US005763691A

United States Patent (19) 11 Patent Number: 5,763,691

Kawabe et al. 45) Date of Patent: Jun. 9, 1998
54 ETHYLENE GLYCOL PROCESS OTHER PUBLICATIONS
75 Inventors: Kazuki Kawabe, Yokkaichi; Kazuhiko Patent Absracts of Japan, 9(197) (C-128), Oct. 6, 1982
Murata, deceased, late of Tokyo, by (abstract of JP 57-106631).
Reiji Murata, Keiko Murata, heirs; Patent Abstract of Japan, 8(98) (C-221), May 9, 1984
Toshiyuki Furuya, Yokkaichi, all of (abstract of JP 59-013741).
Japan
(73) Assignee: Mitsubishi Chemical Corporation, Primary Examiner-Porfirio Nazario-Gonzalez
Tokyo, Japan Assistant Examiner-Karl J. Puttlitz
Attorney, Agent, or Firm-Wenderoth, Lind & Ponack,
L.L.P.
(21) Appl. No.: 756,800
22 Filed: Nov. 26, 1996 (57) ABSTRACT
30 Foreign Application Priority Data The present invention relates to a process for producing
ethylene glycol from ethylene oxide wherein ethylene oxide
Nov. 30, 1995 JP Japan .................................... 7-312631 in a gas resulting from oxidation of ethylene is absorbed in
[51] Int. Cl. ........................... CO7C 27/00 a specific absorbing solution, is allowed to react with carbon
52 U.S. Cl. .............. ... 568/867; 568/858 dioxide, converted into ethylene carbonate, and then sub
jected to hydrolysis to produce ethylene glycol.
58) Field of Search ............................... 568/867; 11/858
56) References Cited According to the present invention, a large energy consum
ing step such as stripping of ethylene oxide and separation
U.S. PATENT DOCUMENTS of excess amounts of water during the ethylene glycol
production becomes unnecessary and the process can be
4,160,116 7/1979 Mieno et al. ....... - 568/867
greatly simplified by combining the ethylene oxide absorp
4,233,221 11/1980 Raines et al. .. was sa 260/340.2
tion step and the carbonation step.
4,508,927 4/1985 Bhise et al..
FOREIGN PATENT DOCUMENTS
2 107712 5/1983 United Kingdom. 9 Claims, 1 Drawing Sheet

ETHYLENE
ABSORBNG GLYCOL (EG)
SOLUTION 12

CO2

ABSORBNG
CARBONATE (EC) SOLUTION
ETHYLENE CONTAINING
OXDE (EO) ETHYENE
CARBONATE
ABSORBNG 18
SOLUTION
CONTAINING 17
EHY ENE
OXDE
 5,763,691
1. 2
ETHYLENE GLYCOL PROCESS sufficiently large enough for the gas used is required. After
the absorption/separation procedure of the ethylene oxide, a
BACKGROUND OF THE INVENTION large amount of this absorption water must then be heated,
1. Field of the Invention usually up to 100°-150° C. in the process for stripping and
The present invention relates to a process for producing separating ethylene, thereby requiring a large amount of heat
ethylene glycol from ethylene oxide. In particular, it relates energy. Further, as more than Small amounts of the absorp
to a process for producing ethylene glycol wherein ethylene tion water is evaporated, even more energy is required.
oxide in a gas resulting from oxidation of ethylene is There is also a method proposed in U.S. Pat. No. 4,273,
absorbed in a specific absorbing solution, is then allowed to 221, in which ethylene carbonate is used instead of water, as
react with carbon dioxide, to be converted into ethylene
O an absorbing solution for ethylene oxide. According to this
carbonate, and then subjected to hydrolysis to produce process, the amount of heat energy necessary for elevating
ethylene glycol. the temperature to the level required for the stripping
The ethylene glycol is used as a raw material for produc procedure can be decreased, since the specific heat of the
ing a polyester or polyurethane type polymer or as anti ethylene carbonate is less than half of that of water.
15 However, since the melting point of ethylene carbonate is as
freeze for engines and the like. high as 39°C., the operation temperature of the absorption
2. Description of the Related Art column cannot be lowered sufficiently, and the absorption
The preparation of monoethylene glycol (hereinafter sim loss of the ethylene oxide is more than a little. Also, since the
ply abbreviated as ethylene glycol) from ethylene through stripping procedure itself is not eliminated even though the
ethylene oxide comprises the following steps. heatenergy required is decreased, the problem still remains.
