2) United States Patent ‘Van Driessche et al (54) HYDROGENATION (75) Inventors: Eddy Theophyle Andrea Van Driessche, Fklo (BE); Philippe Louis Buess, Overijse (BE); Raphael Frans Caers, Edegem (BE), Arie Van Vliet Sterrebook (BE); Ramzi Yanni Saleh, Baton Rouge, LA (US) Jose Manuel Vargas, Prarievillo, A (US); Kenneth Lloyd Riley, Baton Rouge, LA (US) Maggie! Agosto, Gnsenwell Springs, LA ws) (73) Assignoe: ExxonMobil Chemieal Patents Tne, Houston, TX (US) (4) Notice: Suibjct to any disclaimer, the tem of this patent is extended or adjusted under 3 USC. 1540) by 433 days. (21) Appl.Nos — 10682,742 (22) PCT Filed: Dee. 16,2004 (85) PCTNo: — PCT/BPz00014479 $371 M0), (2),(4) Date: Feb. 9, 2007 (87) PCT Pub, Nos WO200S/058782 PCT Pub Date: Jun. 30, 2005 6s) Prior Publication Data $ 200710161829 AL Ju. 12,2007 Related U.S. Application Data Provisional aplication No, 60/530,804, filed on Dec. 18,2008, 2 core 29448 (2006.01) us. ‘S6n/882; 5681883, Field of Classification Search ‘568/882, 568/883 ‘See application file for complete search history. References Cited USS. PATENT DOCUMENTS 611984. Bethen 260168815, ‘US007S86017B2 US 7,586,017 B2 Sep. 8, 2009 (10) Patent No. 4s) Date of Patent: BA88351 A 611965 Lome 20608 337K 590 A 411968. Csamiet a aon sos BaGLMG A 21075 Childetal eis 9 Sacto? A 21978 Manet 240)608 HE O18 41977 Mayer 260683 59 4000725 891977 Geant et a 260638 B 4500237 4 M1982 Kauthold et 68.909 HOR7S0 A RIDET Kewenet a 568.83 5324420 A 611904 De Munck eal 208124 S780 A 11997 Mathys eta Sas's00 SO446D A 41998 Marimangslietal ns $8526 SuLts9 8 $2000 Hallet 585/529 20080114718 AL 62003 Knoop eal 568 855 PORPIGN PATENT DOCUMENTS av aonig7i%6 62002 De 1003512012001 DE 0227998 92003, rp D 188246 71980 Pp OMSK — 121996 Ge 613503 9/1950 Ge. 2142010985 Wo woosien20 L993 (OTHER PUBLICATIONS (Cavanital, mito “Etict of Water inthe Performance ofthe Solid Phosphovic Avi Catalyst for Alkylation of Benzene to Cumene and for Oligomerzation of Propene” Applisd Catalysis A: General levee Scenes vo. 97 pp 177-196 (1995), Amsterdam, NL “New Syatheses with Cabon Moose” by Falls on . 17 abd 71 New York, 1980, USN: US. Appl No, 10582 929, led Jun, 13,2006, Beadle eta. nite “Improvements in or Relating to Catalyse Reactions USN: US. Appl No 10583756 fle Jun 13,200, Beadle eta Ented “Improvement ino Relating to Hydoformylation” Elvis 0 Price Andrew B. Gritis Primary Examiner (74) Attorney, Agent, or Firm 6 ABSTRACT The use ofa controlled amount of water in a hydrogenation stage of the ox process forthe production of alcohols which ‘uses atleast to reactors in series improves the eficiency of the hydrogenation reaction and catalyst life as dacs a reduc- ‘ion in the amount of sulphur chlorine and hydroformylation catalyst residues inthe feed to hydrogenation, 47 Claims, 1 Drawing SheetU.S. Patent Sep. 8, 2009 6,017 B2 10 106 104 Figure 1US 7,586,017 B2 1 HYDROGENATION ‘CROSS REFERENCE OF RELATED PATENT. [APPLICATIONS ‘This application is a National Stage Application of Inter- national Application No. PCTEP2008/014879, fled 16 Dec. 2004, which claims benefit of US. Provisional Application No. 60/530,804, filed 18 Dec. 2003. These applications are incomporated herein by reference, FIELD OF THE INVENTION “The present invention relates to improvements in or rlat- ing to the production of alcohols, particularly, but not exchi- sively, tothe production of aleobols containing from 6 to 1S ‘carbon atoms BACKGROUND C40 Cs alcohols are produced in lage volumes throvgh= ‘out the world by the hydroformylation of olefins to produce aldehydes, followed by hydrogenation of the aldehydes 10 produce aicobols. The olefias that are wed as fees for the hydroformylation are generally oligomers of olefins thst are ‘obtained from petroleum feedstocks. Various processes may bens to prodhesthe olefins used for hydeoformylation. For ‘example, the octenes that are used inthe production of nonyl leohol, which is produced in large