraffin formation (RP1RP7), and aromatic generation (RA1
RA4). Due to the divergent reaction pathways, their rate
expressions are different. For the reversible dehydration and
olefin interconversion (RM and RO), the rates are expressed as

(3)

dCsi;j
2

De;j d
n
dn
n2 dn

De;j

2qs

(4)

NR
X

vjm rm 50

(6)

m51



NR
s
X
ke d
2 dTi
n
rm 2DHm 50
1qs
2 dn
dn
n
m51

(7)

dCsi;j
dTis
50;
50; at n50
dn
dn

(8)





dTis
g
5kg Css
5hg Tiss 2Tig ; at n5rp
i;j 2Ci;j ; ke
dn
dn

dCsi;j

DOI 10.1002/aic

ads
ads
11KM
pM 1KOads pO 1KW
pW

Xvjm<0
2
vjm
j

2v
pj jm 2

vjm <0

(13)

1 Y vjm A
p
Km v >0 j
jm

and for the irreversible methylation (RMO), the rate expression

is
Y 2vjm
km
Xv

rm 5
pj
jm<0


2v
21 vjm <0
jm
ads
ads
j
11KM
pM 1KOads pO 1KW
pW
(14)
Conversely, the rate expression of paraffin cracking (RP6
RP8) and aromatic generation (RA) is
Y 2vjm
km
Xvjm<0
pj
rm 5


2vjm vjm <0
ads
ads
j
11KM
pM 1KOads pO 1KW
pW
(15)
Moreover, the rates of methane generation from methanol
pyrolysis (RP1) and C2C5 paraffin generation from hydrogen
transfer (RP2RP5) are expressed in Eqs. 16 and 17,
respectively.
rm 5 

(9)

Where NR is the number of reactions in kinetic model; vjm is

the stoichiometric coefficient of j-th component in m-th reaction; rm and DHm is the reaction rate and reaction heat of m-th
reaction, respectively. De,j is the effective diffusivity of j-th
308

km


The mass and heat transfer in radius direction of the catalyst

are given by Eqs. 69.

(12)

The kinetic model

rm 5

Pressure drops due to catalytic packing are calculated by

means of the Ergun equation


dPi
ug 12eB 15012eB lg
g
52
11:75qg u
(5)
dz
dp e3B
dp

s
8RT
pMj

This model of fixed-bed reactor was efficiently solved by

Comsol,8 which can be lively linked to Matlab and called like
a function during the process calculation.

3@
at z50

(11)

1=2

PMjk r2jk XD

dpore
DK;j 5
3

with boundary conditions

Ci;j 5C0i;j ;

0:00266T 1:5

km pM

ads
ads
11KM
pM 1KOads pO 1KW
pW

rCn H2n12 5 

km pCn H2n 11a  pM


ads
ads
11KM
pM 1KOads pO 1KW
pW

(16)

(17)

where a denotes the effect of methanol decomposition on

hydrogen transfer rate:

Published on behalf of the AIChE

January 2017 Vol. 63, No. 1

AIChE Journal

Table 1. Kinetic Parameter of the Co-Reaction of Methanol and Olefins

km
No.

Formula
2CH3 OH
CH3 OCH3 1H2 O
C3 H6 1CH3 OH
C4 H8 1H2 O
C4 H8 1CH3 OH
C5 H10 1H2 O
C5 H10 1CH3 OH
C6 H12 1H2 O
C6 H12 1CH3 OH
C7 H14 1H2 O
C3 H6 12CH3 OH
C5 H10 12H2 O
C4 H8 12CH3 OH
C6 H12 12H2 O
C3 H6 13CH3 OH
C6 H12 13H2 O
3C3 H6
C4 H8 1C5 H10
2C4 H8
C3 H6 1C5 H10
C5 H10
C2 H4 1C3 H6
2C5 H10
2C3 H6 1C4 H8
2C5 H10
C4 H8 1C6 H12
C6 H12
C2 H4 1C4 H8
C6 H12
2C3 H6
2C6 H12
C3 H6 1C4 H8 1C5 H10
2C6 H12
3C4 H8
C7 H14
C3 H6 1C4 H8
CH3 OH12Ha ! CH4 1H2 O
C2 H4 12Ha ! C2 H6 *
C3 H6 12Ha ! C3 H8
C4 H8 12Ha ! C4 H10
C5 H10 12Ha ! C5 H12
C4 H10 ! CH4 1C3 H6
C5 H12 ! CH4 1C4 H8
C5 H12 ! C3 H8 1C2 H4
C6 H12 ! C6 H6 16Ha
C3 H6 1C4 H8 ! C7 H8 16Ha
C3 H6 1C5 H10 ! C8 H10 16Ha
C4 H8 1C5 H10 ! C9 H12 16Ha

