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Research Article 1

Bor-Yih Yu
Design and Optimization of the Methanol-
I-Lung Chien
to-Olefin Process
Department of Chemical
Engineering, National Taiwan Part I: Steady-State Design and Optimization
University, Taipei, Taiwan.
The steady-state design and optimization for a methanol-to-olefin (MTO) process
is studied. The MTO process is a novel route for light olefin production, especially
ethylene and propylene. Comparing with the traditional way to produce olefins by
steam cracking, this process offers benefits such as a more flexible range of ethyl-
ene-to-propylene ratio, higher selectivity toward light olefin, and mild reaction
conditions. The design of the overall MTO process is divided into four sections,
namely, reaction section, conditioning section, first separation section, and second
separation section. After the design of each sub-part, optimization is performed,
in which the design and operating variables are thoroughly investigated. By rigor-
ous simulation, a more economically competitive design flowsheet of the overall
MTO process is proposed.

Keywords: Methanol-to-olefin process, Light olefin production, Reactive section, Simulation,

Steady-state design
Received: October 31, 2015; revised: March 21, 2016; accepted: April 01, 2016
Supporting Information
available online DOI: 10.1002/ceat.201500654

1 Introduction an important role in the MTO process. The molecular sieve

Light olefins, including ethylene, propylene, butylene, and bu-
tadiene, are the most important petrochemicals. Among light
olefins, ethylene and propylene are the most demanded chemi-
cals. They are widely used in industries as building blocks of
polymers, plastics, membranes, rubbers, and also chemical
intermediates. The conventional way for producing olefins is
through steam cracking of petroleum products, such as naph-
tha. It is an energy-intensive process which operates at high
temperature. Because of the oil shortage, great efforts have been
made to find an alternative way to produce olefins, being the
background for the methanol-to-olefin (MTO) process to
emerge. Comparing with steam cracking, the MTO process
offers several advantages such as a more flexible range of
ethylene-to-propylene ratio, higher selectivity toward light ole-
fins, and the capability for operating at moderate conditions.
These advantages have made the MTO process to become more
promising recently [1–7].
The raw material of the MTO process is methanol, which
can be produced from syngas. This leads to the possibility of
integrating the MTO process into a coal (or other fuel) gasifica-
tion system, and olefins are also regarded as one of the candi-
dates of poly-generation products [3, 8, 9]. The catalyst plays
– ity because of the occupation of the pores, however; it will
Correspondence: Prof. I-Lung Chien (ilungchien@ntu.edu.tw),
Department of Chemical Engineering, National Taiwan University,
No. 1, Sec. 4, Roosevelt Road, Taipei, 10617 Taiwan.
catalyst has been widely considered as the candidate, especially
SAPO-34. The porous structure of the SAPO-34 catalyst ena-
bles for the MTO process to reach high selectivity toward light
olefins [10–16]. The world’s first coal-to-olefin process based
on the MTO technique was successfully established in China
by The Dalian Institute of Chemical Physics (DICP) in 2010,
which is known as DMTO (DICP’s MTO) process [5, 6, 17, 18].
From the plant, the data indicate that the selectivity toward
ethylene and propylene is up to 80 wt %, which is far better
than the product from conventional steam cracking. The suc-
cessful buildup of the DMTO process not only proves the pos-
sibility of large-scale MTO production, but also pushes the
MTO-related research further.
Although the concept of the MTO process has long been
considered, its kinetics is still under investigation. It is believed
that methanol forms dimethyl ether (DME) first as a chemical
intermediate, and DME is further reacted to form olefins. The
step for DME to olefins is very complex, but it is generally con-
sidered to be of two types of reaction. The first one is olefin for-
mation from lower carbon to higher carbon sequentially, and
the other one is that higher olefins will decompose to form
light olefins [10, 14, 15, 17]. Also, due to the porous structure of
the catalyst, the compound with a size larger than the catalyst
pore is unable to go through and is left inside the catalyst. It
leads to the formation of coke which will reduce the productiv-
increase the selectivity of smaller products. Thus, partial regen-
eration of coked catalyst is considered to have some advantages
in the MTO reaction [17, 19, 20].