First, ethylene is converted into ethylene oxide by vapor Second, as the hydration reaction is carried out under
phase catalytic oxidation using oxygen in the presence of a largely excess conditions, the separation of the excess water
silver catalyst. The gas resulting from the oxidation usually after the hydration reaction requires a large amount of
contains ethylene oxide in an amount of 0.5-5 mol%. The 25
energy for the following reasons. The selectivity of ethylene
gas containing ethylene oxide is contacted with a large oxide to ethylene glycol, diethylene glycol, and triethylene
amount of water so that the ethylene oxide contained in the glycol is determined by the ratio of the ethylene oxide to
gas resulting from the oxidation is absorbed in the water and water supplied to the hydration reactor. The larger the ratio
the ethylene oxide is recovered in the form of an aqueous of water to the ethylene oxide, the higher the selectivity of
solution. Then the obtained diluted aqueous solution of ethylene glycol becomes.
ethylene oxide (the concentration of the ethylene oxide is 30 Generally, among ethylene glycols, diethylene glycol,
usually 1-5 mol%) is heated under reduced pressure so that triethylene glycol or higher polyglycols, they have a nar
the ethylene oxide in the aqueous solution is stripped and rower range of application than that of the ethylene glycol.
separated, and the ethylene oxide is recovered from the top Accordingly, in order to raise the selectivity of ethylene
of the column. The water remaining after removing the oxide to the ethylene glycol which is in great demand, an
ethylene oxide is cooled, and recycled to the absorbing step. 35 excess amount of water, i.e. 10–25 times the molar quantity
Ethylene oxide is isolated from the mixture mainly con of ethylene oxide, is often supplied for hydration reaction as
taining ethylene oxide and water obtained by the stripping described above. Therefore, the concentration of the ethyl
treatment, if necessary, then water in an amount in excess of ene glycol obtained after completion of the reaction is at
that normally used for the ethylene oxide is added (water is 40 most around 10-20% by weight.
usually in an amount of 10-25 moles for each mole of In the recovery and the purification process of the ethyl
ethylene oxide) and ethylene glycol is obtained by hydration ene glycol, this excess amount of water must be removed by
reaction. In the hydration reaction of ethylene oxide, unre a distillation procedure from the mixture of ethylene glycol
acted ethylene oxide and produced ethylene glycol are
allowed to react successively, and in addition to the ethylene 45 and water, and that requires a large amount of energy. For
example, when water in a molar quantity 20 times that of
glycol, diethylene glycol, triethylene glycol and other higher ethylene oxide
polyethylene glycols are produced as by-products. by evaporation isthesupplied, the heat necessary for removing
Accordingly, after the completion of the hydration reaction, 19 times that of ethylene glycol,inisa170
unused water molar quantity about
kcal per mole of
the product can only be obtained after sequentially separat ethylene glycol. That means about 5.5 tons of steam is
ing these glycols by such procedures as distillation. 50 consumed for 1 ton of ethylene glycol. Therefore, in order
As mentioned above, the ethylene glycol production to further improve the selectivity of ethylene glycol, the ratio
according to the prior art requires both an ethylene oxide of water used must be raised more, which increases the
isolation process comprising absorbing and stripping amount of water to be removed by evaporation, so that a
systems, and an ethylene glycol production process con larger amount of energy is required.
prising an ethylene oxide hydration reaction system and a 55 Processes have also been proposed to decrease the amount
glycol separation purification system. of water for ethylene oxide but to keep the selectivity for
However, the conventional process has such deficiencies ethylene glycol at a high level, in which isolated ethylene
that it not only needs a large number of steps for obtaining oxide is allowed to react with carbon dioxide to produce
ethylene glycol as a product, but also consumes a lot of ethylene carbonate, which is then hydrolyzed to produce
energy, as described below, in order to produce the ethylene ethylene glycol with high selectivity. For example, in a
glycol. process proposed in Japanese Patent Publication No.
