Catal Surv Asia (2010) 14:111–115
DOI 10.1007/s10563-010-9094-4
Development of Highly Selective Process for Mono-Ethylene
Glycol Production from Ethylene Oxide via Ethylene
Carbonate Using Phosphonium Salt Catalyst
Kazuki Kawabe
Published online: 8 June 2010
Ó Springer Science+Business Media, LLC 2010
Abstract A new process for the production of mono-
ethylene glycol (MEG; HOCH2CH2OH) was developed
by Mitsubishi Chemical Corporation (MCC) to meet its
growing demand in the world. While the MEG selectivity
of conventional non-catalyzed process is around 89% under
typical conditions, that of the new process exceeds 99%.
The key of the high selectivity is the two-step synthesis via
ethylene carbonate. The first step reaction is catalyzed by
phosphonium salts and generates ethylene carbonate as an
intermediate. This is followed by hydrolysis of ethylene
carbonate in the second step. Several commercial plants of
the new process have already been operated world-wide.
Keywords Mono-ethylene glycol  Phosphonium salt 
Ethylene carbonate  Carbonation  Carbon dioxide
1 Background
MEG is one of the most important chemicals which is
consumed as a raw material of polyester fiber, bottles and
film and also as antifreeze. As more polyester is consumed
year by year, more MEG is required especially in Asia. The
world demand for MEG is estimated to be 17 million tons/
year with the growth rate of approximately 6–7% per year.
Many new plant projects are reported mainly in Asia and
Middle East.
Almost all MEG in the world has been produced by
hydration of ethylene oxide (EO). The hydration reaction
K. Kawabe (&)
Process Technology Laboratory, Petrochemicals Research
Center, Mitsubishi Chemical Corporation, 17-1 Towada,
Kamisu-shi, Ibaraki, Japan
e-mail: 3804641@cc.m-kagaku.co.jp
proceeds at elevated temperature without any catalysts. This
conventional thermal process was started in 1937 by Union
Carbide Corporation (UCC) [1]. In this reaction system,
MEG inevitably reacts with remaining ethylene oxide
generating di-ethylene glycol (DEG; HOCH2CH2OCH2-
CH2OH). Tri-ethylene glycol (TEG) and heavier ethylene
glycols are also generated as by-products in the same
manner.
DEG and TEG are mainly used for unsaturated polyes-
ters and solvents. The demand growth rates of these com-
pounds are limited. The DEG demand increases only 2–3%
per year. More and more new large plants would produce
not only MEG but also DEG and TEG increasing the
demand gap. In order to solve this problem, new selective
processes have long been desired.
\Conventional MEG production scheme[
EO þ H2 O ! MEG
EO þ MEG ! DEG
EO þ DEG ! TEG
EO þ TEG ! Tetra-ethylene glycol
Because of the consecutive reactions which occur
statistically, the selectivity of MEG is determined only by
the feed ratio of ethylene oxide and water. Dilution of
ethylene oxide by large excess of water is the only way
to raise the selectivity of MEG. For example 89%
selectivity of MEG requires 20 mol of excess water to
1 mol of EO.
However, higher water ratio causes lower MEG con-
centration in the reaction mass. To obtain MEG as product,
it is necessary to evaporate all of excess water, which has
large latent heat, in the purification section. As a result it
requires large energy consumption and complicated facil-
ities to remove the water.
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Many studies have been done to improve MEG selec-
tivity. For example a reactive distillation technology was
tried to utilize for hydration of ethylene oxide [2]. But it
was difficult to find appropriate operation conditions.
While the boiling point of EO is only 10.7 °C, the hydra-
tion reaction temperature should be above 200 °C to keep
the proper reaction rate. To condense EO at such high
temperature, extremely high pressure would be necessary.
That means high temperature operation in the bottom
section, which may cause decomposition of MEG and other
undesirable side reactions.
