2) United States Patent Van Ogtrop et al. (54) PROCESSES FOR THE PRODUCTION OF ETHYLENE GLYCOL (75) Inveators: Jan Van Oxteop, Amsterdam (NL) Abraham Adriaan Smaar Amsterdam (NL); Jacqueline Hessing, legal representative, Casticum (NL) Hendrik Stichter, Amsterdam (NL) (73) Assignee: Shell Oil Company, Houston, TX (US) (#) Notice: Suijct to any disclaimer, the teem of this patent is extended or adjusted under 38 USC. 154(b) by 300 days, (21) Appl. Nos 181360,835 (22) Filed: Jan, 31, 2012 6s) Prior Publication Data US 201200197048 Al Aug.2,2012 G0) Forcign Application Priority Data Jan. 31,2011 (EP) 11132780 GI) Me co7C 2909 (2006.01) coz 301722 (2006.01), €07C 29/12 (2006.01) 07D 301704 (2005.01), core 29/10 (2006.01), ~@ U, crc cL 07D 301722 (2013.01); C07C 29/106 (2013.01); €07C 2912 (2013.01), CO7D 301/04 (2013.01) (58) Fleld of Classification Search cre core 29108 Usb 568/858 ‘See application ile for complete search history. (56) References Cited US, PATENT DOCUMENTS Sa22926 4 9/1982 Rett al. 41989 Dy 'US009096564B2 (10) Patent No. 4s) Date of Patent: US 9,096,564 B2 Aug. 4, 2015 5336791 A 81994 Jennings ta sass Som@sor A 62000 Kavabe S68 858 6437199 BL 82002 Okactal FOREIGN PATENT DOCUMENTS oN rans 12006 wo aoowsesss 72004 WO — wo20DsDOD13 + 72008 wo "Wo2mnsoD138 "T2008 com 30110 (OTHER PUBLICATIONS ~Bihylene Oxide”, Ullmann’sEneyclopedia of Indstal Chemis, Sh Ror Bd, vl. A 10, pp. 117-139 1987) IPO Search Report dae Ape 9.2013 for Ref. TS1688 TAL, ROC (ivan) Patent Applicaton No, 097102401 * cited by examiner Primary Examiner —Yoog Chu Assistant Examiner — Sonya Wright 6 ABSTRACT A process foe the production of ethylene glycol comprising (G) supplying ethylene and oxygen anda organic chloride moderator to aa BO reactor, thereby producing a retclor product stream: Gi)supplying the reactor product stream toa EO absorber, thereby preducing a fat absorbent stream: Gi) supplying the fat absorbeat stream to an EO stipper, ‘hereby producing a concentrated liylene oxide strum, ‘anda fean absorbent steam (iv) recirculating the lean absorbent stream to the EO ‘absorber; and (v) supplying the etbylencoxide stream andr the ethylene ‘carbonate stream to hydrolysis reactors with an alk tal salt iydrolysis catalyst to form an elylene glycol ‘wherein the process additionally comprises: (vi) removing a glyco! bleed stream from the ethylene ‘oxide stripper: and (vi) adding a hase othe ethylene oxide stripper such that thepllin the bottom section ofthesteipperis minted fiom 9510 120, 8 Claims, 2 Drawing SheetsU.S. Patent Aug. 4, 2015 Sheet 1 of 2 US 9,096,564 B2U.S. Patent Aug. 4, 2015 Sheet 2 of 2 US 9,096,564 B2US 9,096,564 B2 1 PROCESSES FOR THE PRODUCTION OF ETHYLENE GLYCOL This _pateat application claims the benefit of EPI11S27800 filed Jan. 31, 2011, whieh is incorporated herein by eference. FIELD OF THE INVENTION “The present invention relates to 8 process fr the produc tion of ethylene glycol BACKGROUND OF THE INVENTION ‘Monoethylene glyco is used asa raw materia inthe manu ‘acture of polyester fibres, polyethylene terephthalate PET) pasties and resins. I is also incorporated into automobile fntfreeze liquids. Moncelbiylene glycol istypcally prepared from ethylene oxide, which isin tum prepared from ethylene. Ethylene and oxygen are passed over a silver oxide catalyst, ‘ypieally in the presenee of an organic chloride moderator producing a product stream comprising ethylene oxide, ear bon dioxide, ethylene, oxygen and water The product stream from the ethylene oxide reactor, which may also contain by-produets such as organic chlorides, is then supplied to an ethylene oxide absorber. Typically, the ‘ethylene oxide absorber has an inital quench section such as those described in US, Pat, No, 4822926 A and U.S, Pat. No. $336,791 A ter the quench section, the produt stream passes to the ‘main section of the ethylene oxide absorber in which the ethylene oxide is contacted with and absorbed into a lean absorbent stream, which wmlly comprises water. The esl ‘ant aqueous ethylene oxide stream is referred to as ‘Tat absor- bent” and is supplied 19 an ethylene oxide stripper, wherein ‘ethylene oxides removed asa concentratedaqueous eliylene oxide stream. “The ethylene oxide obtained from the ethylene oxide strp= per may be undergo hydrolysis with water in oder to provide ‘monoethylene glycol nnd also higher glyeols such as dieth- ‘ylene glycol antricthylene glycol. Preferably. the kydrolyss ‘occurs in the presence of a hyrolysis catalyst in onder to Jimprove the selectivity to monoeliylene glycol. Alterna- tively, the etiylene