volumes forthe manufae- ture of plasticiser ester, may be produced by the dimerisati ‘of butenes employing a nickel eontaning catalyst, eg by the ‘Ocrolt or Dimersol® processes, or dimerisation ona zeolite fr other acide catalyst. These are processes which yield substantially pureoctenes.Altematively olefin mixtures aver- ‘aging about eight carbon atoms may be obtained by the of omerisation of olefin mixtures using acid catalysts such as Phosphoric acd eatalysts Inboth these processes, due tothe petroleum origins of the ‘olefins, she olelins typically contain impurities such as sul phur and chlorine which can have a damaging effect on the hhydroformylation reaction and, in particular, the hydrogena- tion rections. The hydrogenation reactions are performed by ‘catalytic hydrogenation at elevated temperature and presse tnd the conditions must be carefilly controlled in order to ‘optimise the yield and selectivity of the hydrogenation ‘ensure sae operation ofthe hydrogenation uni, secure com= mercially viable catalyst life and minimize side reactions. ‘Altemative processes for producing aleohols may’ com- prise the hydroformylation of mer carbon number olefins, suchas ethylene, propylene and butenes tothe eoresponding aldehyde of aldehyde mixtures containing one more carbon ‘number than the starting olefin or olefins. These aldehydes, or mixtures thereof, are then subjected to aldolsationo produce ‘condensation produess typically higheralehydes containing fn extra carbon-carbon double bond, often refered to as ‘ens. These enals or enal mixtures may be hydrogenated (0 the corresponding saturated aldehydes or aldehyde mixtures, ‘or diretly tothe comesponding aleohols or alcohol mixtures, Examples of products prodiced by sich processes are 2-me- thylpentanol, 2thyihexanol, 24-dimethylheptanol and 2-propylheptanol, but other alcohols and aleobiol mixtures produived in this way'are also known, ‘A varioty of catalysts have been proposed and used inthe hydrogenation of aldehydes to produce sleohols and in co ‘ain commercial operation a mixture of catalysts have been used inorserto optimize the selectivity ofthe hydrogenation. Forexample United Kingdom Patent 2142010 employsatwo 0 o 2 stage hydrogenation process en a molybdenum di ‘ulphide on carbon catalyst in the fst stage anda nickeloxide ‘on Kieselgulir catalyst in th second stage. The processis said to hydrogenate an aldebyde feed containing organostlphr ‘mpiities which derive from sulphur impurities in the olefin fed “Australian Patent Application 200197176 AI relates tothe hydrogenation of aldehydes to produce alcohols and di closes that water should be present in the hydrogenstion reactor to hydrolyse formic acd esters, acetal, enol ethers, aldol condensation produets and other hydrolysable sub- ances. According’ to Ausirulian Patent Application 200197176 Al wherea series ofhytitgenation reactors con- ‘ected in series are used, the water my be aed ere the individual reactors and only the amount required may be added at the beginning in order fo prevent formation of 3 ‘second water phase in the hydrogenation rector It is also known from U.S. Pat. No. 5324420 that desul- phurisation of the olefin feed to hydroformylation can enhance catalyst life in the production of alcohols especially in the hydrogenation stage It is also known thatthe production of formic acid esters during hydeofommylation may be reduced if water is present during the hydroformylation reaction as described in “New Syntheses with Carbon Monoxide" by J. Falbe on page 71 Accontingly water may be injectedinto thehydroformylation reactor and, inthis instanee, generally an excess of water is ‘sed. Wateris therefore often present in the produet of hydro- ormylaton, Following hydrofomylation and prior t hydrogenation the product ofhydnoformylation is subject to catalyst removal and water washing which can also result in the presence of ‘water in the material that is fe to