A simpler way to obtain high selectivity is supposed to
use some appropriate catalysts. A lot of efforts were made
with regard to this idea. For example, some metal complex
anions were tested as catalyst by UCC [3]. Using metalate
anion, such as molybdate, metavanadate and so on, they
showed an increase in selectivity up to around 95% at
relatively higher EO concentration. UCC also tried a two-
step indirect process similar to ours [4]. According to the
patent, they selected potassium iodide for the carbonation
catalyst. Several companies continue developing a new
process or find new catalysts even now. However, as far as
we know, the achieved selectivity is limited to around 95%.
2 History
MCC started in the ethylene glycol business by acquiring a
process license from Scientific Design Company, Inc. in
1960. After that, MCC also got a process license from Shell
Chemicals. Both processes were non catalyzed thermal
ones.
The research on the new selective MEG technology by
MCC was started in 1979. The stage of development pro-
ceeded to bench scale study in 1982. But at that time the
MCCs business interest was limited to Japanese domestic
market, in which steady demand growth for DEG and TEG
existed. The R&D project could not find a clear target to
apply this technology and was suspended.
After the 1990s, world wide scale commercial plant
projects started in Middle East area to fill up the huge
demand for MEG. Since the MEG/DEG demand gap
problem was realized, the R&D project restarted in 1995.
After a quick reconfirmation of previous data in bench scale
study, a 1,000 tons/year scale pilot plant was constructed.
The pilot plant operation brought a lot of important infor-
mation including reaction rates, impurity behaviors, product
quality, catalyst consumption and operability.
In 2001, the project proceeded to the next stage. The
demonstration plant, whose capacity is 15 kt/y, was con-
structed in Kashima, Japan to prove that this technology is
available as a commercial process.
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K. Kawabe
A lot of confirmations about the scale up philosophy,
product quality, process performance, process operability
and process stability were achieved by this demonstration
plant. One of the most important outcomes from the
demonstration plant was production of a sufficient amount
of MEG for polyester production test. Based on this suc-
cess, the project moved to commercial production stage.
3 Process Outline
3.1 Reaction Scheme
The new technology consists of two step reaction system as
follows.
\New MEG production scheme[
1st step: Carbonation
EO þ CO2 ! EC
2nd step: Hydrolysis
EC þ H2 O ! EG þ CO2
The overall selectivity reaches more than 99%. Figure 1
shows comparison of the process performance with other
technologies. In spite of the lower water ratio, which is
almost stoichiometric, the selectivity of our new process is
much higher than others. This feature makes it possible to
simplify the purification section and to save a lot of energy
consumption and construction cost.
3.2 Process Description
The simplified process is described in Fig. 2 as block flow
together with the conventional one. The new process
consists of a reaction section and a purification section. The
former section is divided into two sections, the carbonation
section and hydrolysis section.
MCC technology
Technology A
(Patent)
Technology B
(Patent)
Conventional
Technology A
(Patent)
Fig. 1 Comparison of process performance
Development of Highly Selective Process for Mono-ethylene Glycol Production
Fig. 2 Block flow diagram of
conventional and new process
Around 60 wt% EO aqueous solution and CO2 gas are
provided as raw materials to the carbonation section. EO is
produced by ethylene oxidation on silver catalyst and
available as aqueous solution. CO2 is the main by-product
of EO production. They are fed to the carbonation reactor
with the catalyst (a phosphonium salt) solution. In the
reactor, not only carbonation but also other reactions
including hydration proceed simultaneously. All EO is
consumed and converted mainly to ethylene carbonate and
to small amount of ethylene glycols. The carbonation is an
exothermic reaction. The heat of reaction is recovered
properly and utilized in another section of the process.
Unreacted CO2 gas is separated from the reaction liquid,
compressed and recycled to the carbonation reactor.
Compared to the conventional process, the new technology
reaction system does not need high temperature. Both
carbonation and hydrolysis proceed at around 50 °C lower
temperature than that in the conventional process. Thus,
high pressure steam for the raw materials preheat is
unnecessary for the new process.