First, the procedure of stripping and separating ethylene 3-23548, ethylene oxide is converted to ethylene carbonate
oxide absorbed in the absorbing solution consumes a lot of in the presence of a halogenated organic quaternary phos
energy. phonium salt, and in a process proposed in Japanese Patent
As mentioned above, in order to carry out absorption and 65 Publication No. 4-27972, the resulting ethylene carbonate is
separation of ethylene oxide without substantial loss, from subjected to hydrolysis using the same catalyst to give high
the gas obtained by oxidation, absorption waterin an amount purity ethylene glycol. There is also another process pro
 5,763,691
3 4
posed in Japanese Patent Laid-openNo. 57-106631 in which DESCRIPTION OF THE PREFERRED
ethylene oxide is converted to ethylene carbonate using a EMBODIMENT
halide of an alkali metal, followed by hydrolysis. One example of the embodiment of the present invention
According to these processes, it is not necessary to supply will be described in detail with reference to FIG. 1.
water to the reactor in amounts more than is to be consumed (Absorption step of ethylene oxide (Step 1))
by the reaction in order to achieve high selectivity, and as a Absorption of ethylene oxide is carried out in an absorp
result the second drawback, i.e. the large amount of energy tion apparatus I by contacting a gas Supplied via line 1 which
required for removing the excess amount of water by results from a oxidation reaction and contains ethylene
distillation procedures, can be avoided. However, in all of oxide, with an absorbing solution supplied via line 2.
these processes, isolated ethylene oxide is used as the O The gas resulting from the oxidation reaction and con
starting material, and there have been no proposals on taining ethylene oxide is usually obtained by catalytic vapor
absorption procedures or stripping procedures for phase oxidation of ethylene over a silver catalyst, and
recovering, concentrating and isolating the ethylene oxide contains ethylene oxide usually in an amount of 0.5-5 mol
from the gas resulting from oxidation. For recovering eth %. In addition to that, it contains oxygen, ethylene, gener
ylene oxide from the gas containing ethylene oxide accord 15 ated water, carbon dioxide, nitrogen, methane, ethane and
ing to the conventional process, a stripping procedure is trace amounts of aldehydes. The gas containing ethylene
required as mentioned above, and the first drawback, i.e. the oxide is desirably cooled by a heat-exchanger and the like
large amount of energy required, remains unimproved. The usually to 10°-80°0 C., preferably 30°-60° C., before it is
supplied to the absorption apparatus.
whole process from the oxidation of ethylene to the purifi The main components of the absorbing solution are
cation of ethylene glycol is very long and the construction ethylene carbonate and ethylene glycol. Ethylene carbonate
costs are high. This disadvantageously leads to an increase and ethylene glycol usually comprise 50% by weight or
in the ethylene glycol production costs. more of the whole absorbing solution. The weight ratio of
SUMMARY OF THE INVENTION the ethylene glycol to ethylene carbonate is usually 0.1-9,
As a result of intensive research to solve the above
preferably 0.3-4. As an optional component except for the
25 ethylene carbonate and ethylene glycol, the absorbing solu
mentioned problems, the present inventors have discovered tion contains water usually in a range of 1-30% by weight,
a process in which ethylene oxide is separated from a gas preferably 3-15% by weight. Furthermore, when a homo
resulting from oxidation reaction, and ethylene glycol can be geneous type catalyst is used as a carbonation catalyst, the
advantageously produced in a simplified and low-energy catalyst is recycled as it is dissolved in the absorbing
process, to complete the present invention. solution, and the content of the carbonation catalyst is
According to the present invention, there is provided a usually 1-10% by weight, preferably 3-7 w% by weight of
process for producing ethylene glycol from ethylene oxide, the whole absorbing solution.
comprising; As the melting point of ethylene carbonate is as high as
step (1): a step in which ethylene oxide in a gas resulting 39°C., a low ethylene glycol blending ratio may result in
from oxidation of ethylene is absorbed in an absorbing 35 solidification of the absorbing solution in a pipeline, when it
solution mainly containing ethylene carbonate and ethylene is cooled to 50° C. or below, jeopardizing safe operation, but
glycol, too much ethylene glycollowers the absorption efficiency of
step (2): a step in which ethylene oxide in the absorbing ethylene oxide.
