USOO9096564B2

(12) United States Patent (10) Patent No.: US 9,096,564 B2

Van Ogtrop et al. (45) Date of Patent: Aug. 4, 2015

(54) PROCESSES FOR THE PRODUCTION OF S. A

www.
2.8 sts et al. .............. 3.
aWae . . . . . . . . . . . . . . . . . . . . . . . .
ETHYLENE GLYCOL 6, 184423 B1 2/2001 Jen
6,187.972 B1 2/2001 Kawabe et al. ............... 568/858
(75) Inventors: Jan Van Ogtrop, Amsterdam (NL); 6,437,199 B1 8/2002 Oka et al.
Abraham Adriaan Smaardijk,
Amsterdam (NL); Jacqueline Hessing, FOREIGN PATENT DOCUMENTS
legal representative, Castricum (NL);
Hendrik Stichter, Amsterdam (NL) W. 20046 . 13.
WO WO-2008OO9013 * 7/2008
(73) Assignee: Shell Oil Company, Houston, TX (US) WO WO2O08090138 7/2008 ........... CO7D 301/10
(*) Notice: Subject to any disclaimer, the term of this OTHER PUBLICATIONS
patent is extended or adjusted under 35
U.S.C. 154(b) by 300 days. “Ethylene Oxide'. Ullmann's Encyclopedia of Industrial Chemistry,
5th Rev. Ed., vol. A 10, pp. 117-139 (1987).
IPO Search Report dated Apr. 9, 2013 for Ref. TS1658 TAI, ROC
(21) Appl. No.: 13/362,835 (Taiwan) Patent Application No. 097 102401.
(22) Filed: Jan. 31, 2012 c cited by examiner
(65) Prior Publication Data Primary Examiner —Yong Chu
US 2012/O197048A1 Aug. 2, 2012 Assistant Examiner — Sonya Wright
(30) Foreign Application Priority Data (57) ABSTRACT
A process for the production of ethylene glycol comprising:
Jan. 31, 2011 (EP) ..................................... 11 152780 (i) Supplying ethylene and oxygen and an organic chloride
(51) Int. Cl moderator to an EO reactor, thereby producing a reactor
we product stream;
C 5 9.2 30.8; } (ii) supplying the reactor product stream to an EO absorber,
C07C 29/12 (2006. 01) thereby producing a fat absorbent stream;
CO7D 301/04 (2006,015 (iii) Supplying the fat absorbent stream to an EO Stripper,
C07C 29/10 (2006. 01) thereby producing a concentrated ethylene oxide stream
52) U.S. C and a lean absorbent stream;
(52) U.S. Cl. (iv) recirculating the lean absorbent stream to the EO
CPC ............ C07D 301/22 (2013.01); C07C29/106 absorber; and
(2013.01); C07C 29/12 301/04
(2013.01); C07D
(2013.01) (v) Supplying the ethylene oxide stream and/or the ethylene
carbonate stream to hydrolysis reactors with an alkali
(58) Field of Classification Search metal salt hydrolysis catalyst to form an ethylene glycol
CPC ....................................................... CO7C 29/09 Stream;
USPC .......................................................... 568/858 wherein the process additionally comprises:
See application file for complete search history. (vi) removing a glycol bleed stream from the ethylene
oxide stripper; and
(56) References Cited (vii) RE to the ethylene oxide stripper such that
U.S. PATENT DOCUMENTS the pH in the bottom section of the stripper is maintained
from 9.5 to 12.0.
4,349,417 A 9, 1982 Rebsdat et al.
4,822,926 A 4, 1989 Dye .............................. 568,867 8 Claims, 2 Drawing Sheets
U.S. Patent Aug. 4, 2015 Sheet 1 of 2 US 9,096,564 B2

Figure 1
U.S. Patent Aug. 4, 2015 Sheet 2 of 2 US 9,096,564 B2

Figure 2
 US 9,096,564 B2
1. 2
PROCESSES FOR THE PRODUCTION OF The present inventors have, therefore, sought to provide an
ETHYLENE GLYCOL improved process wherein the amount of chloroethanol
present in the process is reduced and also wherein the decom
This patent application claims the benefit of position of the hydrolysis catalyst is decreased or avoided.