oxide may be reacted with carbon dioxide inthe presence of acarboxylationeaalys to provide ethylene ‘carbonate, and the ethylene carbonate may be reacted with, Water in the presence of a hydrolysis eatalyst 10 provide ‘ethylene glycol, Such processes are described in U.S, at,No, 6,080,897 And US. Pat. No. 6,187,972 BI and providehigh selectivity 10 monoethylene glycol Homogencous catalysts that are commonly used to pro= mote hydrolysis of ethylene oxide or ethylene carbonate t0 ‘ethylene glycol include basic alkali metal salts such as pots sium carbonate, potassium hydroxide and potassium bicar- bonate. The present inventors have found that during the ‘operation of process for preparing ethylene glycol, such hydrolysis catalysts ean become deactivated during operation and that atleast part of the desetivation occurs wheat chloro- ‘ethanol, Formed from the reaction of ethylene oxide with ‘chlorides present in the BO reactor, resets with the hydrolysis ‘catalyst to Form inonganie chlorides (sueh as KC), whieh are inactive as hydrolysis catalysts, and ethylene glyco! “This deactivation means that itis necessary to provide ditional fresh catalyst during operation. Further, a catalyst bles stream must be employed in order to remove the deae- tivated catalyst, as wells other decomposition product rom the process. 0 o 2 ‘The present inventors have, therefore, sought to provide aa improved process wherein the amount of ehloroethanol present in the process is reduced and also wherein thedecom- Position ofthe hydrolysis catalyst is decreased or avoided. ‘SUMMARY OF THE INVENTION Accordingly, the present invention pravides a process for the production of ethylene glyeol comprising the steps of () supplying ethylene and oxygen and an organic chloride moderator to an ethylene oxide rector wherein ethylene and ‘oxygen reac inthe presence ofa eaalyst to produce ethylene oxide, thereby producing a reactor product stream: (Gi) supplying the reactor product stream to an ethylene ‘oxide absorber wherein ethylene oxide is recovered from the reactor prxlet stream by absorption in water in the absorber section, thereby producing a ft absorbent steam Gi) supplying the fat absorbent stream oan ethylene oxide stripper wherein the ft absorbent stream is steam stripped, thereby prlocing a concentrated ethylene oxide sream and lean absorbent stream: (Gv) recteulating the lean absorbent stra wo the etiylene oxide absorber; (¥) optionally supplying the concentrated ethylene oxide steam fo one or more carboxylation reactors wherein ethy- ‘ene oxide reacts with carbon dioxide to form an ethylene carbons steam and (vi)supplying the concentrated ethylene oxide steam and or the ethylene carbonate stream to one or more hydrolysis reactors wherein ethylene oxide and/or ethylene carbonate reacts with water in the presence of a hydrolysis catalyst selected from ane or more basic alkali metal salts to form an ethylene glycol steam: ‘wherein the process comprises the additonal steps of (vi) removing a glycol bleed stream from the ethylene oxide stripper and (vill) adding a base tothe ethylene oxide stripper such that the pH inthe bottom seetion of the stepper is maintained in the range of from at least 95 to at most 120. BRIEF DESCRIPTION OF THE DRAWINGS, FIG. isaschematicdiageam showing apreferedembodi- ment othe proces acconding to the invention for producing ethylene glyco. FIG. 2isaschematicdiagram showing apreferredembodi- at ofthe process according tothe invention for producing ethylene glyco. DETAILED DESCRIPTION OF THE INVENTION “The present inventors have surprisingly found that, ia @ process forthe prociction of ethylene oxide from ethylene ‘comprising a catalytic hydrolysis step, the presence ofchlo- ‘methanol inthe process andthe decomposition and deactiva- tion ofthe hydrolysis catalyst can be reduced if the pH inthe bottom section ofthe stepper used fo extract ethylene oxide {rom an aqueous absorbent i sintained ia the range of eo 9.510 120. This ean be achieved by the addition ofa ase t0 the stepper "The reaction of ethylene and oxygen to preface ethylene ‘oxide inan ethylene oxide reactor is well known tothe skilled person. The oxygen may be supplied as oxygen or as ar, but is preferably supplicd as oxygen, Ballast gas, for example methane, is typically supplied to allow operation at high oxygen evels without causing a flammable mixtureUS 9,096,564 B2 3 The organic chloride moderstor is supplied for catalyst. performance control. Preferred organic chloride moderators are chlomliydrocarbons. More preferably, the organi ehlo- Fide