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2 Research Article
For rigorous simulation, reaction kinetics is needed. How-
ever, due to the complexity of MTO reaction mechanisms, the
development of kinetics becomes difficult. There were several
research works taking each individual step of the MTO process
into account. These researches clearly illustrate the details of
the reactions but the establishment of kinetic parameters is
very time-consuming and is nearly impossible for design pur-
pose [16, 21–23]. There is another kind of reaction kinetics, the
so-called lumped models, which are built as a compromise
between simplicity and complexity. The lumped model can be
a choice for the MTO process design [10, 13, 17, 20, 24]. Essen-
tially, the MTO process is a highly exothermic process which is
operated in the range of 350–550 C. Due to the exothermic
nature of the reaction and the coking issue, in the open litera-
ture the fluidized-bed reactor is suggested as a better reactor
configuration over the fixed-bed reactor for it provides well-
mixing and uniform temperature throughout the reactor
[11, 12]. This feature leads to decent conversion of feed metha-
nol and also makes it easier to operate and control.
For separation of the MTO reaction outlet into products, the
traditional way which was applied in steam cracking can be
used. The goal for separation is to obtain pure ethylene and
propylene as main products, with lighter components (CO, H2,
CH4Ketc.) and heavier components (C4–C5 olefins or paraf-
fins) as by-products. Generally, it is a sequential step to sepa-
rate based on different carbon numbers [25–28]. Among the
separations, the recovery of light components is the most com-
plex. The concept of light gas separation is similar to the deme-
thanizer unit in a natural gas liquid (NGL) plant, in which
most of methane is recovered. The demethanizer operates as
cryogenic distillation under high pressure and often requires a
large amount of refrigerant. Thus, the heat integration scheme
is extremely important for recovering the refrigerant, and also
for saving cost and energy [29]. However, the separation of
light gas will cause a certain loss of C2 and C3 components,
mainly C2. The lighter the components to be recovered, the
higher the loss will be. In the MTO process, there is hydrogen
in raw olefins, while ethylene and propylene are the main prod-
ucts. Thus, to decrease the ethylene loss from the light product
is also an important target when designing the separation pro-
cess.
Due to the oil shortage in these years, the MTO process has
received much more attention. In open literature, lots of efforts
have been made to determine the reaction mechanism and cat-
alytic activity [10, 19, 20, 30, 31], to develop the reaction
kinetics [13, 15–17, 20–24], and to simulate the configuration
and performance inside different types of reactors [6, 11–15].
Figure 1. Block flow diagram for the MTO process.
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There are some research works that discuss the conceptual
design, economical assessment, and thermodynamic analysis of
the MTO process [3, 5, 7]. However, the works related to plant-
wide design and operation through rigorous simulation are
rare. Herein, design and optimization of the MTO process are
illustrated, with the design and operating variables thoroughly
investigated. The results of this work could provide another in-
depth basis for further MTO process development.
2 Overview of the Studied MTO Process
The simulation works are performed in ASPEN Plus V8.4. The
Peng-Robinson equation of state is selected as the thermo-
dynamic model throughout this work. The MTO process is
divided into four sections, i.e., reaction section, conditioning
section, first separation section, and second separation section.
Detailed design and optimization of these four sections will be
given in the following sections of the paper.
In the reaction and conditioning section, the methanol feed
is converted to olefin mixtures and then quenched and puri-
fied. In the first separation section, the outlet from the reaction
and conditioning section is separated into three products,
namely, light components, heavy components, and C2–C3
mixture. The C2–C3 mixture then enters the second separation
section, which includes C2-splitting and C3-splitting. The main
goal of the second separation section is to obtain pure ethylene
and propylene as products, with both purities set at a polymer-
grade target, i.e., 99.5 mol %.
The overall block flow diagram of the MTO process is given
in Fig. 1, with each section illustrated in detail in the following
sections. After the steady-state design of each section is estab-
lished, optimization is performed to find a set of ideal design
and operating variables based on minimization of total annual
cost (TAC), with assumption of a three-year payback period.
For evaluating the cost for equipment and utilities, the calcula-
tion basis suggested by Luyben is used [32]. The utility costs
are summarized in Tab. 1.
3 Reaction Section
The reaction section is the first part of the MTO process. In
this section, methanol is converted to olefin in a fluidized-bed
reactor. The lumped kinetic expression with the aid of a porous
catalyst (DMTO catalyst, used in DICP’s MTO process) from
Ying et al. [17] is applied. In their proposed reaction network,
Chem. Eng. Technol. 2016, 39, No. 00, 1–12
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Research Article 3