RM1
RMO1
RMO2
RMO3
RMO4
RMO5
RMO6
RMO7
RO1
RO2
RO3
RO4
RO5
RO6
RO7
RO8
RO9
RO10
RP1
RP2
RP3
RP4
RP5
RP6
RP7
RP8
RA1
RA2
RA3
RA4

Km

Ea;m
36.29
49.68
69.19
53.10
41.99
25.27
11.98
1.10
2173.97
277.47
81.24
280.12
287.62
42.55
77.31
249.23
248.51
11.73
159.34
42.14
269.20
240.35
224.43
217.38
43.80
64.68
50.60
269.46
265.22
251.74

km;0
6.78
2.11
5.20
7.80
7.50
7.80
9.24
1.83
4.55
5.35
1.30
1.70
2.44
4.47
1.59
1.18
5.14
2.79
2.19
1.72
0.80
0.83
1.31
1.53
4.21
1.30
9.25
2.09
1.14
0.84

3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3

10203
10203
10203
10203
10203
10205
10204
10204
10207
10205
10203
10204
10204
10203
10202
10203
10205
10201
1024
1024
1024
1023
1023
1025
1023
1023
1025
1025
1024
1024

DHm

Km;0

215.85

1.19

285.93
5.01
103.45
83.92
1.38
91.61
57.89
81.42
81.17
61.82

3.72
3.12
6.08
7.10
3.25
1.12
7.24
2.45
7.01
1.05

3 10203
3 10201
3
3
3
3
3
3

10201
10101
10101
10101
10101
10102

*Ha denotes the transferred hydrogen atom.

a513:0331024 kPa21 exp




64:683103 J  mol21  1 1
2
R
T T0
(18)

All the kinetic constant km and the chemical equilibrium constant Km mentioned above are expressed in Arrhenius or Vant
Hoff equation with reference temperature:



Ea;m 1 1
2
km 5km;0 exp 2
R T T0

(19)




DHm 1 1
Km 5Km;0 exp 2
2
R
T T0

(20)

where T0 5733.15 K. The adsorption constants of methanol,

ads
ads
, KOads , and KW
) are as follows
olefin and water (KM
ads
KM
54:3660:3531022 exp

KOads 52:2060:5931022 exp

ads
KW
52:2160:1031022 exp

AIChE Journal



47:5064:593103 1 1
2
R
T T0
(21)



65:5866:103103 1 1
2
R
T T0
(22)



11:1962:193103 1 1
2
R
T T0
(23)

January 2017 Vol. 63, No. 1

Results and Discussion

Model validation
As can be seen that the reactor model above mentioned is
heterogeneous with internal diffusion included. For an adiabatic fixed-bed reactor, the reactor performance can be defined by
the following parameters: the contact time of reactant mixture
with the packed catalyst bed, inlet temperature and compositions, provided the intrinsic kinetic constants and the diffusion
effect are validated. In this section, the model based calculations were compared with two sets of experimental data,
which were obtained in an isothermal lab-scale fixed-bed reactor loaded with randomly packed cylindrical HZSM-5 (/3 3
5 mm). The experimental setup has been described in our previous work,22 with a reactor of 25 mm in diameter and 1 m in
length heated by electric heating wires. The catalyst was the
same as used in our kinetic study, which was extruded with
the binder of 30% alumina and possesses macropores of a
mean diameter of 129 nm and a porosity of 0.61. The experiments were carried out at atmospheric pressure and 4608C.
The comparison is shown in Figure 2, which reveals that the
calculated product distribution fits the experimental observations excellently in both cases, meaning the model can be adequately accurate for simulating the reactors.

Optimization of the olefin recycle

As has been revealed that the byproducts are substantially
due to the side reactions of olefins through the hydride transfer
reaction mechanism, thus reducing the contact time of the olefins, both the main product, propylene and ethene, and the
undesired higher olefins, C4C6, can be an effective means to
enhance the yields of the main products. The variables of

Published on behalf of the AIChE

DOI 10.1002/aic

309

Figure 2. Composition of experimental and calculated data.

