Petroleum Science and Technology

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Methanol-to-olefins process technology: current

status and future prospects

Makarand R. Gogate

To cite this article: Makarand R. Gogate (2019) Methanol-to-olefins process technology:

current status and future prospects, Petroleum Science and Technology, 37:5, 559-565, DOI:
10.1080/10916466.2018.1555589

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Published online: 26 Jan 2019.

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PETROLEUM SCIENCE AND TECHNOLOGY
2019, VOL. 37, NO. 5, 559–565
https://doi.org/10.1080/10916466.2018.1555589

REVIEW

Methanol-to-olefins process technology: current status and

future prospects
Makarand R. Gogate
Department of Chemical Engineering, Jawaharlal Nehru College of Engineering, Aurangabad, India

ABSTRACT KEYWORDS
The methanol-to-gasoline (MTG) and methanol-to-olefins (MTO) process coal; DICP; dimethyl ether;
are 2 epochal technological discoveries in the synfuels arena, first intro- ethylene; light olefins; lurgi;
duced by Mobil Oil Corporation, some 50 years after the Fischer-Tropsch methanol; MTO; natural gas;
propylene; syngas;
process. Apart from the technological breakthroughs, the MTG and MTO UOP/Norsk
processes have also provided a rich tableau for scientific research and pur-
suits. In this report, we will first provide anecdotal information pertaining
to the discovery and development of these 2 processes. We will then focus
on how the MTO process has evolved into a stand-alone technology in its
own right for the 2 value-added products, ethylene, and propylene.
Currently, UOP/Hydro is the world’s leading commercial technology sup-
plier/licensor, for the MTO process, with Dalian Institute of Chemical
Physics (DICP) and Sinopec, as its close competitors. It appears that the
MTO technology is now primed for future advancements and expansions.
Two recent MTO production sites put in place with UOP/Norsk technology
licensors, became operational recently, both in China: The newest is a
0.8 MM MTPA venture, licensed and operated by Jiangsu Sailboat
Petrochemical Company, and the 0.3 MM MTPA Wison China Clean Energy
venture started in 2013, licensed and operated by Wison Energy.

1. Introduction
The methanol-to-gasoline process (MTG, as introduced first by Mobil researchers’, in 1977), and
its companion, methanol-to-olefins (MTO, as introduced first by Union Carbide, in 1981) are 2
seminal and indeed epochal technological breakthroughs in synfuels research, some 50 years after
the Fischer–Tropsch process. Initially developed in the United States in response to the energy
crisis of the 1970s (oil embargo with the accompanying gasoline price volatility and uncertain
supply chain), these 2 technological wonders are now viewed upon as a “synfuels factory”, ready
to put in place as technological and economic demands warrant. The genesis and evolution of the
methanol-to-hydrocarbons (MTH) technology, from its discovery up until successful commercial
implementation/practice, has also provided a rich tableau for scientific research and pursuits,
filled with research controversies/challenges and advances.
In the overall mechanism of the methanol-to-gasoline (MTG) process (Derouane 1984; Chang
1983; Chen and Reagan 1979), it is conclusively proven by most experimental studies to date that
methanol is first dehydrated/converted to an equilibrium mixture of methanol, dimethyl ether
(DME), and water, over the acidic HZSM-5, which is subsequently converted to a mixture of ole-
fins, aliphatics, and aromatics, upto C10, at reaction conditions of 350–400
C, and atmospheric

CONTACT Makarand R. Gogate mgogate66@gmail.com Department of Chemical Engineering, Jawaharlal Nehru College
of Engineering, N-6 CIDCO, MGM Medical College Campus, 259 Samarthnagar, Oppo. S.B.I. Branch, Aurangabad, India.
Color versions of one or more of the figures in the article can be found online at www.tandfonline.com/lpet.
ß 2019 Taylor & Francis Group, LLC
560 M. R. GOGATE

Figure 1. A general reaction scheme for the methanol-to-gasoline (MTG) process. As can be seen from the scheme, an interrup-
tion of the overall reaction leads to production of primarily light olefins, so-called methanol-to-olefins (MTO) process (adapted
from Keil 1999; Chang and Silvestri 1977).