hydrogenation DESCRIPTION OF THE FIGURE FIG. 1 illustrates a process described herein, DETAILED DESCRIPTION We have found however th fice water should not be present during the hydrogenation eacton, paul ifthe ‘hydrogenation reaction is performed in the liquid phase. Although he presence of waters beneficial in converting the esters and certain heavy products to the desire alcohols ad ‘hyds, and in preventing the formation of een undes- dra by-produts a a esl of reactions involving Water for ‘ato, foe water en deactivate thehydrogenaton estas, particularly when vsing a cuprous chrome hydrogenation Catalyst, whichis prefered boease it improves the abilty ofthe hydrogenation reaction and provides improved conver sion and selectivity In ado, the presence ofa separate ‘water phaeunder reaction condiinsisundeirable Pte thors, since carbon dioxide formed during hydrogeation by a mechanism comprising the hydrolysis of the formate crters any fre water present could fom carbonic acid with {hecarbon dioxide, which in un could eorode the reactors ‘The water may be ieduced ito the fed to the second reactor anda his stage tho amount of water may exceed the Solubility Knit providing the amount doesnot exces the Solubility iit at rection conditions The preset inventions therfore concemed withthe op aisation of the hydrogenation stage in the production of Alcohols ina process that involves hydrofoil followed by hydrogenation “The present invention therefore provides a process forthe production o alcohols comprising the hydrofomation ofUS 7,586,017 B2 3 olefin or olefin mixture followed by catalytic hydrogens tion, wherein the hydrogenation s performed ina series of at least two reactors and water is added (0 the material dis- ‘charge rom the first reactor thats to be hydrogenated inthe Second reetor, inn amount such tat inthe second reactor all the water presen is dseolved in the organic phase Ina preferred embodiment the present invention provides process for the production of sleohols comprising the hydro- ormylation of an olefin of olefin mixture followed by cata- Iytic hydrogenation wherein the hydrogenation is performed ina seriesofat least two reactors wherein water isalded tothe hydroformylation reactor and no Further wate is added i the fist hydrogenation reactor and water is added tothe second hydrogenation reactor In this preferred embodiment water will be caried over ‘rom the hydroformylation reactor ora demetalling or wash- step downstream ofthe hydroformyation recto, into the first hydrogenation reactor, the amount of water cartied over being such that all the water present is, under reaetion eon tions, dissolved inthe organi phase to be hydrogenated, Tn the first hydrogenation reactor @ namber of side eac- tions wil take place under the hydrogenation conditions. For ‘example formate esters will be hydrolysed to form aleabals, ormic acid, carbon monoxide, carbon dioxide, hydrogen and methanol, and acetals wll e hydrolysed to form alcohols ‘and aldelivdes. Both of these reactions consume water and accordingly the water is depleted during hydrogenation and Jurher waters preferably added tothe material entering the second hydrogenation reaetor to optimise the hydrogenation Jnthat reactor: Theamount of water added shouldbe such that the total amount of water present in the second reactor is dissolved in the organic phase to be hydrogenated under reaction conditions In a further embodiment of the present invention the sul= phur content of the material fed to th first hydrogenation Feacor is below 10 ppm by weight, preferably below 5 ppm, ‘more preferably below 1 ppm. Sulphur can be present in the product of hydroformylation because of sulphur present in the syngas wsed in the hydroformylaion and particularly becatse of sulphur present inthe olefin that is hyeofoemy- lated. Accordingly in further embodiment of the present invention the olefin used for hydroformylation followed by hydrogenation