Feed: (a) 10% olefin 1 30% water 1 60% N2; (b) 5% methanol 1 10% olefin 1 22.5% water 1 62.5% N2. [Color figure can be
viewed at wileyonlinelibrary.com]

olefin recycle are the flow rates of individual olefins, which

thereby stimulate two methods: modulating the total flow rate
of the recycle olefins and regulating the species in the recycled
olefin stream.
Strategy 1: Reducing the Total Recycle Flow Rate. The
first strategy to optimize the MTP process is to modulate the
recycle flow rate of all the C4C6 olefins. For the convenience
of calculation and analysis, two parameters were defined:
RR43 as the ratio of olefin flow rate in stream F4 to that in F3,
and RR41 as the ratio of olefin flow rate in the outlet F1 to that
at the inlet F4 of the main reactor. Six cases were conceived
and simulated to compare the effect of changing the recycle
flow rate on product selectivity. As shown in Table 2, RR41 is
unity in Case 1, i.e., all the C4C6 olefins are recycled back
into the main reactor and no cracking reactor was used. As a
base case, ethylene is also recycled and only propylene is
drawn out as the main product, which is the same as Lurgi process. It can be noticed that the propylene selectivity is 62.01%
and the space velocity in the main reactor is 0.75 kgMeOH/
kgcath, both of which are quite close to the industrial achievements (61.62% and 0.69 kgMeOH/kgcath, respectively) from a
1.5 Mt/y plant.7 This implies that by choosing the proper temperature rise (208C) and methanol conversion (99.9%), the calculated results of the simulated MTP reactor are comparable
to the practical ones of a commercialized reactor and the following optimization can be applied to current reactors.
Ethylene is the smallest olefin and cannot be efficiently converted in the cracking reactor under the investigated temperature. It is also a desired olefin as an ingredient in some case for
copolymer production and as the raw material for polyethylene, therefore can also be drawn out as final product. As a
comparison case, ethylene is not recycled back into the main
reactor in Case 2 and it was found that the total yield of

propylene and ethene can increases slightly to 63.37%, a little

higher than Case 1, indicating this modification is rational in
process optimization. As a result, ethylene is regarded as a
final product together with propylene in the rest case studies.
By decreasing olefin recycle rate, the total yield of low olefins can reach higher than 70% when RR43 is smaller than 0.1,
indicating the reactor performance is significantly improved
by reducing the recycle flow rate. With RR43 decreasing to
0.05 and equally RR41 to 0.12 in Case 6, the yields of ethylene
and propylene increase to 14.41 and 56.07%, respectively, and
the total olefin yield in the main reactor is increased to 78.55%
while that of the cracking reactor is 81%. However, when
decreasing RR41 from 0.1 to 0.05, product yield changes very
little, because the methylation rate will be decreased due to
the lower olefin content at the inlet and the consequently
increased contact time in the main reactor as shown by the
space velocity of the main reactor (SV1) decreasing from 0.81
to 0.56 kgMeOH/kgcath.
Wcat,2/FM is the ratio of the catalyst weight in the cracking
reactor to the mass flow rate of feed methanol, which is used
to represent the amount of extra catalyst required by the new
reactor. As the olefin content in the cracking reactor is fixed to
10%, reducing RR43 means more olefins are handled by the
cracking reactor, leading to higher Wcat,2/FM, and higher
investment cost of catalyst and equipment. As a result, 0.1 is
the most proper choice for RR43, and correspondingly 0.23 for
the recycle ratio of the olefins, RR41.
Figure 3 depicts the profiles of the olefins, C2C7, in the
main and appended reactors in Case 5 with both ethylene and
propylene as the desired products. For each recycled olefin,
the sum of its flow rate at the inlets of two reactors equals that
at the outlets, which means the overall circulation of the olefins converged. As shown in Figure 3a, one can notice that the

Table 2. Result of Different Recycle Ratio

Yield (%)
Case

RR43

RR41

C5
2

1
2
3
4
5
6

1
1
0.5
0.25
0.1
0.05

1
1
0.73
0.47
0.23
0.12

0
11.93
13.38
13.96
14.32
14.41

310

DOI 10.1002/aic

C5
3
62.01
51.44
53.06
55.00
56.03
56.07

Published on behalf of the AIChE

5
C5
2 1C3

62.01
62.82
66.43
68.95
70.35
70.48

SV1kgMeOH/
kgcath
0.75
0.81
0.75
0.70
0.61
0.56

January 2017 Vol. 63, No. 1

Wcat,2/
FMkgcath/kgMeOH
0
0
0.12
0.22
0.30
0.34

AIChE Journal

Figure 3. Relative flow rates along the reactor length with RR41 5 0.1.
(a) The main reactor; (b) The cracking reactor. [Color figure can be viewed at wileyonlinelibrary.com]