EP11 152780.0 filed Jan. 31, 2011, which is incorporated 5
herein by reference. SUMMARY OF THE INVENTION

FIELD OF THE INVENTION Accordingly, the present invention provides a process for
the production of ethylene glycol comprising the steps of:
The present invention relates to a process for the produc 10
(i) Supplying ethylene and oxygen and an organic chloride
tion of ethylene glycol. moderator to an ethylene oxide reactor wherein ethylene and
BACKGROUND OF THE INVENTION
oxygen react in the presence of a catalyst to produce ethylene
oxide, thereby producing a reactor product stream;
Monoethylene glycol is used as a raw material in the manu 15
(ii) Supplying the reactor product stream to an ethylene
facture of polyester fibres, polyethylene terephthalate (PET) oxide absorber wherein ethylene oxide is recovered from the
plastics and resins. It is also incorporated into automobile reactor product stream by absorption in water in the absorber
antifreeze liquids. Monoethylene glycol is typically prepared section, thereby producing a fat absorbent stream;
from ethylene oxide, which is in turn prepared from ethylene. (iii) Supplying the fatabsorbent stream to an ethylene oxide
Ethylene and oxygen are passed over a silver oxide catalyst, stripper wherein the fat absorbent stream is steam stripped,
typically in the presence of an organic chloride moderator, thereby producing a concentrated ethylene oxide stream and
producing a product stream comprising ethylene oxide, car a lean absorbent stream;
bon dioxide, ethylene, oxygen and water. (iv) recirculating the lean absorbent stream to the ethylene
The product stream from the ethylene oxide reactor, which oxide absorber;
may also contain by-products Such as organic chlorides, is 25 (V) optionally supplying the concentrated ethylene oxide
then supplied to an ethylene oxide absorber. Typically, the stream to one or more carboxylation reactors wherein ethyl
ethylene oxide absorber has an initial quench section Such as ene oxide reacts with carbon dioxide to form an ethylene
those described in U.S. Pat. No. 4,822,926 A and U.S. Pat. carbonate stream; and
No. 5,336,791 A. (vi) Supplying the concentrated ethylene oxide stream and/
After the quench section, the product stream passes to the 30 or the ethylene carbonate stream to one or more hydrolysis
main section of the ethylene oxide absorber in which the reactors wherein ethylene oxide and/or ethylene carbonate
ethylene oxide is contacted with and absorbed into a lean reacts with water in the presence of a hydrolysis catalyst
absorbent stream, which usually comprises water. The result selected from one or more basic alkali metal salts to form an
antaqueous ethylene oxide stream is referred to as fat absor ethylene glycol stream;
bent and is Supplied to an ethylene oxide stripper, wherein 35 wherein the process comprises the additional steps of:
ethylene oxide is removed as a concentrated aqueous ethylene (vii) removing a glycol bleed stream from the ethylene
oxide stream. oxide stripper; and
The ethylene oxide obtained from the ethylene oxide strip (viii) adding a base to the ethylene oxide stripper Such that
per may be undergo hydrolysis with water in order to provide the pH in the bottom section of the stripper is maintained in
monoethylene glycol and also higher glycols such as dieth 40
the range of from at least 9.5 to at most 12.0.
ylene glycol and triethylene glycol. Preferably, the hydrolysis
occurs in the presence of a hydrolysis catalyst in order to BRIEF DESCRIPTION OF THE DRAWINGS
improve the selectivity to monoethylene glycol. Alterna
tively, the ethylene oxide may be reacted with carbon dioxide FIG. 1 is a schematic diagram showing a preferred embodi
in the presence of a carboxylation catalyst to provide ethylene 45 ment of the process according to the invention for producing
carbonate, and the ethylene carbonate may be reacted with ethylene glycol.
water in the presence of a hydrolysis catalyst to provide FIG. 2 is a schematic diagram showing a preferred embodi
ethylene glycol. Such processes are described in U.S. Pat. No. ment of the process according to the invention for producing
6,080,897 A and U.S. Pat. No. 6,187.972 B1 and provide high ethylene glycol.
selectivity to monoethylene glycol. 50
Homogeneous catalysts that are commonly used to pro DETAILED DESCRIPTION OF THE INVENTION
mote hydrolysis of ethylene oxide or ethylene carbonate to
ethylene glycol include basic alkali metal salts such as potas The present inventors have surprisingly found that, in a
sium carbonate, potassium hydroxide and potassium bicar process for the production of ethylene oxide from ethylene
bonate. The present inventors have found that during the 55 comprising a catalytic hydrolysis step, the presence of chlo
operation of a process for preparing ethylene glycol, Such roethanol in the process and the decomposition and deactiva
hydrolysis catalysts can become deactivated during operation tion of the hydrolysis catalyst can be reduced if the pH in the
and that at least part of the deactivation occurs when chloro bottom section of the stripper used to extract ethylene oxide
ethanol, formed from the reaction of ethylene oxide with from an aqueous absorbent is maintained in the range of from
chlorides present in the EO reactor, reacts with the hydrolysis 60 9.5 to 12.0. This can be achieved by the addition of a base to
catalyst to forminorganic chlorides (such as KC1), which are the stripper.