pressure. The MTG process offers the following unique advantages: (a) Hydrocarbons are pro-
duced in a rather narrow compositional range; little methane and no hydrocarbons larger than
C11 are formed, (b) A high conversion of methanol can be combined with a high selectivity for
isoparaffins and aromatics of higher octane value, and, (c) ZSM-5 based catalysts are character-
ized by a very low aging rate. The MTG process (Chang and Silvestri 1977) was considered to be
a new and simpler route to gasoline-range hydrocarbons from methanol. The gasoline derived
from the MTG process is chemically conventional, in a narrow boiling range (C4–C10, no C11þ),
and is substantially superior in yield and quality from conventional F–T processes, with RON’s
exceeding 90–95.
A general mechanistic model of the MTG process is given in Figure 1. At the outset, it is interest-
ing to invoke the experimental data and representative reaction surveys from the original Mobil Oil
contribution (Chang 1984; Chang 1983; Chang and Silvestri 1977), to glean further insights into the
general mechanistic pathways of methanol conversion. The reaction pathway for methanol conversion
to hydrocarbons, at 371
C, in terms of product distribution vs. contact time, is given in Figure 2.
The effect of contact times of over three-orders of magnitude (LHSV of 1080 to 1) on the product
distribution of methanol conversion at 371
C is covered. The results at the lowest contact time (1/
LHSV, in volumes of feed per volume cat per hr, 1080) show the time-resolved progress of the ether-
forming reaction on H-ZSM-5. Clearly, methanol is first converted to an equilibrium mixture of
DME, methanol, and H2O, over the H-ZSM-5 catalyst. However, it is also clearly seen from the reac-
tion profile that there is a pronounced effect of product inhibition by H2O, as evidenced by a shift in
the reaction order in methanol profile, in the range of contact times between 0.0001 and 0.001 h
(LHSVs between 1080 and 108). After this sequence of initiation, light-off, and product inhibition—
which occurs in a very fairly narrow range of contact times—the autocatalysis feature of the MTG
reaction, for further conversion—DME/CH3OH to C2–C5 olefins to C5-C10 gasoline-boiling range
HCs—is also clearly evident, from the time-resolved profile (Figure 2).

2. Methanol-to-olefins (MTO) process – discovery and development

As stated above, the development the methanol-to-hydrocarbons reaction, and, in particular, the
methanol-to-gasoline (MTG) process was a fortuitous yet adventitious discovery by Mobil Oil
Corporation (now ExxonMobil). Two research groups, one at Mobil Corporate Research (Edison,
NJ) and the other at Mobil Central Research Laboratories (Princeton, NJ), were independently
working on 2 unrelated reactions, methanol to ethylene oxide, and the reaction with methanol
with isobutylene to form neopentane (an aliphatic hydrocarbon, C5þ), respectively. While the
methylation of isobutylene did not proceed according to their reaction hypothesis, the second
group working at Mobil’s Central Research Labs discovered that the conversion of methanol was
complete and quantitative, over the ZSM-5 catalyst used. The overall reaction stoichiometry could
be represented by the following reaction:
CH3 OH ! ½CH2  þ H2 O (1)
The conversion of methanol is essentially complete and stoichiometric, and the product select-
ivity is 56% (w/w) towards hydrocarbons (HCs) and 44% to H2O. It is interesting to note here
that [CH2] is the average oligomeric branch of an olefin hydrocarbon, and consistent with the
 PETROLEUM SCIENCE AND TECHNOLOGY 561

Figure 2. A representative reaction survey of the methanol-to-gasoline process (MTG) at 371
C and 1 atm. The product yields
(wt%) are plotted vs. the inverse liquid hourly space velocity (1/h). As proposed by the simplified reaction model, the overall
H2O yield is 56% (adapted from Chang and Silvestri 1977).