olefin flow rates oscillate along the reactor. In the first stage,
as the feed butene concentration is high and the propylene
concentration is low, butene is converted to pentene and then
to hexene by methylation, and further to propylene by hexene
cracking, which results in the obvious decrease of butene and
the sharp increase of propylene near the inlet. In the following
stages, the flow rates of C4 olefins increase initially by the
methylation of propylene due to high methanol concentration,
and decreases later as the methylation reactions become slow
while its cracking reaction becomes dominant because of
methanol consumption. Due to similar reasons, the concentration of C5 and C6 olefins behaves as does C4 in stage 46. The
flow rate of propylene always increases along the reactor,
except the inlet of stage 26, where its methylation rate is
somewhat obvious.
For the olefin cracking reactor as can be seen in Figure 3b,
due to the different cracking activity, hexene reaches a high
conversion quickly while butene changes slowly, resulting in a
rather long contact time to achieve high cracking conversion.
Strategy 2: Reducing Recycle Species. The second optimization strategy is to regulate the recycle species. Three
cases were conceived and simulated to compare the reactor
performance where C4C6 were recycled individually, and the
results are listed in Table 3. It can be found that when only
butene is recycled, the product yield is 70.81%, slightly higher
than the best case 6 shown in Table 2 where R43 5 0.05, and
much higher than Case 8 and 9 where only pentene or hexene
is recycled. Besides, the space velocity of the main reactor is
also higher while the ratio Wcat,2/FM is significantly lower in
Case 7 than the other cases, indicating less catalyst is required
for the cracking reactor. This is because the methylation of
butene is faster than others while the cracking of pentene and
hexene is easier than butene in the view of both kinetics and
thermodynamics,9,22,23 thus in both reactor the contact time is
reduced. Furthermore, the performance of Case 9 is better than
Case 8, because less hexene is produced than pentene in the

main reactor and thus the recycle flow rate into the main reactor is smaller.
Figure 4 shows the olefin flow rate profiles in the two reactors when only butene is recycled. As illustrated in Figure 4a,
butene flow rate drops sharply near the inlet of first stage due
to the rapid methylation reactions, resulting in the sharp
increase of other olefins. Nevertheless, the flow rate of butene
increases continuously from second stage to sixth stage, and
the reason is that the propylene content increases up to about
twice of the butene and the methylation of propylene to butene
becomes significant. The behavior of other components is similar to Figure 3 and can also be explained by methylationcracking mechanism. In the cracking reactor as illustrated in
Figure 4b, the total olefin flow rate at the inlet is smaller than
that in Figure 3b, leading to lower reactor load. Due to the
faster cracking rate of pentene and hexene, the residence time
in cracking reactor is 0.28 s, much lower than the value of
Case 6 (0.85 s) by the first strategy, which makes the catalyst
requirement in cracking reactor seven times less than that
for the Case 6, and thus the Strategy 2 is more efficient than
Strategy 1.
The above discussion shows that the yield of light olefins
(C2 and C3) can be improved to higher than 70% by reducing
either the recycle flow rate or species. However, due to the
smaller catalyst requirement in the cracking reactor, the best
choice is to recycle only butene into the main reactor while
pentene and hexene crack into lighter olefins in the appended
cracking reactor. Besides, this retrofit has very little impact on
the main reactor and the downstream separation system,
and the life time of the catalyst can be expected to be the same
as the current configuration since the space velocity of the
main reactor has not been changed significantly.

Parameter optimization of cracking reactor

The effects of olefin conversion and inlet content of the
cracking reactor were investigated based on the same condition as Case 7 in Table 2, where only butene is recycled back

Table 3. Result of Different Recycle Species

Yield (%)
Case

Recycle species

C5
2

C5
3

Butene
Pentene
Hexene

15.32
12.72
13.80

55.50
52.66
54.07

7
8
9

AIChE Journal

January 2017 Vol. 63, No. 1

5
C5
2 1C3

70.81
65.37
67.87

SV1kgMeOH/kgcath
0.71
0.66
0.62

Published on behalf of the AIChE

Wcat,2/FMkgcath/kgMeOH
0.05
0.45
0.36

DOI 10.1002/aic

311

Figure 4. Relative flow rates along the reactor length with only butene recycled.
(a) The main reactor; (b) The cracking reactor. [Color figure can be viewed at wileyonlinelibrary.com]

into the main reactor and the other higher olefins are converted
into lower olefins (C2C4) in the cracking reactor packed with
the same zeolite catalyst.
Effect of Single-Pass Conversion. As shown in Figure 5a,
when increasing olefin conversion in cracking reactor, the
overall yield of ethylene and propylene increases slightly at
first but then decreases, with the highest yield exists at 20%
conversion. Conversely, the value of Wcat,2/FM increases exponentially with the conversion, indicating much larger amount
of catalyst will be required, because the rates of cracking reactions decrease with conversion due to the restriction of chemical equilibrium. Meanwhile, the space velocity of the main
reactor remains almost the same, as the cracking of pentene