moderator is selected from the group of methyl chloride, ‘ethyl chloride, ethylene dichloride, vinyl chloride, and mix: tures thereof. Themost preferredorganic chloride moderators ate ethyl chloride and ethylene dichloride The ethylene, oxygen, ballast gas and organic chloride moderator are preferably supplied to recycle gos thats sup- plied tothe ellylene oxide reactor from the ethylene oxide absorber, “The elylene oxide reaetor i suitably a mulitubulr, fixed bed reactor. The catalyst is preferably finely dispersed silver ‘and optionally promoter mictals on a support material, for ‘example, alumina. The restion is preferably canied out at pressures of greater than 10 bar and less than 30 bar and temperatures of greater than 200° C. and less than 300° C. ‘Most of the ethylene reacts to form ethylene oxide, but 3 portion ofthe ethene will be oxidised fly: providing ear bon dioxide and water "The reactor product sttvam is supplied to the quench seo tion ofan ehylene oxide absorher. After the quench section, the product stream passes to the main section af the ethylene ‘oxide absorber in which the ethylene oxide is contacted with and absorbed into lean absorbent stream, which ‘comprises water. The resultant aqueous ethylene oxide stream is referred to as “fat absorbent” and is supplied to an ‘ethylene oxide stripper, wherein ethylene oxide s removed as ‘concentrated agueous ethylene oxide stream. Preferably, overhead vapours from the ethylene oxide absorber ae recycled to the ethylene oxide reactor portion ‘of this recycle gas is preferably diverted through an absorber {or earhon dionce removal ands then retumed tothe reeycle stream. A veo steam is typically taken from the reeyele gas to reduce the build-up of inerts such as elhane, argon and nitrogen and to remove impurities "The agucous stream exiting the ethylene oxide absorber, the fat absorbent stream, is supplid to an ethylene oxide ripper. In a typical ethylene oxide stripper, a concentrated ‘ethslene oxide stream leaves the top of the tipper and lean, absorbent stream leaves the bottom of the stripper. The lean absorbent stream is recirculated 10 the etlivlene oxide absorber and is preferably cooled before its supplied to the ‘ethylene oxide absorber, ‘A glycol bleed sieam is removed from the stipper. This stream comprises glycols formed from the reaction of the ‘ethslene oxide with water and is removes to prevent ld up ‘of glycols this stage inthe process. MEG may be separated ‘rom this stream and purified with the rest of the MEG pro- ‘duced in the overall process. The glycol bleed steam may also contain heavy glycols and salts. ‘The concentrated aqueous ethylene oxide stream is then supplied to the ethylene oxide to ethylene glycol section of the process, which comprises a eatalytie hyolysis step In a preferred embodiment of the present invention, in ‘which the ethylene oxide is transformed to ethylene carbon- ate before the hydrolysis step, the aqueous ethylene oxide stream is provided to one of more carboxylation reactors. ‘Carbon dioxide and a catalyst stream are also supplied. The catalyst stream comprises one or more catalysts that proniote carboxylation and, optionally, hydrolysis. Ina pre- fered embodiment of the present invention, the catalyst stream comprises one or mote catalysts that promote ear- boxslation and hydrolysis. In this embodiment, if only one ‘catalyst is present, then the catalyst must promote carboxy lation and hydrolysis. If two oF more catalysts are present then each catalyst ean promote carboxylation or hydrolysis or 4 ‘can promote both reactions (provided that atleast one catalyst promotes carboxylation and at least one catalyst promotes hydrolysis), Tn the present invention, preferably the one or more cata- Iysts that promote carboxylation and, optionally hydrolysis {is/are homogeneous. Homogeneous catalysts that are known to promote carboxylation include alkali meta halides such as potassium iodide and potassium bromide, and halogenated ‘organic phosphonium or ammonium salts such as tibutylm- cliylphosphonium iodide, terbutylphosphoniam iodide, ‘eiphenylmethylphosphonium iodide, triphenyl-propylphos- phoaium bromide, lriphenylbenzylphosphonium chloride, fetraethylammonium bromide, teizamethylammonium beo- mide, benzyltiethylammonium bromide, teabutylammo- ‘nium bromide and tbutyimethytammonium iodide. Home zencous catalysts that ae known to promote hydrolysis Jnclude base alkali metal salts such as potassinm carbonate, potassium hydroxide and potassium bicarbonate, or alkali ‘metal metalstes such as potassium molybdate. Preferred