Table 1. Utilities used in this work [32]. activity. On the other hand, the positive influence is that the
plugged pore can enhance the selectivity toward the light ole-
Utility Price Tin Tout Assumed fins. This is because the components with a larger size than the
[USD/GJ] [C] [C] minimum pore size will be stuck inside. Thus, coking has relatively small
T-difference influence for the production of light olefins, and the selectivity
LP steam 7.78 160 160 10 will become even higher as the pore is plugged by coke. There-
a)
fore, if the coked catalyst can be partly regenerated, the selec-
Cooling water 0.354 35 45 X tivity toward light olefins can be enhanced without losing cata-
Chilled water 4.43 5 15 10 lyst activity.
The design flowsheet of reaction and conditioning section
High-T refrigerant 7.89 –20 –19 3 is displayed in Fig. 2. The pure methanol feed (T = 25 C,
Low-T refrigerant P = 2.2 bar) enters the system. It is first heated by heat
(C3 refrigerant) 13.11 –49 –48 3 exchanging with high-temperature vapor stream in an inter-
condenser after first-stage quenching. The heated methanol
Electricity 16.8 X X X
feed is vaporized, further heated by the reactor outlet stream
a)
The operating temperature for cooling water is assumed to be to the required temperature (352.2 C), and then fed into the
averaged as 42 C (~ 315 K). reactor. For simplicity, the fluidized-bed reactor is modeled
as an isothermal plug-flow reactor (RPLUG) in this work,
methanol is converted to methane, ethylene, propylene, pro- with the necessary heat removal calculated to maintain the
pane, C4, C5+, and coke. C4 is a lumped category which con- reactor operating at the desired temperature. Besides, due to
tains butylene, butadiene, and butane. C5+ is another lumped the incapability of including the solid catalyst in the RPLUG
category involving ethane and any other hydrocarbons with model in Aspen Plus, only the behavior of coke is studied
5-plus carbons. here. Therefore, in this work, the coke formed in the reactor
Some modifications are necessary in order to be applicable is separated from the MTO outlet using the ASPEN built-in
in Aspen Plus. First, hydrogen is required for formation of par- SEP unit.
affins, but it is not present in this reaction network. Hydrogen After the SEP unit, part of the coke is cooled to 352.2 C and
may come from decomposition of methanol under high tem- sent back to the reactor with the methanol feed, while the
perature, thus the methanol decomposition reaction is added remainder undergoes complete combustion. Although the
into this network, with the kinetic parameters cited from behavior of the solid catalyst is not included in the simulation,
Najafabadi et al. [13]. Second, in order to study the perform- it is not neglected in the energy balance calculation. With prop-
ance of the de-ethanizer, ethane is separat-
ed from the C5+ category. This is based on
Table 2. Information of reaction and kinetics.
the plant data from DICP that ethane yield
is about 1/3 of other C5+ hydrocarbons Reaction No. Reactions ki ai
[18]. In this work, butylene (C4H8) is used
to represent the C4 category, pentene 1 CH3OH+H2fiCH4+H2O exp(7.327–6549.8/T) 0.06
stands for the remainder of C5+, and 2 CH3OHfi(1/2)C2H4+H2O exp(11.633–7150.0/T) 0.14
C6H12 for coke. The modified reaction
mechanism of this kinetic set is given in 3 CH3OHfi(1/3)C3H6+H2O exp(9.064–5023.5/T) 0.21
Tab. 2. 4 CH3OH+H2fi(1/3)C3H8+H2O exp(3.423–2804.2/T) 0.20
The ratio between ethylene and propyl-
ene is greatly affected by the reaction con- 5 CH3OHfi(1/4)C4H8+H2O exp(5.345–3069.2/T) 0.24
ditions, i.e., temperature, pressure, and 6 CH3OHfi(1/5)C5H10+H2O exp(0.020–1064.8/T) 0.27
coke content. Generally, higher tempera-
ture and higher pressure leads to greater 7 CH3OH+H2fi(1/2)C2H6+H2O exp(–0.450–1064.8/T) 0.27
propylene formation. As for coke, it has 8 CH3OHfi(1/6)C6H12+H2O exp(9.702–6410.8/T) 0.31
both positive and negative influences on
9 CH3OHfiCO+2H2 exp(17.098–13591.5/T) 0.06
the MTO reaction as suggested in literature
[11, 12, 17, 19, 20]. The negative one is that 10 CO+H2OfiCO2+H2 exp(24.229–14313.2/T) –
the coke leads to plugging of the pores of
Rate forms Parameters
the catalyst and reduction of the reaction
kinetics. Once the coke content exceeds the 1–9 ri ¼ ki CMeOH qw fi Kw = 3.05;
critical value, i.e., the parameter D in the A = 9;
qw ¼ 1=1 þ Kw Xw
kinetic expression proposed by Ying et al. B = 2;
expðai Cc Þ D = 7.8
[17], the catalyst is no more active. This fi ¼
1 þ Aexp½BðCc  DÞ
critical coke content is also one of the
important characteristics for different cata- 10 ri ¼ ki CCO CH2O qw
lysts. Thus, the coked catalyst needs to be qw ¼ 1=1 þ Kw Xw
continuously regenerated to ensure enough

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4 Research Article

Purified
Olefins

Water

Unreacted
T=85.2 (°C) Methanol
Raw Olefin-1
T=470 (°C) Feed
Vaporizer Liq. pump-around -1
QT2 T=35 (°C)
NT=6
D=1.53 (m) C2-STR-R
Coked Catalyst Raw Olefin-2 (-1114.5 kw)

MTO Reactor Burner T=245 (°C) Liq. pump-around -2

T=114.1(°C)
T=470 (°C) Air T=35 (°C) Cooler
Cooler T=105.3(°C) (-1958.8 kw)
(-1464.9 kw) Inter Vap. frac=0.6
Condenser
Cat.
Cooler Feed
QT1
T=104.7 (°C)
NT=3 Methanol
D=1.88 (m) T=25(°C)
Heated Feed P=2.2 bar REB-C2 REB-HPC
T=352.2 (°C) F=875 (kmol/h) (-846.4 kw) (-604.4 kw)
Raw Olefin-3
T=150 (°C) To Wastewater
Treatment