solution is allowed to react with carbon dioxide in the The temperature of the absorbing solution to be supplied
presence of a carbonation catalyst, . is usually 10°-60° C. preferably 15°-40°C. from the view
step (3): a step in which a part of ethylene carbonate point of absorption efficiency. When a homogeneous type
resulting in the absorbing solution is subjected to hydrolysis catalystis dissolved in an absorbing solution and used as the
in the presence of a hydrolytic catalyst and the remaining carbonation catalyst, the carbonation catalyst contained in
ethylene carbonate is allowed to recycle as an absorbing the absorbing solution is replenished via line 3 together with
solution, and 45 ethylene glycol, so that the loss caused by a discharge via
step (4): a step in which ethylene glycolis recovered from line 17 to prevent heavy components from accumulating, is
the hydrolysate by distillation. recovered to maintain the concentration. When a heteroge
The features of the present invention are as follows. First, neous type carbonation catalyst is used, a part of ethylene
a mixed solvent mainly containing ethylene glycol and glycol is drawn via line 17 by the discharge for the same
ethylene carbonate is used as an ethylene oxide absorbing 50 reason, but the catalyst need not be replenished.
solution. Second, the ethylene oxide is absorbed and sepa The absorption process of ethylene oxide is not particu
rated from the gas containing ethylene oxide using the larly limited, but a counter-current contact type absorption
absorbing solution, then without stripping and separating the column having high efficiency and little recovery loss is
ethylene oxide, the absorbing solution is directly used as a preferable. The form of the absorbing layer can be either a
reactor feed, and the ethylene oxide in the absorbing solution 55 packed column type or a plate column type. In order to raise
is converted into ethylene carbonate. Third, the major por the absorption efficiency of ethylene oxide, the operating
tion of the solution resulting from the carbonation reaction conditions of the absorption apparatus are preferably a high
is recycled to the absorbing operation as an absorbing pressure and a low temperature; illustrative operating pres
solution. Fourth, a part of the solution resulting from the sure is usually 5-40 kg/cm G (0.59–4.02 MPa), preferably
carbonation reaction is drawn out and ethylene carbonate in 10–30 kg/cm’G (1.08-3.04MPa), and the operating tem
the solution is hydrolyzed by adding a much smaller amount perature is usually 10°-80° C., preferably 15°-60° C. The
of water than that used conventionally in order to carry out gas/liquid ratio in moles is L/V of 0.1-2, preferably 0.2-1.
selective and low-energy production of ethylene glycol. By this absorbing procedure, substantially all the ethylene
oxide in the gas resulting from the reaction and trace
BRIEF DESCRIPTION OF THE DRAWING 65 amounts of other co-existing gasses such as oxygen,
FIG. 1 is a flow diagram of an embodiment of the present ethylene, carbon dioxide, methane and ethane are absorbed
invention. in the liquid phase.
 5,763,691
S 6
The remaining gas left after absorption/separation of carbon dioxide to be supplied via line 10, the carbon dioxide
ethylene oxide, i.e. a gas mainly containing oxygen, is separated from the recycling gas to the ethylene oxide
ethylene, carbon dioxide, methane and ethane, is drawn out reactor, which is left after absorbing ethylene oxide, and can
via line 5, and a part or all of it is recycled to the reaction be used without further treatment.