homogeneous catalyst systems include a combination of potassium fodide and potassium carbonate, and a eombina- ‘ionof tibutylmethyIphosphonium iodide and potassium car- bonate Allematively, a Beterogeneous catalyst system may be used. Such 2 catalyst system would suitably comprise ions seh as halides, hydroxide or carbonates immobilised on solid support such s an ion exchange resin Carboxylation of the aqueous eiyene oxide stream inthe presence of carbon dioxide to proioce a seam comprising the coresponding ethylene carbonate oceurs in ane or more carboxylation reactors. If more than one reactor is preset they are preferably arrange in series. “The carboxylation reactors are suitably two-phase Avy reactors operating aa pressure in the range of from 0.8 (03.0 (MPs and temperature in the range of from 50 to 180° C. “The carboxylation reactors will preferably each be peo= vided witha liquid recycle, svherein liquid is removed from the reactor and then recycle tothe bottom of the reaetor, The recycle sticam can be heated or cooled in order to provide improved temperature contro othe carboxylation rector. ‘Step (i) ofthe process of the present invention comprises suppl¥ing ether the aqueous ethylene oxide stream from the ‘tripperor the stream comprising ethylene carbonatetooneor more hydrolysis reactors, wherein the ethylene oxide andor ethylene carbonate present rect with Water the presenceor catalyst to form an aqueous ethylene glycol stream, Ifrequired, a hydrolysis catalyst stream is supplied tothe fone oF more hydrolysis reactors. Sueh a stream may be required ifthe aqueous ethylene oxide stream was supplied 10 the hydrolysis reactors without fist undergoing the eptional carboxylation reaction of step (v)- Alternatively the hydroly- sis atalyst may be required the catalyst stream supplied to the carboxylation reators did not comin catalyst hat pro- :moted hyerolysis toa sufficient extent or if, For any reason, ‘ot enough hydrolysis catalysts present in the stream sup” plied tothe one or more hydrolysis reactors In the present invention, the hydrolysis catalyst is suitably homogeneous. Homogeneous catalysts that ar known to pro- note hydrolysis include basic alkali metal salts such ts potas- sium carbonate, potassium hydroxide and potassium bicar- bonate, of alkali metal metalates such as potassinm ‘molybdate, In the present process, prefered homiogeneots catalysts that are known to promote hydrolysis include basie alkali metal salts such as potassium carbonate, potassinm hydroxide and potassium bicarbonate. “The one ar more hydrolysis reaetors may be any suitable reactor type, Preferably, the hydrolysis reactors are bailedUS 9,096,564 B2 5 reactors, If there is more than one hydrolysis regtor itis prefered that the hydrolysis reactors are connected in eres. Tone embodiment ofthe invention, at least one of the one ‘or more hydrolysis reactors is @ baffled reactor, whervin the baffled reactor has atleast 3, preferably atleast 4 eompart- mens, the compartments are formed by intemal bales and the intemal baffles provide a sinuous route for reaction Mid through the reactor ‘Optionally, steam is injected into the baffled reactor. ‘The temperature inthe one or more hydrolysis reactors is ‘ypically from 100 t0 206” C., preferably from 100 0 180°C. ‘The pressure in the one or more hydrolysis reactors is typi- cally from 01103 MPa, ‘The ethylene plycol provuet stream emerzng from the one ‘or more hydrolysis reactors is then supplied to a dehy ration ‘and purification section i order to remove Water ad to pros ‘duce the desired MEG. The base that is added in step (vit) of the invention is preferably an aqueous alkaline solution, for example, an ‘aqueous sodium hydroxide or potassium hydroxide solution, ‘The eoncentration of the agucous alkaline solution is prefer- ably at least $ wt %, more preferably at least 10 Wt %. Proferably'it is at mos! S0wt%. more preferably at most 0 wt %, The aqueous alkaline solution i a liguid and is added to liquids (ie. itis not alded to reactants oF products in the gaseous phase) “The base is added o te ethylene oxide stripper sueh that the pl inthe bottom section of the stripper is maintained in the range of from atleast 9.5 to at most 12.0, Proferably, the lin the hottom section ofthe strippers maintained at more than 9.5. Also preferably, the pl i at most 10.5 "As used herein, the term “Bottom section ofthe stripper” refers to the downstream portion of the stipper. Suitable locations for measurement of the pH within the bottom sec- tion of the stripper incinde in the stipper