To waste water
Quench treatment
Water
T=35 (°C)

Cooler

Figure 2. Design flowsheet of reaction and conditioning section for the MTO process.

er assumptions, the overall energy balance of the MTO reactor
can be performed, and the required feed temperature under
these assumptions can be calculated. By this way, although the
fluidized-bed reactor cannot be completely studied, the simpli-
fied model in this work can still properly describe its character-
istics, with accurate description of coking influences on the
reaction performances. Due to the limitation of paper size, all
detailed calculations and assumptions about the MTO reactor
are included in the Supporting Information (Part 1 and
Fig. S1).
In this work, the MTO reactor is designed to operate at
470 C, under a pressure of 2.2 bar, and with 875 kmol h–1 pure
methanol processed as feed. For operating under these condi-
tions, 4654.5 kW of thermal energy has to be continuously
removed from the reactor. The desired reaction conversion for
methanol is targeted at 99.8 %. The reactor is 3.6 m in length
and 1 m in diameter. However, in this work, the fluidized-bed
reactor is simplified to be an isothermal plug-flow reactor, thus
the size may not equal to the real one. The initial coke content
at 0.89 wt %, with about 80 % coked catalyst regenerated. From
these operating conditions, the propylene-to-ethylene mass
ratio will be around 1.1 at the MTO reactor outlet. The coke
content at the reactor outlet is 4.44 wt % and does not exceed
the critical coke content of 7.8 wt %.
4 Conditioning Section
After the MTO reaction, the reactor outlet is cooled to 150 C
for the quenching and purification step, and some low-pressure
steam is produced through this cooling step. The quenching
and purification step is a two-staged process, and the configu-
ration proposed by Miller and Senetar [33] is adopted in this
work. The Aspen built-in RADFRAC model is used for the
description of two quenching towers. In the first quenching
tower (QT1), the cooled MTO outlet stream enters at the bot-
tom, while the quench water enters at the top. Impurities to be
removed, including catalyst fines, carboxylic acids, and heavy
hydrocarbons, come out with water at the bottom. The bottom
stream is then split, and the major portion is sent back to QT1
at the upper section, while the remainder is sent to waste water
treatment. Due to the existence of carboxylic acids, some neu-
tralization agent could be added to this recycle stream if
needed. The portion of water that is sent to waste water treat-
ment could be recycled back to QT1 after treatment to serve as
the quench water input, but the discussion of this section is
beyond the scope of this work.
The vapor product from QT1 is first cooled in the inter-
condenser to be partial vapor-liquid through heat exchange
with feed, and is then sent to the second quench tower (QT2).
From QT2, a hydrocarbon vapor stream is produced at the top,
which is sent to the downstream separation process, while the