reaction model proposed for the MTG process (Figure 1), as stated above, an interruption of the
methanol-to-hydrocarbons reaction, by careful control over process conditions (T, space velocity),
led to the now-common methanol-to-olefins process (MTO). As can been seen from the reaction
scheme and experimental reaction surveys (Figures 1 and 2), and as stated above, an interruption
of the reaction leads to production of primarily light olefins instead of gasoline. This is the then
so-called and now hugely successful MTO process. As stated earlier, the bench-scale studies on
the MTO process were carried out by researchers’ at Mobil Oil Corporation (Chang et al. 1984;
Schoenfelder et al. 1994; Tshabalala and Squires 1996), primarily over a ZSM-5 catalyst, in a
fixed-bed configuration. The researchers’ at Union Carbide were the first to show the excellent
shape selectivity and control over a product distribution of light olefins, C2–C4 over a novel
SAPO-34 catalyst. The discovery of novel silicoaluminophopshate materials, and, in particular,
SAPO-34, provided a technology breakthrough, due to their unique pore size and geometry, a
milder acidity—compared to ZSM-5. The reduced pore size of SAPO-34, 3.5 Å, limits the diffu-
sion of heavy and branched hydrocarbons, and increases the selectivity to light olefins. The
milder acidity of SAPO-34 lowers the extent of hydrogen transfer reactions, which minimizes the
yield of paraffinic products, and increases the yield of olefinic product slate. However, on account
of pore diffusional gradients, the SAPO-34 catalysts are also prone to severe deactivation. The
Union Carbide research group that developed the MTO technology later became part of UOP/
Norsk joint venture. A few recent reviews on the MTO processes are cited here as being most
noteworthy (Tian et al. 2015; Khadzhiev et al. 2015; Kvisle et al. 2008; Keil 1999; Stocker 1999).

3. MTO process – commercial technologies

The UOP/Norsk Hydro in-house technology, developed jointly by UOP (now Honeywell UOP,
based in Des Plaines, IL, USA), and Hydro (based in Oslo, Norway) is the first and now most
popular technology available to the licensors of the MTO process. There are 4 major methanol-
to-olefin (MTO) technologies, of 4 which all are being used in China’s burgeoning coal-to-olefins
industry. These technologies are as follows; (a) D-MTO/-MTO-II, (b) S-MTO, (c) MTO by UOP/
Norsk Hydro, and (d) MTP by Lurgi.
Figure 3 provides an overview of the four MTO technologies. “D-MTO/D-MTO-II” and “S-MTO”
are technologies developed in China by Chinese Corporations/Institutes. For example, D-MTO
562 M. R. GOGATE

Figure 3. Overview of the methanol-to-olefins process (MTO), with four primary technologies available for commercial
installations.

technology was originally developed by the researchers’ at Dalian Institute of Chemical Physics
(DICP), with funding from Sinopec. The Sinopec-developed technology, S-MTO, is also a major
player in MTO technology and licensing. Currently, the D-MTO/D-MTO-II technology has the larg-
est market share in China (64% and 70% in terms of number of units and capacity, respectively).
The essential technology blocks and providers for the China Baotou coal-to-olefins process are
shown in Figure 4. The reactor and process conditions for the methanol-to-olefins technology
block are as follows: The reaction under D-MTO/D-MTO-II technology is an acid catalyzed reac-
tion with a 100% methanol conversion rate. This reaction occurs at high temperature and
medium pressure (400–500
C and 0.1–0.3MPa) and is exothermic. The D-MTO/D-MTO-II sys-
tem(s) consist of a fluidized catalytic reactor, a catalyst regenerator, a unit for separating ethylene
(C2)/propylene (C3) and heavier hydrocarbons (þC4), and peripheral equipment (e.g., utilities,
air compression units). The key difference in D-MTO/D-MTO-II technologies and S-MTO is that
S-MTO technology uses a novel (patented) version of SAPO-34 as a catalyst which is able to alter
the product mix (yield) of ethylene vs. propylene. The ratio of ethylene and propylene can be
adjusted from 0.6 to 1.3. A product ratio of ethylene and propylene of 1.3 suggests a product
yield of ethylene to propylene of 57% and 43%.
In the UOP/Norsk technology (Hurd et al. 2014; Funk et al. 2004; Vora et al. 1998), methanol
is pre-heated to gaseous phase and introduced into the MTO reactorfor olefins synthesis (Figure
5). The reactor operates in the vapor phase at temperature of 340–540
C and pressure of
0.1–0.3 MPa. The reactor effluent (i.e., ethylene, propylene, heavier olefins, and water) is then
cooled. Water is separated from the product gas stream. The effluent is then fed into a light ole-
fin recovery unit which separates ethylene (C2) & propylene (C3) while the heavier olefins C4 to
C6 (olefins with 4 to 6 carbon atoms at each olefins molecule) are sent to be cracked into either
C3 (propylene) or C4 (butadiene) olefins. The propylene is recycled for light olefin recovery while
the C4 is used as fuel for the MTO process or other processes.
In the Lurgi MTP process (Figure 6, Hurd et al. 2014), methanol is first pre-heated to 260
C
before being fed into the DME reactor, where, under the presence of an acidic dehydration catalyst,
75% of the methanol feed is converted toDME and water. The remaining 25% of reactor effluent is
unreacted methanol. The reaction mixture is then heated to 470
C and fed into the first MTP reactor
with steam (0.3–0.8 kg steam of reaction mixture, or, 0.75–2kmol steam/kmol reaction mixture). The
first MTP reactor converts more than 99% of the methanol/DME mix into propylene. The reaction
mixture is then fed into a second and third MTP reactor to further increase the propylene yield.