inactive as hydrolysis catalysts, and ethylene glycol. The reaction of ethylene and oxygen to produce ethylene
This deactivation means that it is necessary to provide oxide in an ethylene oxide reactor is well known to the skilled
additional fresh catalyst during operation. Further, a catalyst person. The oxygen may be supplied as oxygen or as air, but
bleed stream must be employed in order to remove the deac 65 is preferably Supplied as oxygen. Ballast gas, for example
tivated catalyst, as well as other decomposition products from methane, is typically Supplied to allow operation at high
the process. oxygen levels without causing a flammable mixture.
 US 9,096,564 B2
3 4
The organic chloride moderator is Supplied for catalyst can promote both reactions (provided that at least one catalyst
performance control. Preferred organic chloride moderators promotes carboxylation and at least one catalyst promotes
are chlorohydrocarbons. More preferably, the organic chlo hydrolysis).
ride moderator is selected from the group of methyl chloride, In the present invention, preferably the one or more cata
ethyl chloride, ethylene dichloride, vinyl chloride, and mix lysts that promote carboxylation and, optionally, hydrolysis
tures thereof. The most preferred organic chloride moderators is/are homogeneous. Homogeneous catalysts that are known
are ethyl chloride and ethylene dichloride. to promote carboxylation include alkali metalhalides such as
The ethylene, oxygen, ballast gas and organic chloride potassium iodide and potassium bromide, and halogenated
moderator are preferably Supplied to recycle gas that is Sup organic phosphonium or ammonium salts such as tributylm
plied to the ethylene oxide reactor from the ethylene oxide 10 ethylphosphonium iodide, tetrabutylphosphonium iodide,
absorber. triphenylmethylphosphonium iodide, triphenyl-propylphos
The ethylene oxide reactor is suitably a multitubular, fixed phonium bromide, triphenylbenzylphosphonium chloride,
bed reactor. The catalyst is preferably finely dispersed silver tetraethylammonium bromide, tetramethylammonium bro
and optionally promoter metals on a Support material, for mide, benzyltriethylammonium bromide, tetrabutylammo
example, alumina. The reaction is preferably carried out at 15 nium bromide and tributylmethylammonium iodide. Homo
pressures of greater than 10 bar and less than 30 bar and geneous catalysts that are known to promote hydrolysis
temperatures of greater than 200° C. and less than 300° C. include basic alkali metal salts such as potassium carbonate,
Most of the ethylene reacts to form ethylene oxide, but a potassium hydroxide and potassium bicarbonate, or alkali
portion of the ethylene will be oxidised fully, providing car metal metalates such as potassium molybdate. Preferred
bon dioxide and water. homogeneous catalyst systems include a combination of
The reactor product stream is Supplied to the quench sec potassium iodide and potassium carbonate, and a combina
tion of an ethylene oxide absorber. After the quench section, tion of tributylmethylphosphonium iodide and potassium car
the product stream passes to the main section of the ethylene bonate.
oxide absorber in which the ethylene oxide is contacted with Alternatively, a heterogeneous catalyst system may be
and absorbed into a lean absorbent stream, which usually 25 used. Such a catalyst system would suitably comprise ions
comprises water. The resultant aqueous ethylene oxide Such as halides, hydroxide or carbonates immobilised on a
stream is referred to as fat absorbent and is supplied to an Solid Support Such as an ion exchange resin.
ethylene oxide stripper, wherein ethylene oxide is removed as Carboxylation of the aqueous ethylene oxide stream in the
a concentrated aqueous ethylene oxide stream. presence of carbon dioxide to produce a stream comprising
Preferably, overhead vapours from the ethylene oxide 30 the corresponding ethylene carbonate occurs in one or more
absorber are recycled to the ethylene oxide reactor. A portion carboxylation reactors. If more than one reactor is present,
of this recycle gas is preferably diverted through an absorber they are preferably arranged in series.
for carbon dioxide removal and is then returned to the recycle The carboxylation reactors are suitably two-phase flow
stream. A vent stream is typically taken from the recycle gas reactors operating at a pressure in the range of from 0.8 to 3.0
to reduce the build-up of inerts such as ethane, argon and 35 MPa and a temperature in the range of from 50 to 180° C.
nitrogen and to remove impurities. The carboxylation reactors will preferably each be pro
The aqueous stream exiting the ethylene oxide absorber, vided with a liquid recycle, wherein liquid is removed from
the fat absorbent stream, is supplied to an ethylene oxide the reactor and then recycled to the bottom of the reactor. The
stripper. In a typical ethylene oxide stripper, a concentrated recycle stream can be heated or cooled in order to provide
ethylene oxide stream leaves the top of the stripper and a lean 40 improved temperature control to the carboxylation reactor.