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Research Article
bottom stream is a relatively pure water stream. This bottom
stream is further split into three streams. One of them is sent
back to QT1, another one to the water treatment section, and
the last one serves as liquid pump-around, which is cooled by
the secondary cooler and sent back to QT2 in the lower section.
Also, there is a side-draw stream from the middle of QT2. This
side draw stream also serves as liquid pump-around and is
cooled by another secondary cooler. Through secondary cool-
ing, it is possible to reduce the amount of the required quench-
ing water. Also, the cooling duties of the secondary coolers can
be integrated in the olefin separation section to meet the energy
requirement. Under real condition, the removal of catalyst
fines is difficult. According to Miller and Senetar [33], one of
the advantages of this two-staged quenching process is the
decoupling of the impurity removal and the pure water recy-
cling. Thus, to ensure the separation performance, the flow rate
of the drag stream, i.e., the portion of QT1 bottom to waste
water treatment, could be used for adjustment. Also, the recir-
culation amount of water can be employed to maintain the
purification performance. By adjustment of these two key vari-
ables, long production cycles of the quenching system can be
maintained.
Although in this work catalyst fines (incapability of descrip-
tion) and carboxylic acid (not included in the lumped kinetic
model) are not present, the two-staged process is still included
to maintain the completeness of the whole MTO process. Sev-
eral other important design variables are listed in Tab. S1. From
the two secondary coolers in the lower part of QT2, one is inte-
grated in the reboiler of the C2-Stripper (REB-C2STR) and the
other one in the reboiler of the high-pressure column in the
de-ethanization part (REB-HPC). The outlet temperature from
REB-HPC is about 75 C and is further cooled to 35 C before
sending back to QT2. The secondary cooler in the upper part is
integrated in the reboiler of the de-ethanizer (REB-DEE), and
the outlet temperature is also 35 C.
There are several design specifications in this conditioning
step. First, the flow rate of the quench water input to QT1 is
used to maintain that 10 % of the water content from the MTO
outlet is sent to water treatment. This quench water flow rate
can be adjusted from the bottom split fraction of QT2 that
recycles back to QT1. Second, in QT2, the portion of the bot-
tom product as liquid pump-around is used to adjust the water
content in the vapor outlet from QT2, which is set to be 3 % of
water from the input stream to QT2. Third, the side-draw flow
rate from QT2 is used to adjust the cooling duty of the side
cooler (REB-DEE) to be equal to the reboiler duty of the de-
ethanizer. The reboiler duty will be determined from the opti-
mization of C2-STR in the later part.
Before being sent downstream for olefin separation, the va-
por product from the second quench tower needs further puri-
fication, in which the small amounts of unreacted species and
water are removed [33]. In a real process, adsorption using
molecular sieves can be applied to remove these small amounts.
In this work, another ASPEN built-in SEP unit is employed to
simulate this further purification and drying step. After that,
the olefin stream is ready for separation.
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5
5 First Separation Section
In the first separation section, the treated raw olefin stream
from the conditioning section is separated into three product
streams. One of them contains the light components, including
methane, H2, CO, etc. This light stream can be used as fuel gas
to produce some extra amount of energy. Another stream
involves the heavy products, including C4–C5 components.
This stream could be taken as raw material for production of
higher-carbon liquid fuel, or be cracked to form light hydrocar-
bons to enhance ethylene and propylene selectivity. The third
type of stream consists of a C2–C3 mixture, which contains
majorly ethylene, ethane, propylene, and propane, and is the
main product from this section. This stream is sent to the sec-
ond separation section for obtaining the high-purity ethylene
and propylene products.
The MTO reactor outlet stream involves mainly light hydro-
carbons, and its composition is much simpler compared with
the outlet gas from the conventional cracking process. Due to
the wide boiling point distribution of the components in this
raw olefin stream, still there is a need to discuss about the
design and operation. In this work, the process configuration
by Wang et al. is adopted for discussion [28], which includes
three columns, namely, a high-pressure column (HPC), a low-
pressure column (LPC), and a demethanizer (DEM).
The process is illustrated in the flowsheet of Fig. 3. The
cooled, purified raw olefin stream from the conditioning sec-
tion serves as feed. It is first compressed to the HPC pressure
and then cooled by heat exchanging with the DEM reboiler.
Afterwards, it is chilled to become partial vapor-liquid and is
then separated to be saturated vapor and liquid. These two sat-
urated streams are then sent to the HPC, in which lighter com-
ponents ( £ C2) and heavier components ( ‡ C3) are separated.
The heavier components ( ‡ C3) are then sent to the LPC, in
which C3 is separated from the other heavier components as
the top product, while the remaining C4 and C5 form the bot-
tom product.
According to the literature, propylene will be helpful in strip-
ping light components in the DEM, which can lead to lower
ethylene loss [26, 27]. Thus, the liquid C3 distillate from the
LPC is then pumped to higher pressure, chilled, refrigerated,
and sent to the top of the DEM. On the other hand, the top
vapor product from the HPC is also compressed to a pressure
higher than the DEM pressure. It is then chilled, refrigerated to
become partial vapor-liquid, and then separated to convert into
another two saturated vapor and liquid streams. After that, the
vapor stream is expanded through a turbine to let the tempera-
ture become even lower, and is then sent to the middle section
of the DEM. Similarly, the liquid stream is depressurized and
sent to the DEM, with the feed position lower than the vapor
feed. In the DEM, light components are collected as the top
product, while the bottom product is the C2–C3 mixture to be
sent to the second separation section. As mentioned, one of the
major targets in designing is to reduce the ethylene loss from
the light components due to the existence of hydrogen in the
olefin stream. In this work, the ethylene loss from the DEM is
targeted to be within 1 %.
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6 Research Article

Chw-3 HTRef-2 LTRef-2

LPC-COND (-124.0 kw) (-101.8 kw) (-58 kw)
Qc=-840.6 (kw)
T=-37 (°C) Light
T=15 (°C) T=-17 (°C) DEM-COND Product
(-22.6 kw)
HPC-COND T=-36 (°C) T=-13 (°C) T=-30 (°C)
Pump
C3-Products Qc=-699.1 (kw)
(3.71 kw)
T=46 (°C)
Comp-2 Turbine
1
LPC 67.4 (kw) -4.4(kw)
P=19 (bar) Vap-2 5
32 NT=48 Vap-1 DEM
11 10
T=-34 (°C) P=30 (bar)
14 NT=34
HTRef-1
HPC (-197.5 kw)
P=20(bar)
Chw-1 NT=35 Liq-2 33
(-387.1kw) V-1
Heavy LTREF-1
Product Liq-1 Comp-1 Purified
(-207.5kw)
Olefin
LPC-REB T=66 (°C)
T=-17 (°C)
Qr=867.1 (kw) P=20 (bar)

HPC-REB T=13 (°C)

Qr=604.4(kw) DEM-REB
C2/C3 (313.3 kw)
Mixture

T=31 (°C)

Figure 3. Design flowsheet of the first separation section for the MTO process with optimized results.