The hydrolysis reaction section follows the carbonation
section and ethylene carbonate is hydrolyzed to ethylene
glycol generating CO2. Most of the generated CO2 is
recycled to the carbonation section. A part of CO2 is purged
to prevent impurity accumulation in the recycle loop. Water
accompanied by EO in the raw material stream is sufficient
to complete the hydrolysis. However, additional water feed
to the process is preferable to accelerate the reaction.
The phosphonium salt itself acts as a week hydrolysis
catalyst. To accelerate the reaction, additional catalyst can
be chosen among alkali metal salts.
113
The purification section consists of dehydration, catalyst
separation and product purification.
The reaction solution is fed to dehydration column in
order to remove the excess water, which is necessary to
accelerate reaction in the hydrolysis step. This section is
much simpler compared to the conventional process due to
the low water concentration. The new technology does not
require the complicated distillation system which is
essential in the conventional process. The reaction solution
can be treated with a simple dehydration column. The
simplicity of this section brings many advantages. It is
possible to reduce energy consumption and construction
cost, as well as to improve operability.
The catalyst is then separated from the dehydrated
solution by evaporation and recycled to the carbonation
section. MEG needs to be highly purified to meet a severe
specification in the application to polyester fiber.
Small amounts of DEG and heavier glycols are obtained
from the bottom as residue. Usually they are disposed and
utilized as fuel in the industrial complex. Alternatively
DEG can be recovered as a by-product.
As a consequence of the higher selectivity, it is possible
to reduce the scale of the EO production unit by more than
10% compared to the conventional process to produce the
same amount of MEG. In addition, the dehydration unit and
heavier glycol recovering unit can be simplified. Consid-
ering these merit, the construction cost can be reduced by
10%. The steam and water consumption are also much
reduced compared to the conventional process. From an
ecological point of view, the large reduction of waste water
is also advantageous.
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3.3 Quality
The quality of MEG obtained by the new process is iden-
tical to that from the conventional process. This is con-
firmed by several commercial plant tests by ourselves and
users. All tests were completed successfully and showed
that it is applicable to any kinds of polyester including
bottle, film and fiber as well as antifreeze.
4 Catalyst
A variety of compounds have been proposed as carbonation
catalyst. The earliest known catalyst is NaOH supported on
active carbon which was reported in the German patent in
1943. The catalyst is not active enough and forms a lot of
impurities. In addition it is deactivated easily. Alkali metal
halides, amines, organotin compounds were also proposed.
In 1958 the usage of quaternary ammonium halides in a
commercial scale equipment was reported by Peppel [5].
They have sufficient activities but their thermal stabilities
are not enough. But considering the severe ethylene glycol
specification including color and odor, there was some
concern that even very slight catalyst decomposition could
damage the MEG quality. We endeavored to find more
active and stable catalysts.
As a result of investigation and many tests, phospho-
nium salts described below were selected as carbonation
catalyst.
R1R2R3R4P?X-
Ri: Alkyl group, allyl group
X-: Halide ion
The reasons of this selection are as follows.
– Organic onium salts are highly soluble in the reaction
solution and their melting points are relatively low as
well. These properties contribute to reduce the possi-
bility of plugging in the process.
– Organic onium salts have so high boiling points that
they can be separated easily by simple distillation and
never contaminate the product.
– Phosphonium salts are more stable than ammonium
salts under the reaction conditions. This is an important
property to ensure good product quality and good
process economy. Although a phosphonium salt is
known to decompose thermally into a phosphine and
alkyl halides [6], the decomposition rate under our
reaction conditions is acceptably small.
– Iodides and bromides have much higher activities than
chlorides [7].
– Not corrosive. It was confirmed not only under static
conditions by the laboratory test but also under the
123
K. Kawabe
dynamic liquid flow conditions by the pilot plant and
the demonstration plant tests.