system of ethylene oxide as a feed gas or a diluting gas after The total amount of the carbon dioxide supplied via each
the amount of the carbon dioxide contained therein is line is usually 0.1-12 times, preferably 0.3-10 times, par
decreased by carbon dioxide removing treatment. ticularly preferably 0.5-5 times the molar quantity of eth
The absorbing solution having absorbed ethylene oxide is ylene oxide in the absorbing solution. In order to carry out
supplied to ethylene carbonate reactor via line 4. As the the reaction quickly, sufficient diffusion of the carbon diox
carbonation reactor, any reactor including a tubular type 10 ide into the solution must be carried out, thus the higher
flow reactor and a vessel type batch reactor can be used. pressure is preferable for the reaction conditions, and car
However, a tubular type flow reactor, in which a heat bonation reaction is carried out under a pressure of 1-50
medium flows outside of the dual tube to allow the removal kg/cmC (020-5.01 MPa), preferably 3–20 kg/cm’G
of the heat is preferable from the view point of the conver (0.40-2.06 MPa). The reaction is usually carried out at a
sion rate of ethylene oxide, the removal of reaction heat, and 15 temperature of 50°-200° C. at a low temperature, the
continuous operation. The carbonation reaction is an exo reaction rate becomes low and the reaction time is
thermic reaction of 26 kcal/mole, and if the removal of the prolonged, thus making the reactor larger and therefore
reaction heat is not properly done, an extraordinary rise in uneconomical. On the other hand, at a high temperature, the
temperature may occur due to a runaway reaction to heat of the reaction may not be removed in time which may
adversely effect the quality of the product. When a hetero 20 cause a runaway reaction, and the high temperature reaction
geneous type solid catalyst is employed as the carbonation itself may impart bad effects on the quality of the produced
catalyst, the catalyst is packed in the reactor to form a layer, ethylene glycol, i.e. it is desirable to carry out the reaction
and the reaction is carried out. usually at 80°-150° C. The required retention time in the
(Carbonation step of ethylene oxide (step 2)) reactor depends on the reaction temperature. However it
The carbonation catalyst used can be either a homoge usually is 5-180 minutes, preferably 12-120 minutes. w
neous type dissolved in the absorbing solution or a hetero In addition, in the carbonate step, the direct reaction of
geneous type comprising a packed layer of a solid catalyst. ethylene oxide to ethylene glycol can be carried out together
Illustrative examples of the homogeneous type carbonation with the carbonation reaction when the higher temperature
catalyst include a bromide or iodide of an alkali metal and the lower pressure within the range of temperature and
(Japanese Patent Publication No. 38-23175), a halide of an 30 pressure mentioned above are employed as reaction condi
alkaline earth metal (U.S. Pat. No. 2,667,497), an alkyl tions.
amine, a quaternary ammonium salt (U.S. Pat. No. 2.773, (Step for recovering carbon dioxide)
070), an organic tin, germanium or tellurium compound After the carbonate step of ethylene oxide, the absorbing
(Japanese Patent Laid-open No. 57-183784), and a haloge solution (hereinafter simply referred to as a reaction
nated organic phosphonium salt (Japanese Patent Laid-open 35 solution, so that the absorbing solution prior to the carbon
No. 58-126884), and among them, a halide of an alkalimetal ating step can be distinguished therefrom) which almost all
such as potassium bromide and potassium iodide, and a amounts of ethylene oxide are consumed, is supplied via line
halogenated organic phosphonium salt such as tributylmeth 7 to the carbon dioxide recovery apparatus in order to
ylphosphonium iodide, tetrabutylphosphonium iodide, separate unconsumed excess carbon dioxide.
triphenylmethylphosphonium iodide, triphenylpropylphos The reaction solution supplied to the carbon dioxide
phonium bromide, triphenylbenzylphosphonium chloride recovery apparatus is flushed by lowering the pressure
are preferable from the view point of activity and selectivity. usually to 0-15 kg/cmG (0.10-1.57 MPa), preferably 0-4
In the case of a heterogeneous catalyst, illustrative examples kg/cm’G (0.10-0.49 MPa), and unused carbon dioxide, as
include such known substances as an anion exchange resin well as oxygen, ethylene, carbon dioxide, methane and
having a quaternary ammonium salt as an exchange group 45 ethane and the like which are absorbed in the absorbing step
(Japanese Patent Laid-openNo. 3-120270), a heteropolyacid and are accompanying the reaction solution are separated
based on an oxide of tungsten or an oxide of molybdenum into the gas phase.
and a salt thereof (Japanese Patent Laid-open No. The separated carbon dioxide gas is partly discharged via
7-206847). line 9 in order to avoid the accumulation of gasses such as
The absorbing operation is usually carried out at such low 50 oxygen, ethylene, carbon dioxide, methane and ethane, and
temperature as 10°-80° C., therefore the probability of the the rest is recycled to the ethylene carbonate reactor IV via
reaction taking place between the ethylene glycol in the line 6. The carbon dioxide is consumed by the reaction but
absorbing solution and the absorbed ethylene oxide during the carbon dioxide generated in the hydrolysis reactor is
the absorbing operation, to generate diethylene glycol or recycled via line 11 and the carbon dioxide lost by the
higher polyglycols, is very small, and it is possible to 55 discharge is replenished by the fresh carbon dioxide sent via
substantially control the generation of these by-products. line 10 and the supply of the carbon dioxide to the reactor
In the case of a homogeneous catalyst, it is sent to the next is kept constant.