There are several design specifications in the first separation
section which are collected in Tab. 3 (variable status:
DS/VARY). Besides, it is assumed that the highest grade of
refrigerant accessible is the propylene refrigerant, with the boil-
ing point at about –47.5 C. In Luyben’s work, the application
of a low-temperature refrigerant takes place at –50 C, which is
very close to the industrial-grade propylene refrigerant [32].
Thus, for considering the cost of this refrigerant, the authors
assume the same cost as that for Luyben’s low-temperature
refrigerant.
After the design, optimization work is performed based on
each sub-section, i.e., HPC, LPC, and DEM. In order to better
illustrate the overall works done by the authors, only the opti-
mization algorithms and the final results are included in the
text, other detailed optimization results can be found in the
Supporting Information.
The algorithm for the optimization of this section is illustrat-
ed in Fig. 4. Prior to optimization, all the design variables in
each sub-section and their status are analyzed, with the results
recorded in Tab. 3. For the HPC sub-section, four variables are
listed as optimization variables, including column pressure
(HPC-P), flash temperature (T-Flash), total number of trays
(HPC-NT), and vapor feed location (HPC-NFV). From the pre-
liminary test, the location differences between vapor feed and liq-
uid feed (HPC-NFL) have no significant impact on the TAC, thus
it is fixed at three trays in optimization works (NFL-NFV = 3).
For the flash temperature, it is assumed that only chilled water
is used, thus the temperature is not allowed to be lower than
15 C.
The final optimization results under HPC-P = 19–22 bar are
illustrated in Fig. 5 a, with the detailed results given in
Figs. S2–S5. From the data it can be concluded that lower pres-
sure leads to less TAC. However, the column pressure has a
more complex influence on the system. As the HPC pressure
increases, the compression cost of the raw olefin feed stream
becomes higher, but the further compression cost decreases.
Besides, the selection of HPC pressure will also affect the oper-
ation of the LPC, as the higher HPC pressure leads to a higher
bottom temperature and lower reboiler duty of the LPC. Thus,
due to the interactive behavior, the pressure of the HPC is
determined after the optimization of LPC and DEM and is the
last variable to be decided.
Optimization of the LPC is simpler, with only three design
variables, i.e., the column pressure (LPC-P), feed location
(LPC-NF), and total number of trays (LPC-NT). For the selec-
tion of LPC-P, it is assumed that cooling water is used, under
which the corresponding column pressure is 19 bar. After opti-
mization, the optimal design conditions are at LPC-NT = 48,
and LPC-NF = 32, with the detailed results described in Fig. S6.
However, as these two variables vary, the impact on TAC is not
obvious. Thus, it is assumed that when calculating the TAC
under different HPC pressure, the same optimal conditions still
hold. The influence of HPC pressure on LPC is indicated in
Fig. 5 b, which demonstrates that the TAC decreases at higher
HPC pressure.
The last part of the optimization work in this section is the
DEM, in which lots of variables have to be determined.
Through preliminary test, two variables, namely, the further
compression pressure and the refrigeration temperature of liq-
uid C3 distillate from the LPC, can be determined. The calcula-
tion of further compression is a compromise between the elec-
tricity used for the compressor and the refrigeration duty. As
the pressure becomes higher, less refrigeration duty is required.
Thus, from the preliminary test, the further compression pres-
sure is set at 40 bar. The determination of refrigeration temper-
ature is a trade-off between the separation efficiency in the
DEM and the refrigerant requirement, as a greater refrigeration
extent will lead to better separation. Thus, the liquid C3 distil-
late refrigeration temperature is reasonably determined to be
–37 C, at which the propylene refrigerant is applicable.
After the preliminary test, four variables are listed as optimi-
zation variables, including column pressure (DEM-P), vapor

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Research Article 7

Table 3. Status of variables in first separation section.

Variables Status Specifications and description (constraint for optimization work)

HPC

HPC-P Optimization ( ‡ LPC-P)

T-Flash Optimization ( ‡ 15 C)

HPC-NT Optimization (X)

HPC-NV Optimization (X)

HPC-NL Fixed HPC-NL = HPC-NV + 3

HPC-RR DS/VARY Adjust to make C1–C2 recovery = 99.9 % at HPC top

HPC-QREB DS/VARY Adjust to make C3–C5 recovery = 99.9 % at HPC bottom

LPC

LPC-P Optimization ( ‡ 19 bar)

LPC-NF Optimization (X)

LPC-NV Optimization (X)

LPC-RR DS/VARY Adjust to make C3 recovery = 99.9 % at LPC top

LPC-QREB DS/VARY Adjust to make C4–C5 recovery = 99.9% at LPC bottom

DEM

Further compression pressure Fixed Set at 40 bar

Pump outlet pressure Fixed Equal to DEM-P

C3-refrigeration temperature Fixed Set at –37.5 C

HPC top product refrigeration temperature DS/Vary Adjust to make C2 recovery = 99 % at DEM bottom