4. Conclusions
The methanol-to-gasoline process (MTG, as introduced first by Mobil researchers’, in 1977), and
its companion, methanol-to-olefins (MTO, as introduced first by Union Carbide, in 1981) are 2
 PETROLEUM SCIENCE AND TECHNOLOGY 563

Figure 4. Technology providers for the Shenhua Baotou China coal-to-olefins project with Installed capacity of 0.6 MM MTPA
(adapted from Hurd et al. 2014).

Figure 5. Process flow diagram of the UOP/hydro MTO process (adapted from Keil 1999).

Figure 6. An overview of the Lurgi MTP process. The use of a separate DME reactor to convert gaseous methanol stream into an
equilibrium mixture of methanol, DME, and water is noteworthy (adapted from Hurd et al. 2014).

seminal and indeed epochal technological breakthroughs in synfuels research, some 50 years after
the Fischer–Tropsch process. While several recent perspectives on the MTO process provide
details on reaction mechanism, catalyst development, and reactor design and scale-up, MTO
564 M. R. GOGATE

Table 1. Industrial Installations of the methanol-to-olefins technology (pilot/demonstration-scale or commercial-scale,

post-2000)
Process Catalyst
conditions (T, performance (C,
No. MTO technology Licensor/operator Scale Catalyst P, WHSV) S, Y)
1 UOP/hydro UOP (Feluy, Belgium) 0.2 MM MTPA SAPO-34 (attri- 400–550
C, 100%, 80%þ C-
advanced MTO tion-resistant 1–4 atm selectivity to
(with ole- formulation) C2, C3, olefins
fin cracking)
2 D-MTO (Dalian Shenhua China 0.6 TPA SAPO-34 400–550
C, N/A
Institute of Energy 4–5 atm
Chemical (Mongolia, China)
Physics)
3 S-MTO Sinopec 0.2 MM TPA SAPO-34 400–550
C, N/A
(Sinopec MTO) 1–5 atm
4 MTP (Lurgi) Shenhua Group with 0.5 MM TPA SAPO-34 N/A N/A
Ningxia Provincial
Govt.
(Ningxia, China)
5 MTP (Lurgi) Datang Int’l Power 0.5 MM TPA SAPO-34 N/A N/A
with China
Datang
(Mongolia, China)
6 Honeywell UOP Jiangsu Sailboat 0.8 MM TPA SAPO-34 400–550
C, 100%, 85%
Petrochemical 1–5 atm to C2 þ C3
company (Jiangsu
Province, China)
7 Honeywell UOP Wison China Energy 0.3 MM TPA SAPO-34 400–550
C, 100%, 85%
(Nangxin 1–5 atm to C2 þ C3
Province, China)

technology development and commercialization is the focus and narrative of this presentation. As
an anecdotal note, it is interesting to note that while Mobil Oil Corporation’s MTO technology
was the first to make it over to the Pilot stage—a 0.4 KTPA demonstration unit at Wesseling,
Germany, the leadership role in world-scale MTO plants—coal-to-olefins—now belongs to UOP
(now, Honywell UOP). The partnership operates at least 5 world-scale MTO plants in China
alone, with capacities ranging from 0.3 to 0.8 MM MTPA. While other regions (Asia Pacific, US
Gulf Coast, etc.) have been slow to adapt to this rapidly shifting landscape, the MTO technology
seems to poised for tremendous advances and growth in China. To this end, a recent announce-
ment—by Honeywell UOP—of the world’s largest single-train MTO process technology imple-
mentation, a 0.8 MM MTPA world-scale olefins plant, licensed to Jiangsu Sailboat Petrochemical
Company, is the most noteworthy.

ORCID
Makarand R. Gogate http://orcid.org/0000-0001-6147-8161

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