step, i.e. to the carbonation reactor II while it is present in The major portion of the reaction solution left after the
the absorbing solution, and works there as a catalyst for the separation and recovery of the carbon dioxide is recycled to
reaction between the ethylene oxide in the absorbing solu the absorption column and the rest is supplied to the hydro
tion and carbon dioxide to convert the ethylene oxide to lytic reactor via line 8. The ratio of the flow rate a at which
ethylene carbonate. the reaction solution is recycled to the absorption column, to
As the carbon dioxide used for the reaction, recycled the flow rate bat which the reaction solution is sent to the
carbon dioxide from the carbon dioxide recovery apparatus hydrolytic reactor is defined as bla=di?c, wherein c is the
III is supplied via line 6 and carbon dioxide generated in the 65 molar quantity of ethylene carbonate in the absorbing solu
hydrolysis step is recycled and supplied via line 11. Also, tion of line 4 and d is the molar quantity of newly produced
fresh carbon dioxide is supplied via line 10. As the fresh ethylene carbonate. Accordingly, when the quantity of eth
 5,763,691
7 8
ylene oxide in the reaction gas and the quantity of the All of the reaction solution obtained after completion of
absorbing solution remain the same, the operation at a higher the hydrolysis is introduced to a carbon dioxide separator V,
ethylene carbonate concentration in the absorbing solution wherein the pressure is lowered to 0-4 kg/cm’G (0.10-0.49
of line 4 results in a smaller amount of the reaction solution MPa), and the carbon dioxide resulting from the hydrolysis
to be drawn out for the hydrolytic reaction step, i.e. the is separated into a gas phase. The separated carbon dioxide
hydrolysis step, and the subsequent steps can be carried out is recycled to the carbonation reaction system via line 11.
on a smaller scale. The ratio of the reaction solution to be The reaction solution after the separation of the carbon
drawn out for the hydrolysis step is usually 1-40% of the dioxide is introduced to the dehydration column VI via line
total amount. 14. In the dehydration column, excess water which is not
The reaction solution which is recycled as the absorbing 10 consumed in the hydrolysis reaction is separated through the
solution to the absorption column, is added to the stream via top of the column. The separated water is directly stripped
line 18 consisting of ethylene glycol of amount required to via line 19, although it is possible to recycle a part or all of
keep the constant concentration of ethylene glycol in the the water to the hydrolytic reactor via line 12.
reaction solution and the solution containing the catalyst The solution at the bottom of the column is introduced to
through the hydrolytic reaction step, and then the losses of 15 the ethylene glycol recovery column VII via line 15. The
the catalyst and ethylene glycol caused by the discharge via
line 17 are recovered by replenishing via line 3 so that the Solution at the bottom of the dehydration column contains
composition of the reaction solution is returned to that ethylene glycol and a trace amount of diethylene glycol as
before the absorption procedure, and the reaction solution is well as a catalyst when a homogeneous type catalyst is used.
usually cooled then supplied to the absorption column as the In the ethylene glycol recovery column, the purified ethyl
absorbing solution. ene glycol is recovered through the top of the column and all
(Hydrolysis step of ethylene carbonate (Step 3)) of the by-produced diethylene glycol as well as ethylene
The reaction solution mainly containing ethylene carbon glycol containing a high concentration of the catalyst, when
ate and ethylene glycol, drawn via line 8 is supplied to the a homogeneous type catalyst is used, are recovered through
hydrolytic reactor together with water. The water necessary the bottom of the column. The solution recovered through
for the hydrolysis comprises the water present in the mixed 25 the bottom of the column is added to line 2 and recycled,
solution resulting from the oxidation reaction, the water after a part of it is discharged via line 17 in order to avoid
recovered in the dehydration step and supplied via line 12. accumulation of heavy components such as diethylene gly
and fresh water supplied via line 13. The total amount of col.