The phosphonium catalyst is so active that the reaction
rate of carbonation is much higher than those of hydration
and dimerization, which generate MEG and DEG respec-
tively. Especially under mild reaction conditions, dimer-
ization hardly proceeds, so that EO reacts almost selectively
with CO2 to generate only ethylene carbonate. This is the
reason of high MEG selectivity.
This reaction rate difference between carbonation and
dimerization makes it possible to feed EO as aqueous
solution. The existence of water causes generation of MEG
by hydrolysis of ethylene carbonate and hydration of EO.
But further dimerization does not proceed. Utilization of
aqueous EO solution directly obtained from EO plant as
feed without any dehydration step contributes to further
process simplification.
A sufficient CO2 supply to the liquid phase is critically
essential to make sure the reaction rate difference. If CO2
supply is insufficient, the carbonation rate drops and the
rates of side reactions relatively increase, thus lowering
MEG selectivity and deteriorating the product quality by
contamination of generated impurities [8]. Figure 3 shows
an example of laboratory test result.
The high pressure condition is preferable to accelerate
the CO2 dissolving. Some mechanical CO2 dispersion
facilities also help the CO2 dissolving.
The catalyst shows high activity in a sufficient amount
of protic solvent i.e. water and glycols. This property
makes it possible to utilize the aqueous EO solution as feed
directly.
The pilot and commercial process tests showed that the
stability of the catalyst is satisfactory. Only a small amount
of decomposed catalyst is easily purged without any
accumulation and operational problem.
Shesko [9] proposed the carbonation mechanism. Con-
sidering the fact that activity depends on the anion species,
the carbonation reaction seemed to start by attack of halogen
EO consumption
rate constant
Aldehyde
yield
DEG yield
Fig. 3 Influence of CO2 pressure on the reaction performance
Development of Highly Selective Process for Mono-ethylene Glycol Production
X
O
+
+ R4P X
-
- + + O=C=O O O + R P+ X -
O P R4
O
Fig. 4 Assumed reaction mechanism
anion on the epoxy ring as shown in Fig. 4. The alkoxide ion
will attack the carbon atom of carbon dioxide and the
resulting carboxylate ion will attack the terminal carbon
atom to close the ring. The cation might have some role to
induce the ring opening. The difference of cation species
does not have major impact on catalyst performance.
5 Application of the New Technology
MCC has a long relationship with Shell Chemicals as the
conventional process licensee. In 2002 our new technology
was combined with Shell’s EO technology to realize this
technology and named OMEGA process. The name comes
from the feature, ‘‘Only MEG Advantage.’’
Now OMEGA process is licensed by Shell Chemicals to
all over the world. Already three world wide scale com-
mercial plants were constructed and operated smoothly in
Korea, Saudi Arabia and Singapore. The plant capacities
115
are 400, 600 and 750 kt/y, respectively. The last one is the
biggest scale in the world. This technology has a possibility
4
to produce not only MEG but also ethylene carbonate as a
product. This intermediate is an important ingredient of Li
battery cells. The technology to produce high purity eth-
ylene carbonate to meet the quality for the battery cell
use has been developed and the production has started in
Kashima, Japan.
Acknowledgments The author is grateful for the cooperation by
Shell Global Solutions in applying this technology to real commercial
plants.
References
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3. Robson JH to Union Carbide Corporation. US Patent 4,551,566
4. Foster RD to Union Carbide Corporation. US Patent 4,117,250
5. Peppel WJ (1958) Ind Eng Chem 50:767
6. Kosolapoff GM, Maier L Phosphorus. Wiley, p 207
7. Shapio AL, Ryzhenkov AM, v sb., Alkilenkarbonaty (1975) 17–24
8. Kawabe K to Mitsubishi Chemical Corporation. US Patent
6,080,897
9. Shesko TE et al (1973) React Org Compd 10(1):299–306
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