itself, inthe lean absorbent steam which is removed from the bottom of the stripper or in the glycol bleed steam, “The pl may be monitored by sampling t regular intervals ‘or by continuous online monitoring IG. 1 isaschematicdligram showing a preferred embod ‘mento the process according the present invention. One oF ore feeds containing ethylene and oxyzen (1) are supplied to an ethylene oxide reactor 2). The eaetor pret stream (@) from the ethylene oxide revctor (2) is then fed to ua “absorber (4) where it is contacted with lean absorbent (7). The fa absorbent stream (S) is provided to an ethylene oxide stripper (6), wherein the ethylene oxide is separated and the Jean absorbent (7) recycled to the absorber (4). Thestripper has a glycol bleed stream (9) and base (8) is alded t0 the ripper (6) in order to maintain the pH ofthe glycol bleed stream (9) in the range of from at leat 9.5 to at most 12.0. In this embodiment the concentrated ethylene oxide stream (10) from the stripper (6) is supplied to one or more carboxylation reactors (11), each of which has a liguid reeyele (12). The stream comprising ethylene earbonste (13) produced in the ‘one or more carboxylation reactors (11) is supplied to one oF more hydrolysis reactors (14) wherein hytrolysis occurs in the presence ofa hydrolysis catalyst. The resultant ethyl alyeo! stream is then subjected to dehydration and purifea- tion in the debydration and purification seeton (16) of the process in order to produce purified ethylene glycols (17). FIG. 2isa schematic diagram showing apreterred embodi- ‘mento the process according othe present invention. Inthis ‘embodiment the concentrated ethylene oxide stream (10) 0 o 6 {rom the stripper (6 is supplied t one oF more hydrolysis reactors (14) wherein hydrolysis oecus inthe presence of a hydrolysis catalyst. It will be clear to the skilled person, that as schematic Gagrams these figures do not show all necessary inputs and recycle steams that may be present in the process. ‘What is claimed is 1A process forthe production of ethylene glycol eompri ing the steps of: () supplying ethylene and oxygen and an organic chloride -mgderator to anethylene oxide reactor wherein ethylene and oxygen react inthe presence ofa catalyst to produce clhyleae oxide, thereby producing a reactor product Gi) supplying the reactor procict stream to an ethylene ‘oie absorber comprising an absorber section, wherein clylene oxide is recovered from the reactor product stream by absorption in water inthe absorber section, thereby producing fat absorbent stream, Gi) supplying the fat absorbent stream an ethylene oxide Stripper wherein the fat absorbent stream #8 steam stripped, thereby producing a concentrated ethylene oxide stream and a lean absorbent stream: (iv) reciteulatng the lean absorbent stream tothe ethylene ‘oxide absorber, (¥) optionally supplying the concentrated ethylene oxide stream fo one or more carboxylation reactors wherein ciylene oxide reacts with earbon dioxide to form an clylene carbonate stream; and (vi)supplying the concentrated ethylene oxide steam and ‘ortle ethylene carbonate stream to one ot morehydkoly- sis reactors wherein ethylene oxide and/or ethylene car- Donate resets with water inthe presence ofa hyceolysis coalalyst selected from one or more basi alkali metal salts to form an ethylene glyco stream; ‘wherein the process comprises the additional steps of (vi) removing a plyeol bleed stream ffom the ethylene ide strippers and (ll) adding a base othe ethylene oxide stepper sueh that the pl inthe botlom section of thesteippers maintained at more than 95 1 at most 12.0. 2..A process according to claim 1, wherein the concen- trated ethylene oxide steam is supplied to one oF more cat boxylation reactors wherein ethylene oxide reacts with car bon dioxice to form an ethylene carbonate stream instep (¥). 3.A process according to claim 1, wherein the hydrolysis catalyst is selected from potassium carbonate, potasinm hydroxide and potassium bicarbonate. 4. process according t claim 3, wherein the pH is mea- sured in the glycol bleed stream. 5. A process according fo claim 1, wherein the base is selected Irom the group consisting of potassinm hydroxide and sodium hydroxide. 16. Apmocess according ica 105. 7..A process uoconding wo claim 1, wherein the ompanic chloride moderator i a chlorohydrocarbon. 8A process according to elim 1, wherein the organic chloride moderator is selected from the group consisting of vethsl chloride, ethyl ehloride, ethylene dichloride, vinyl chloride, and mixtures thereof 1, whereinthe pHisat most