water must be at least equimolar to the ethylene carbonate in The ethylene glycol obtained through the top of the
the drawn mixed solution. In practice, water 1-5 times, 30 column is drawn via line 16 and used as the product without
preferably 1-2 times molar quantity of ethylene carbonate is any further treatment. However, it is possible to purify it
supplied to carry out the reaction smoothly. further by conventionally employed processes such as dis
When a homogeneous type halogenated organic phospho tillation,
nium salt is used as a carbonation catalyst, the carbonation EXAMPLES
catalyst is effective as a catalyst to be used in the hydrolysis 35
step, so it is not always necessary to replenish with fresh To further illustrate the present invention, the following
catalyst in this step. As the hydrolytic catalyst supplied when examples are given, but they are not to be construed as
necessary via line 13, a basic Substance including a hydrox limiting the present invention.
ide of an alkali metal or alkaline earth metal such as sodium
hydroxide, potassium hydroxide, calcium hydroxide, and Example 1
magnesium hydroxide, a carbonate of an alkalimetal such as (1) Absorption of Ethylene Oxide
Sodium carbonate, potassium carbonate, and amines such as A gas having a temperature of 30° C., obtained by
triethylamine, tributylamine and triisopropylamine, can be oxidation of ethylene, containing 3 mol% of ethylene oxide
used, or a solid catalyst such as alumina and an inorganicion was introduced at the rate of 15 kg/hour through the bottom
exchanger can be packed in a reactor and used. 45 of a counterflow catalyst packed absorption column having
The reaction temperature is usually 100°-250° C., pref 30 stages (operation pressure: 14 kg/cmC (1.47 MPa) and
erably 120°-180° C. from the view point of the reaction rate. a mixed solution of ethylene carbonate and ethylene glycol
It is desirable that the pressure not be too high to remove the (mixed at 50:50 by weight) containing 5% by weight of
generating carbon dioxide smoothly into the gas phase, and tributylmethylphosphonium iodide as a catalyst and 3.8% by
usually it is 0–10 kg/cm’G (0.10-1.08 MPa), preferably 0-5 50 weight of water, was made to flow down from the top of the
kg/cm’G (0.10-0.59 MPa). The reaction time depends on column at 30 kg/hour at 30° C. as an absorbing solution, and
the reaction temperature and the catalyst used, however, it the ethylene oxide in the gas was absorbed in the solution.
must be within 5-240 minutes, preferably 10-180 minutes. As a result of the analysis of the effluent, the ethylene oxide
(Ethylene glycol recovery step) concentration in the gas at the top of the column was found
After the hydrolysis is completed, the reaction solution is 55 to be 100 ppm and the absorption efficiency of the ethylene
sent to a separation step wherein the excess water which is oxide was found to be 99% or more.
not consumed by the reaction, produced ethylene glycol and (2) Ethylene Carbonate Conversion Reaction
the catalyst when a homogeneous type catalyst is used are Carbon dioxide was mixed at 20 moles/hour with the
separated respectively. The details of the separation step mixed solution having absorbed ethylene oxide in (1) and it
differ according to the order of the separation, and for was supplied to a tubular type flow reactor (10 reaction tubes
example, it is possible to structure the process wherein the having a diameter of 3 cm, a length of 200 cm and retention
separation of the catalyst takes precedence. However, the time of 30 minutes). This was then heated to 100° C. using
order of the separation of each component does not affect the an external heat medium, so that the ethylene oxide in the
constitution of the process as a whole. Here, a process will absorbing solution was allowed to react with carbon dioxide
be described in which the separation of water takes 65 and converted into ethylene carbonate. The conversion rate
precedence, and the produced ethylene glycol and the cata of the ethylene oxide at the outlet of the reactor was 99% or
lyst are then separated. more and only a trace amount of diethylene glycol was
 5,763,691
9 10
produced as a by-product and no heavy components were ration of excess amounts of water during the ethylene glycol
found to be generated. production becomes unnecessary and the process can be
(3) Removal of Unreacted Carbon Dioxide Gas greatly simplified by combining the ethylene oxide absorp
The ethylene carbonatefethylene glycol mixed solution tion step and the carbonation step.