has a sulphur conteat below 10 ppm by Weight, preferably below 5 ppm more preferably below 1 Phim, most prefenbly below 0.1 pa. Ina further embodiment ofthe present invention the chlo Fine content of the material fod tothe frst hydrogenation reactor is below 10 ppm by weight, preferably bolaw 5 ppm, more preferably below 1 ppm, most preferably below 0.1 ‘ppm. Chlorine can bo present because of chlorine present in the catalyst added 19 the hyéroformplation, or because of ‘chlorine present in any other chemical or wash water used in, the hydroformlation catalyst removal step and particularly boeatise of ehlorine present in the olefin whieh is the raw material for hydroformylation. Accordingly in a further ‘embodiment ofthe present invention the chlorine content of the olefin used for hydrofomylation followed by hydrozena- tion has a chlorine content below 10 ppm by weight, prefer= ably below S ppm, more preferably below I ppm, most pref ‘erably below 0.1 ppm. "The present invention therefore further provides an oleia ‘rolefn mixture containing from to [3 carbon atoms wef Jn the production af alcohols by hydroformylation of the ‘olefin followed by hyerogenation, sad olefin containing no ‘more than 10 ppm by weight, preferably 0 more than S ppm, ‘ore preferahly no more than 1 ppm most preferably below 0.1 ppm, sulphur and ao more than 10 ppm preferably no 0 o 4 nore than 5 ppm and more preferably no more than 1 ppm, siost preferably below 0.1 ppm chlorine. In particular the reset invention provides sch aa olefin having eight earboa ‘toms useful in the production of C, aleohols. Te will be understood that such olefin or olefin mixture consfitites # feedsteam to be used in commercial hydro ormylation operations which ae generally lange sale and continous, Sch streams may beclerived from petrochemical andlor refinery operations such as steam cracking of cat ‘racking, Typically, they comprise mixtures of olefins that not ‘only have different carbon numbers, but wether of not the ‘arbon numbers are different, comprise linear and branched olefins, Other, non-olefinie, components may be present, for ‘example saturated ydrocartons. ‘Whilst the present invention is applicable to any process involving hydroformylation of olefins to produce aldehydes followed by hydrogenation to produce alcohols, itis parien- larly applicable to the production of, to C,sleohols from 10 C., olefins or olefin mixtures, preferably of Cw Cs aleoos from C; to C olefins or olefin mixtures. The iven- tion is especially useful in the production of C, 40 Cy aleo- hols from C, 10 C, olefins or olefin mixtures. “The olefin mixtures according to the invention typically comprise not more than 90 wt % of noma or linear olefins the remainder being branches olefins, typically @ mixture of atleast isomers with different skeletal structures, preferably at least 5, more preferably a least 8 and most preferably at Teast 10 isomers ith different backbone structures, ierespec- tive of the location ofthe double bond. The content of normal olefins is readily determined using a capillary gas chroma- tography (GC) analysis technique, preferably with on-line or ‘n-it ydrogenation of the feed olefins before they enter the GC column, or more preferably even a combination of the ‘0. This echniqueinvolving hydrozenztion isalso knowns “hydro-GC" and initsspectrumall the normal olefins, ie. the ‘normal alpha olefins and the nomal internal olefins com- bined, show up as one peak per carbon number as the equiva- Jentnormal ptaffins and which elute typically a8 the last peak within the same carbon number. The same technique is also capable of separating isomers with different backbone stme- tures, many of which may be identified by calibrating the GC column with model compounds andor by applying GC-MS. Preferably the content of nonnalolefins in the olefin mixture isnot more than 70 wt %, more preferably not more than 3S 1W1%, even more preferably