DEM-NT Optimization (X)

DEM-NV Optimization (X)

DEM-NL Optimization (X)

DEM-P Optimization (X)

DEM-RR DS/VARY Adjust to make CH4 recovery = 99 % at DEM top

DEM-QREB DS/VARY Adjust to make C3 recovery = 97 % at the DEM bottom

feed location (DEM-NFV), liquid feed location (DEM-NFL),
and total stages (DEM-NT). Because HPC-P affects the
operation of the DEM, thus in the first run of optimization the
HPC pressure is assumed to be at 24 bar. Under this
assumption, the optimal set of design and operating variables
is at DEM-P = 30 bar, DEM-NT = 34, DEM-NFV = 5, and
DEM-NFL = 10. However, because the further compression
pressure is fixed at 40 bar, thus only the cost of a further com-
pressor is varied under different HPC pressure. When calculat-
ing the TAC under different HPC pressure, the correction of
the further compression cost is included based on the optimal
operating condition which is obtained at an HPC pressure of
24 bar. This correction is indicated in the correction block on
the right-most side in Fig. 4.
The detailed optimization results are collected in
Figs. S7–S10. Fig. 5 c illustrates the relationship between HPC
pressure and TAC of the DEM, as the TAC is decreased under
higher HPC pressure. After the optimization works of LPC and
DEM are completed, the TACs for each part under different
HPC pressures are summed. The results are displayed in Fig. 5
d, from which it is obvious that the best operating pressure of
the HPC is 20 bar. Under this pressure, the optimized set of
design and operating variables for HPC is at HPC-NT = 35,
HPC-NFV = 11 (HPC-NFL = 14), and HPC-T = 15 C. The
optimized total TAC for the first separation section is
2273.4 kUSD.
6 Second Separation Section
In the second separation section, two major blocks are
included, i.e., C2-splitting and C3-splitting. The process config-
uration for this section with optimized results is illustrated in
Fig. 6. There are two columns included in C2-splitting, namely,

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8 Research Article

Figure 4. Optimization algorithms for the first separation section.

a) b)
1450
HPC TAC 410 LPC TAC 410
1440
408 408
HPC TAC (1000 USD)

LPC TAC (1000 USD)

1430
406 406

1420
404 404

1410 402 402

1400 400 400

1390 398 398

19.0 19.5 20.0 20.5 21.0 21.5 22.0 19.0 19.5 20.0 20.5 21.0 21.5 22.0
HPC pressure (Bar) HPC pressure (Bar)

c) d)
475 2400
DEM TAC Total TAC
470 2399
465
DEM TAC (1000 USD)

Total TAC (1000 USD)

2398
460
2397
455
2396
450
2395
445

440 2394

435 2393
19.0 19.5 20.0 20.5 21.0 21.5 22.0 19.0 19.5 20.0 20.5 21.0 21.5 22.0
HPC pressure (Bar) HPC pressure (Bar)

Figure 5. Optimization results for the first separation section.

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Research Article 9

DEE-COND
Qc=-1120.6 (kw)
T=-16.2(°C)

Ethylene
F=144.39 (kmol/h)
(99.5 mol%)

C2 Mixtures Deethanizer
C2-STR COND 30 P=28 (bar)
Qc=-723.84(kw)
NT=60
T=-14.4(°C) C3-COND
Qc=-4340.8 (kw)
Tail gas-1 T=43.5(°C)
(rich in ethane)
F=4.208 (kmol/h)
C2H4=17.2 mol% Propylene
C2H6=80.4 mol% F=102.97 (kmol/h)
DEE-REB
C2-Stripper C3H6=2.5 mol% 99.5 mol%
C2/C3 Mixture Qr=1114.52 (kw)
17 P=29 (bar) T=3.0 (°C) C3H8=239 ppm
T=13.4 (°C)
NT=38
P=30.1 (bar)
F=259.8 (kmol/h)
C2H4=55.6 mol%
C2H6=1.6 mol%
C3H6=39.9 mol% C3 Mixtures 135 C3-Splitter
C3H8=2.9 mol%
C4H8=95 ppm P=18(bar)
CH4=429 ppm C2-STR Reb NT=195
Qr=846.44 D=1.68(m)
T=67.1 (°C)
Tail gas-2
F=8.5 (kmol/h)
C3H6=12.6 mol%
C3H8=87.1 mol%
C3-Reb C4H8=0.3 mol%
Qr=4259.6(kw)
T=53.3(°C)

Figure 6. Design flowsheet of the second separation section with optimized results.