produced in (2) was flushed at 100° C., 1 kg/cm’G (0.20 What is claimed is:
MPa) so that the carbon dioxide in the mixed solution was 1. A process for producing ethylene glycol from ethylene
removed. The carbon dioxide concentration in the mixed oxide without employing a scrubbing or stripping ethylene
solution after the removal procedure was 0.1% by weight or oxide step, comprising the steps of:
less and the carbon dioxide removal rate was 90% or more. a directly absorbing ethylene oxide in a gas formed by
(4) Hydrolytic Reaction 10 oxidation of ethylene in an absorbing solution mainly
About 10% by weight of the mixed solution after the containing ethylene carbonate and ethylene glycol
removal of the carbon dioxide was split and water was added without scrubbing and stripping ethylene oxide,
at 400 g/hour (1.2 times the molar quantity of ethylene b. reacting the ethylene oxide in the absorbing solution
carbonate contained in the mixed solution) and supplied to with carbon dioxide in the presence of a carbonation
a hydrolytic reactor (8 reaction tubes having a diameter of 3 15 catalyst to convert ethylene oxide to ethylene
cm, a length of 120 cm, retention time of 120 minutes). This carbonate,
was then heated to 150° C. using an external heat medium c. subjecting a part of ethylene carbonate to hydrolysis in
to carry out the hydrolytic reaction. The ethylene carbonate the presence of a hydrolytic catalyst to form a hydroly
conversion rate at the outlet of the reactor was nearly 100%, sate containing ethylene glycol and allowing the
the selectivity of ethylene glycol was 99% or more. The 20 remaining ethylene carbonate to recycle as the absorb
diethylene glycol was produced in an amount of 1% or less ing Solution, and
and no heavy components were found to be generated. d. recovering the ethylene glycol from the hydrolysate by
(5) Recovery of the Reaction Product distillation.
Carbon dioxide was removed from the reaction mixture 2. A process for producing ethylene glycol according to
containing the catalyst obtained in (4) by a gas/liquid 25 claim 1, further comprising recovering the unreacted carbon
separator and the resulting liquid phase was subjected to dioxide after step b.
vacuum distillation in a dehydration column having 15 3. A process for producing ethylene glycol according to
stages to remove the water from the reaction mixture. Then claim 1, wherein the total amount of the ethylene carbonate
the liquid at the bottom of the column was further subjected and the ethylene glycol contained in the absorbing solution
to the vacuum distillation and purified ethylene glycol was used in step ais not less than 50% by weight of the absorbing
obtained through the top of the column at a constant rate of solution.
980 g/hour. Ethylene glycol containing the catalyst in a high 4. A process for producing ethylene glycol according to
concentration was drawn out through the bottom of the claim 1, wherein the weight ratio of the ethylene glycol to
column. the ethylene carbonate is 0.1-9.
(6) Recycling of the Absorbing Solution 35 5. A process for producing ethylene glycol according to
90% by weight of the mixed solution left after the removal claim 1, wherein the absorbing solution mainly contains
of the carbon dioxide was cooled to 30° C. and recycled to ethylene carbonate, ethylene glycol and water.
the absorption column as an absorbing solution. The ethyl 6. A process for producing ethylene glycol according to
ene glycol containing the catalyst of high concentration claim 1, wherein the gas resulting from the oxidation of
obtainedin (5) was discharged at 160 g/hour and the rest was 40 ethylene contains 0.5-5 mol % of ethylene oxide.
recycled as a part of the absorbing solution after the catalyst 7. A process for producing ethylene glycol according to
was replenished. The recycling of carbon dioxide via line 6 claim 5, wherein the amount of water contained in the
and line 11 and recycling of water via line 12 shown in the absorbing solution used in step a is 1-30% by weight of the
FIGURE were not carried out and fresh carbon dioxide and absorbing solution.
fresh water were supplied. 45 8. A process for producing ethylene glycol according to
The above-mentioned recycling system was constructed claim 1, wherein the absorption of ethylene oxide is carried
and an experiment was carried out for 3 consecutive weeks. out at a temperature of 10°-80°C. in step a.
However, no loss of ethylene oxide, lowering of selectivity, 9. A process for producing ethylene glycol according to
generation or accumulation of heavy components were claim 1, wherein the carbonation catalyst is a halogenated
observed, and stabilized operation could be carried out. 50 organic phosphonium salt.
According to the present invention, a large energy con
suming step such as releasing of ethylene oxide and sepa