not more han 15 wi and most preferably not more than 9 1% of noemal oF linear olefins. IF there are normal paraffins present inthe tating olefin mix- ture, the content thereof may be determined from the equiva Jent spectrum without the hydrogenation. Usually these are Jow in the commercial mixtures of intrest derived fom pet- rochemical andor refinery operations Irom petroleum feed- stocks, and there is foo mech overap inthe GC spectrum, ‘he amount of normal parilins present in the starting celia ‘mixture may be neglected, ‘The branched olefins subjected to hydoformylation fal- lowed by hydrogenation result in branched alcohols; with ‘normal olefins certain amount of their derivatives are nor: ‘mal alcohols. When a cobalt catalyst is used in hydroformy Jation, there will he more normal alcohols produced than ‘whe rhodium catalyst is used, 36 the cobalt eatalyst will tend (move any intemal double bond tsvards an end ofthe olefin backbone structure before hydroformylating. the ‘double bond. ‘Whore the olefin mixture isa mixture of C7 to C9 olefins, the C8 olefin content is preferably atleast $0 wt %, more preferably 75 w1%, even more preferably 90 wi %, and most preferably 97 wt %. The carbon number dstibution of theUS 7,586,017 B2 ‘ography (GC), prelerably again by * ‘agzin usually expressed in weight %. Standard industry proc tice is to split the GC spectrum into carbon number regions ‘corresponding to the individual normal parufias such as heptane, n-octane, n-nonane and ndecane. The region cut- ing before a particular normal paraffin but after the nonnl paraffin having one less carbon atom than that particular iydro-GC”, and is ommal paralfin is assigned to the branched paraffins branched olefin ona hydro-GC spectrum—having the nu berof carbon atomsor te particule (higher) normal pata. For example, the GC region between n-octane and n-nonane, and the region including the m-nonane, are considered 10 ‘correspond to all the C9 paraffins, and therefore to the C9 ‘olefins in the starting olefin mixture. Sue lechnigue my oF ‘may’ ot neglect any paraffins that were preseot in the olefin mixture, depending on whether an ushydrogenated GC spec: ‘eum isobiained in parallel, and onthe quality and resolution thereof, “The invention also particularly applicable to processesin ‘which the hydoformylaton is performed at elevated fem- peratures and pressures using a cobalt ora rhodium catalyst. However, in order to achieve optimum performance in the hhydrogetsation section its desirable to remove the cobalt oF rhodium species from the product of hydroformylation prior ‘o hydrogenation in the fist hydrogenation reactor. Whea using cobalt, i is preferred thatthe cabalt lovel be below $ pm, more preferably below 2 ppm. Accondingly in a furher Preferment of the present invention the product of hydro- Tomaslaton is treated to remove cobalt species so that the ‘cobalt contents below 1 ppm prior to hydrogenation. When sodium, its preferred thatthe rhodium level be below (0.1 ppm by weigh, more preferably below 50 ppb, even more preferably below 10 ppb, most preferably below 5 ppb by ‘weight Inanother process forthe production of C6,7,C8,CDand C10 aleohols particularly the C, alcohol 2-methyipentano, the C; aleokol mixture primarily of 2-cthylpentano! and 2-methylhexanol, the Cy aleohols. 2-ethylhexanol andor 2ethyl-4-methylpentanol, the C, alcool 2.4-dimethyliep- ‘anol, the C,» aleohols 2-propytheptanol andlor 2-propyled- smethyibexabel, and mixtures thereof, C,,C,and/orC, olefins aresubjeettohydroformylationat low pressure, Thealdehyde ‘oraldehyde mixtures produced may then be subject o hydro- tenaion for proicing the coresponding Cs, C, or C, aleo- hols, or the aldehydes may be subject to one oF more aldol ‘condensation reactions to produce higher and unsaturated aldehydes which are then hydrogenated to produce the ‘desired aleohols or saturated aldehydes. The saturated aldo hhydes may then be further