absorbent stream leaves the bottom of the stripper. The lean Step (vi) of the process of the present invention comprises
absorbent stream is recirculated to the ethylene oxide Supplying either the aqueous ethylene oxide stream from the
absorber and is preferably cooled before it is supplied to the stripperor the stream comprising ethylene carbonate to one or
ethylene oxide absorber. more hydrolysis reactors, wherein the ethylene oxide and/or
A glycol bleed stream is removed from the stripper. This 45 ethylene carbonate present react with water in the presence of
stream comprises glycols formed from the reaction of the a catalyst to form an aqueous ethylene glycol stream.
ethylene oxide with water and is removed to prevent build up If required, a hydrolysis catalyst stream is Supplied to the
of glycols at this stage in the process. MEG may be separated one or more hydrolysis reactors. Such a stream may be
from this stream and purified with the rest of the MEG pro required if the aqueous ethylene oxide stream was Supplied to
duced in the overall process. The glycol bleed stream may 50 the hydrolysis reactors without first undergoing the optional
also contain heavy glycols and salts. carboxylation reaction of step (v). Alternatively, the hydroly
The concentrated aqueous ethylene oxide stream is then sis catalyst may be required if the catalyst stream Supplied to
supplied to the ethylene oxide to ethylene glycol section of the carboxylation reactors did not contain a catalyst that pro
the process, which comprises a catalytic hydrolysis step. moted hydrolysis to a Sufficient extent or if, for any reason,
In a preferred embodiment of the present invention, in 55 not enough hydrolysis catalyst is present in the stream Sup
which the ethylene oxide is transformed to ethylene carbon plied to the one or more hydrolysis reactors.
ate before the hydrolysis step, the aqueous ethylene oxide In the present invention, the hydrolysis catalyst is Suitably
stream is provided to one or more carboxylation reactors. homogeneous. Homogeneous catalysts that are known to pro
Carbon dioxide and a catalyst stream are also supplied. mote hydrolysis include basic alkali metal salts such as potas
The catalyst stream comprises one or more catalysts that 60 sium carbonate, potassium hydroxide and potassium bicar
promote carboxylation and, optionally, hydrolysis. In a pre bonate, or alkali metal metalates Such as potassium
ferred embodiment of the present invention, the catalyst molybdate. In the present process, preferred homogeneous
stream comprises one or more catalysts that promote car catalysts that are known to promote hydrolysis include basic
boxylation and hydrolysis. In this embodiment, if only one alkali metal salts such as potassium carbonate, potassium
catalyst is present, then the catalyst must promote carboxy 65 hydroxide and potassium bicarbonate.
lation and hydrolysis. If two or more catalysts are present, The one or more hydrolysis reactors may be any suitable
then each catalyst can promote carboxylation or hydrolysis or reactor type. Preferably, the hydrolysis reactors are baffled
 US 9,096,564 B2
5 6
reactors. If there is more than one hydrolysis reactor it is from the stripper (6) is supplied to one or more hydrolysis
preferred that the hydrolysis reactors are connected in series. reactors (14) wherein hydrolysis occurs in the presence of a
In one embodiment of the invention, at least one of the one hydrolysis catalyst.
or more hydrolysis reactors is a baffled reactor, wherein the It will be clear to the skilled person, that as schematic
baffled reactor has at least 3, preferably at least 4 compart 5 diagrams these figures do not show all necessary inputs and
ments, the compartments are formed by internal baffles and recycle streams that may be present in the process.