and hexene into lighter olefins has little impact on the flow
rate of butene at the inlet of main reactor. Besides, lower
single-pass conversion results in more recycle flow rate at the
inlet, and further leads to a larger diameter of the cracking
reactor. Consequently, the conversion should be controlled
under 40% to obtain a total C2C3 yield over 70% and relatively low catalyst requirement in cracking reactor.
Effect of Inlet Olefin Content. The inlet olefin content can
be adjusted by adding different amount of steam. As shown in
Figure 5b, by decreasing inlet olefin content, the overall yield
is increased high up to 74.5% mainly due to the decrease of
heptene, since its cracking are thermodynamically favored at
lower partial pressure. To obtain a high product yield, the inlet
olefin content should be less than 10%. However, the ratio
Wcat,2/FM also increases at smaller inlet olefin concentration,
and consequently more catalyst is required.
It can be found that the optimized light olefin yield reaches
7375%, about 13% higher than the current industrial propylene yield, which is of great significance to the existing MTP
plant with an annual throughput of 1.5 Mt methanol and an
expected production of 0.5 Mt propylene.

Conclusion

Figure 5. Effect of olefin conversion (a) and inlet olefin

fraction (b) in cracking reactor on the C2C3
olefin yield of the overall process and the
required catalyst for cracking.
[Color figure can be viewed at wileyonlinelibrary.com]

312

DOI 10.1002/aic

As the current practice of the Lurgi-type process for MTP

has large margins to improve as compared to the MTO process
using SAPO-34 catalyst, two strategies in accordance with the
control of olefin recycle have been simulated and analyzed
based on our previous kinetic works. Hereby we conclude as
follows.
First, mathematical modeling of the industrial MTP process
reveals that the yield of ethylene and propylene can be
improved greatly by reducing either the total flow rate or species in the recycled olefin stream back into the main reactor
and appending a cracking reactor for the rest olefins. When the
recycle ratio is lower than 23% or only butene is recycled, the
yield is increased up to 70%, significantly larger than the current level of 62% in industrial process. Second, the strategy
reducing the species to only butene is much more competitive
to that reducing the total recycle ratio to the optimal value of
23%, with a catalyst requirement reduction by 7 times. The
further parameter study shows that the yield can be further
improved to 7375% by decreasing the single-pass conversion
and the inlet content of olefins in the cracking reactor. Third,
the detailed theoretical analysis indicates the proposed strategies have very limited impact on the space velocity of the

Published on behalf of the AIChE

January 2017 Vol. 63, No. 1

AIChE Journal

main reactor, thus the operation lifetime of the catalyst is

expected to change little. In a word, the proposed optimization
strategy can be of great significance to the current MTP
process.

Notation
av = external particle surface area per unit reactor volume,
m2/m3
DME = dimethyl ether
Ci,j = gas-phase concentration of j-th component in i-th stage,
mol/m3
Csij = solid-phase concentration of j-th component in i-th stage,
mol/m3
cgp = mass specific heat of the gas phase, J/kgK
De;j = effective diffusion coefficient of i-th species, m2/s
dpore = pore diameter of catalyst, m
Ea,m = activation energy of m-th reaction, kJ/mol
FM = total feed rate of methanol, kg/h
hg = gas-solid heat transfer coefficient, W/mK
km,0 = pre-exponential factor of m-th reaction
kg = gassolid mass transfer coefficient, kg/ms
pj = partial pressure of j-th component, kPa
pM , pO , pW = partial pressure of methanol, olefin and water, kPa
rm = rate of m-th reaction, mol/kgs
rp = catalyst diameter, m
RR43, RR41 = recycle ratio
SV1 = space velocity of main reactor, kgMeOHh/kgcat
Ti = temperature of i-th stage, K
ug = superficial velocity, m/s
Wcat,2 = catalyst weight in cracking reactor, kg

Greek letters
eB =
ep =
n=
DHm =
s=
XD =

bed voidage
catalyst porosity
radial position of the catalyst, m
reaction heat of m-th reaction, J/mol
tortuosity factor
collision integral

Superscripts and subscripts

0=
g=
s=
ss =

inlet
gas phase
solid phase
surface of solid phase

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Manuscript received Apr. 4, 2016, and revision received Oct. 24, 2016.

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DOI 10.1002/aic

313