hydrogenated to the desired aleo- hols or alcoho! mixtures, or they may be oxidived to the ‘corresponding carboxylic acids or acid mixtures. Catalysts tsed fbr the hydrogenation of such streams containing sat- rated or unsaturated aldehydes or enals, may be based on ‘copper. chrome, cobalt, nickel, molybdenum, aluminum ‘oxide, and combinations thereof. Also thee hydrogenation, reactions benefit from the presence of water by reducing or suppressing alcohol dehydration, formation of hemiacetals ‘or acetals. A further embodiment ofthe present invention is therefore to hydrogenate in the Higuid phase, saturated oF ‘unsaturated aldehydes produced by the low pressure hyro- ormylation process, which in the case of unsaturated alde- hydes is followed by one or more aldoisaion steps. The hydrogenation is performed ina series ofat least 0 aeons, and waters add tothe material to he hydrogensted in the reactor in an amount such that the total amount of 0 o 6 te present is under reation conditions dissolved in the ‘organic phase in the second hydrogenation reactor. “The invention futher provides apparatus forthe operation cof the various processes of this invention ‘The hydrofommylation reaction of the present invention may he performed at elevated temperature and pressure inthe presence of s hytroformylation catalyst. The optimum tem perature and pressure will depend upon the selection and Sosing of the catalyst, the nature ofthe olefin feed, both in fem ofthe carbon number(s) of the olefins, the structure of the olefin (inear or branched) and the concentration of the olefin in the feed whichis typically a mixture of saturated and ‘unsaturated (predominately olefinie) materials, Typical pres- sures forthe high pressure process are from SO to 380 barg. preferably 1500 350 bar, most preferably from 275 to 325 ‘ag. Typical temperatures range from 120 10 190°C, pre erably from 165 oF 1700 188° C.,e.g. 165 to 185° C. more preferably from 170t0 185° C.,<.¢. 1700 180° C., although certain olefin feeds may preferably be hydroformylated at lower temperatures such as from 100 oF 120 140° C. yp cally for reasons of olefin reactivity or reaction selectivity. ‘The catalyst use inthe high pressure hydroformylation is ‘usally a cobalt ora rhodium catalyst and generally the active cobalt catalyst is hydr(docobal(e- or tetra-)earbonyl and cobalt concentrations of up fo 0.8 wt % cobalt onthe olefin contentof the feed are used, preferably from 001 or 0. w1% 00.5% cobalt. Using dhodium under such high pressures, ‘much lower concentrations may be used, such as 0.1 to 200 ppm by eight relative tothe olefin feed, preferably 0.2 to 50 ‘hm, more preferably 0.3 © 20 ppm, even more preferably (04 to ppm by weight, Also the temperatures may be lseer ‘when using rhodium, using the benefit of its higher activity compared to cobsit, and may be 10, 20, 30 or even 40° C lower than those when using cobalt, Hydroformlation reactions of lower olefins such as the vyleae, propylene and butenes have generally. employed thodium catalyst, stabilised by phosphorus-containing ligands and operated in whats known asthe lows pressure ONO technology originally developed by Union Carbide Corpora- ‘ion and curently available under licence from Davy Process ‘Technology Ltd, The hydroformylation is preferably cari ‘out inthe presence ofa hodiu catalyst complex inconjune- tion with an onganophosphorus ligand. This organopbospbo- ris ligand may bea tertiary orzanophiosphine or an organo- phosphite, "The tsionganophosphine ligand can be ‘eialky phosphine such as tibutylphosphine, a C1-Cé alkyl- iarylphosphine such as butylliphenylphosphine, an aryl- ialky}phosphine such as phenyl-dibutylphosphine, an aryl alkyl diphosphine such as eyelohexyldipheny! phoshine ‘etraphenyldiphosphino-methane, 1,2-bis(diphenyl phos: phino) ethane, 13-bis(dipheny! phosphino) propane, 14-bis (diphenyl phosphino) butane, and the bisphosphine ligands escribed in EP-A 