the internal baffles provide a sinuous route for reaction fluid
through the reactor. What is claimed is:
Optionally, steam is injected into the baffled reactor. 1. A process for the production of ethylene glycol compris
The temperature in the one or more hydrolysis reactors is 10
ing the steps of
typically from 100 to 200° C., preferably from 100 to 180° C. (i) Supplying ethylene and oxygen and an organic chloride
The pressure in the one or more hydrolysis reactors is typi
cally from 0.1 to 3 MPa. moderator to an ethylene oxide reactor wherein ethylene
The ethylene glycol product stream emerging from the one and oxygen react in the presence of a catalyst to produce
or more hydrolysis reactors is then Supplied to a dehydration 15 ethylene oxide, thereby producing a reactor product
and purification section in order to remove water and to pro Stream;
duce the desired MEG. (ii) Supplying the reactor product stream to an ethylene
The base that is added in step (vii) of the invention is oxide absorber comprising an absorber section, wherein
preferably an aqueous alkaline Solution, for example, an ethylene oxide is recovered from the reactor product
aqueous Sodium hydroxide or potassium hydroxide solution. stream by absorption in water in the absorber section,
The concentration of the aqueous alkaline Solution is prefer thereby producing a fat absorbent stream;
ably at least 5 wt %, more preferably at least 10 wt %. (iii) Supplying the fatabsorbent stream to an ethylene oxide
Preferably it is at most 50 wt %, more preferably at most 30 wt stripper wherein the fat absorbent stream is steam
%. stripped, thereby producing a concentrated ethylene
The aqueous alkaline solution is a liquid and is added to 25
oxide stream and a lean absorbent stream;
liquids (i.e. it is not added to reactants or products in the (iv) recirculating the lean absorbent stream to the ethylene
gaseous phase). oxide absorber;
The base is added to the ethylene oxide stripper such that (V) optionally supplying the concentrated ethylene oxide
the pH in the bottom section of the stripper is maintained in stream to one or more carboxylation reactors wherein
the range of from at least 9.5 to at most 12.0. Preferably, the 30
ethylene oxide reacts with carbon dioxide to form an
pH in the bottom section of the stripper is maintained at more ethylene carbonate stream; and
than 9.5. Also preferably, the pH is at most 10.5. (vi) Supplying the concentrated ethylene oxide stream and/
As used herein, the term bottom section of the stripper or the ethylene carbonate stream to one or more hydroly
refers to the downstream portion of the stripper. Suitable sis reactors wherein ethylene oxide and/or ethylene car
locations for measurement of the pH within the bottom sec 35
bonate reacts with water in the presence of a hydrolysis
tion of the stripper include in the stripper itself, in the lean
absorbent stream which is removed from the bottom of the catalyst selected from one or more basic alkali metal
stripper or in the glycol bleed stream. salts to form an ethylene glycol stream;
The pH may be monitored by sampling at regular intervals wherein the process comprises the additional steps of:
or by continuous online monitoring. 40 (vii) removing a glycol bleed stream from the ethylene
FIG. 1 is a schematic diagram showing a preferred embodi oxide stripper; and
ment of the process according to the present invention. One or (viii) adding a base to the ethylene oxide stripper Such that
more feeds containing ethylene and oxygen (1) are Supplied the pH in the bottom section of the stripper is maintained
at more than 9.5 to at most 12.0.
to an ethylene oxide reactor (2). The reactor product stream 2. A process according to claim 1, wherein the concen
(3) from the ethylene oxide reactor (2) is then fed to an 45
trated ethylene oxide stream is Supplied to one or more car
absorber (4) where it is contacted with lean absorbent (7). The boxylation reactors wherein ethylene oxide reacts with car
fat absorbent stream (5) is provided to an ethylene oxide
stripper (6), wherein the ethylene oxide is separated and the bon dioxide to form an ethylene carbonate stream in step (V).
lean absorbent (7) is recycled to the absorber (4). The stripper 3. A process according to claim 1, wherein the hydrolysis
has a glycol bleed stream (9) and base (8) is added to the 50 catalyst is selected from potassium carbonate, potassium
stripper (6) in order to maintain the pH of the glycol bleed hydroxide and potassium bicarbonate.
stream (9) in the range of from at least 9.5 to at most 12.0. In 4. A process according to claim 3, wherein the pH is mea
this embodiment the concentrated ethylene oxide stream (10) Sured in the glycol bleed stream.
from the stripper (6) is supplied to one or more carboxylation 5. A process according to claim 1, wherein the base is
reactors (11), each of which has a liquid recycle (12). The 55 selected from the group consisting of potassium hydroxide
stream comprising ethylene carbonate (13) produced in the and sodium hydroxide.
one or more carboxylation reactors (11) is Supplied to one or 6. A process according to claim 1, wherein the pH is at most
10.5.
more hydrolysis reactors (14) wherein hydrolysis occurs in 7. A process according to claim 1, wherein the organic
the presence of a hydrolysis catalyst. The resultant ethylene
glycol stream is then Subjected to dehydration and purifica 60 chloride moderator is a chlorohydrocarbon.
tion in the dehydration and purification section (16) of the 8. A process according to claim 1, wherein the organic
process in order to produce purified ethylene glycols (17). chloride moderator is selected from the group consisting of
FIG.2 is a schematic diagram showing a preferred embodi methyl chloride, ethyl chloride, ethylene dichloride, vinyl
ment of the process according to the present invention. In this chloride, and mixtures thereof.
embodiment the concentrated ethylene oxide stream (10) k k k k k