C2-stripper and de-ethanizer. In the C2-stripper, C2 compo- be less than or at least equal to the C2-stripper pressure. The
nents in the C2–C3 mixture are separated out, and this C2 optimization algorithms for two columns are the same, using
mixture is sent to the de-ethanizer for further separation of the following steps:
ethylene and ethane. The design specifications for these two (1) Guess a value of column pressure.
columns are collected in Tab. 4. (2) Guess a value of NT.
(3) Change the value of NF to minimize TAC. For each case,
Table 4. Design specifications in second separation section. the design specification should be met. The design specifi-
cations for each column are mentioned above.
Column Specification Variable to adjust (4) Go back to (2) and change NT until TAC is minimized.
(5) Go back to (1) and change column pressure until TAC is
C2-Stripper C2 Recovery = 99.9 % (top) Reflux ratio
minimized.
C3 Recovery = 99.9 % (bottom) Reboiler duty By this algorithm, the optimal design and operating variables
De-ethanizer C2H4 Recovery = 99.9 % (top) Reflux ratio
for two columns can be obtained. The optimization results are
recorded in Figs. S11 and S12. From the results, the best set of
C2H4 Purity = 99.5 mol % (bottom) Reboiler duty design and operating variables for the C2-stripper is P = 29 bar,
C3-Stripper C3H6 Recovery = 99.9 % (top) Reflux ratio NT = 38, and NF = 17. On the other hand, the best set of design
and operating variables for the de-ethanizer is P = 28 bar,
C3H6 Purity = 99.5 mol % (bottom) Reboiler duty NT = 60, and NF = 30. The optimized TAC for the C2-stripper
is 363.41 kUSD, and is 524.21 kUSD for the DEE. After optimi-
zation, the reboiler of both columns is integrated in the secon-
For each column, there are three optimization variables, dary coolers of the second quenching tower (QT2), as illustrat-
including column pressure (P), total number of stages (NT), ed previously in Sect. 4.
and feed location (NF). The column pressure for the C2-strip- C3 product from C2-Splitter is sent to C3-splitting section
per should be less than or at least equal to the demethanizer for propylene and propane separation. Traditionally, a single
pressure, whereas the de-ethanizer pressure is also designed to column (C3-stripper) is used for C3-splitting. The typical oper-

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’’ These are not the final page numbers!

10 Research Article

ating pressure is at near 20 (bar), for which cooling water is NFV [–] vapor feed location
allowed to be used in condenser, and industrial low pressure NT [–] total number of trays
steam is used as reboiler heat source. However, C3-splitting is a P [bar] pressure
close-boiling system, thus it requires large amount of theoreti- Qi [kW] heat duty
cal trays and energy for separation. The specifications of ri [kmol kgcat–1min–1] reaction rate
C3-splitting are also collected in Tab.4. For application of cool- T-Flash [–] flash temperature
ing water in condenser, the column pressure should not be over Xw [–] water mole fraction
18 (bar), at which it is fixed in this work. Thus, only two varia-
bles, total number of trays (NT) and feed location (NF) are left Greek letters
as optimization variables. From the optimization results, the
a [–] parameter in coke deactivation
best set of design variables is at NT=195 and NF= 135, with the
function
optimal TAC to be 1882.55 (kUSD). The detailed optimization
q [–] water attenuation function
results are collected in Fig. S13.
j [–] coke deactivation factor

Abbreviations
7 Conclusion
Ci components with i carbons (i = 1–5), including
The steady-state design and optimization of the methanol-to- paraffins, olefins, and isomers if any
olefin (MTO) process is studied and the design and operating C2-STR C2-stripper
variables are thoroughly investigated. The optimal design and C3-STR C3-stripper
operating variables are found by minimizing the total annual DEM demethanizer
cost (TAC), with the assumption of a three-year payback peri- HPC high-pressure column
od. The overall MTO process is divided into four sections, i.e., LPC low-pressure column
reaction section, conditioning section, first separation section, QT1 first quench tower
and second separation section. In this process, the goal is to QT2 second quench tower
convert methanol into an olefin mixture, and then to separate REB-i reboiler of columns (i = C2-STR, DEE, or HPC)
ethylene and propylene as the final main products. In each TAC total annual cost
sub-part, a heat integration strategy is also proposed for better
energy usage. Through these rigorous design and optimization
proposals, the MTO process could become more economically References
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12 Research Article

2400
Research Article: The methanol-to- Design and Optimization of Methanol-
Total TAC
olefin (MTO) process provides an to-Olefin Process. 2399
efficient alternative route to produce Part I: Steady-State Design and

Total TAC (1000 USD)

2398
light olefins. The steady-state design Optimization
2397
and optimization of this process as well
as the corresponding design and B.-Y. Yu, I-L. Chien* 2396
operating variables are investigated. 2395
Through rigorous design and Chem. Eng. Technol. 2016, 39 (XX),
optimization proposals, the MTO XXX K XXX 2394

process could become more 2393

19.0 19.5 20.0 20.5 21.0 21.5 22.0
economically attractive and also be DOI: 10.1002/ceat.201500654
HPC pressure (Bar)
improved in energy saving.

Supporting Information
available online

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