279.018, EP-A 311,619, WO 9006810 and EP-A 71,281. However particular phosphines such as ‘eiphenylphosphine, trp-folylphosphine, trinaphhylphos- phine, phenyldinaphthyiphosphine, diphonylnaplihylph phine, tri(p-methoxypheny)-phosphine, tri(p-cyanopheny!) phosphine, tr(p-nittopheny!)phosphine, _pN,N-cimethyl- aminophenylbisphenyl-phosphine andthe like are prefered Triphenylphosphine is most preferred. “The phosphine may also be made water soluble, by pro= viding t with one or more onie functions, Examples of sch phosphines ae trpheny Iphosphine monosulfonate (IPPMS) or triphenyiphosphine trsulphonate(TPPTS), but many other ionic ligands are known. ‘Organophosphite ligands that can be wd are disclose in US. Pat, No, 4599,206, US. Pat, No, 4,668,651, U.S. Pa.US 7,586,017 B2 1 No, 4,797,588, US. Pat. No 4,748,261, U.S, Pat. No. 4,769, 498, US. Pat, No. 4.774361, US. Pat No. 4,789,753, US. Pat, No, 4,835,299, US, Pat, No, 4,871,880, US. Pat. No. 4885,401, US. Pat. No, £179,085, US. Pat. No. 8.288.918, US. Pat, No, 5,312,996, U.S. Pat, No, 5,364,950, US. Pat. No. .681,473, US. Pat No. 5.756.858, WO 97/20793, Pre- ferred ip 6,6¢{[3.3555-tetakis( 1 Llimethyethy)1,1 pheayl]2.2- pressure, typically after separating atleast a portion of the asses that are contained in the hydeoformylation product. ‘The acidic methods typically apply low molecular organic ids ike formic acid andor acti ac, They may adiion- ally involve a stripping step, wherein part ofthe cobalt in a volatile form like H Co (CO} is stripped using a gas fom the Tiguid hydroformylation product, and carried into an absorber swhereit may he absorhed into suitable liquid like feed olefin ‘or heavy byproducts, The oxidative methods may involve the use of oxygen oran oxygen containing gas, or air. The meth- ‘ds may convert all or only a portion of the eobalt values 10 their zero valency andor to their +2 valeney equivalents. Part ‘or all of the eobalt values may be converted to cobalt salts, preferably a sal that issoluble in water, more preferably salt ‘roman organic aeid like cobalt formate oracetate, The cobalt values may be fed or recycled to the hydroformylation reac- tion in a form dissolved in organie liquid such as olefin feed, heavy byproducts or another suitable liquid, i the form of & ‘carbouy] ora a salt, which may be Water oF ol soluble, and may be formate, aceite, oleate, naplihenate of any ether suitable carboxylate dissolved ina suitable organic catier ot Following decobalting the decobalted product, which com= prises dissolved gs, entrained gas, water and the hydro- yormylation product mixture, maybe fe, possibly'atercool- ing to a high pressure separtor which separates he fee pas as high pressure offgas fom the iguid phase. Typically, the high pressure separator operates ut a pressure of 250 bang oF higher. referred prossure'sin the range 250 w 300 barg with 260 to 270 barg being most prefered. In another variety, the inydroformylation pressure may be not more than 210 barg ‘andthe high presse separator may he at apresture of 20-30, bar below that, The gs is separated off and where gas reeyele js used the amount required for recyele is seat to an offgas recycle compressor system. Any excess gas may be disposed ‘of Inaddivon, unwanted gasses such as excess nitrogen and ‘other inert may’also be removed to ensure that the recyele of asses does not result in an undesirable build up of inert “gasses such as nitrogen inthe hyroformylaton reactors ‘The Tiguid left in the high pressure separator may then be {Edtoan intermediate pressure separator where the presse is reduced (0 a level that 1 major portion of the gasses stil 12 dissolved or entrained inthe liquid from the high pressure scparator are released st intermediate pressure oflgas. In ‘erin processes it may be useful to employ more than one high pressure separator in which case two intermediate pres sure separators may be employe or the liquid proguets from the high pressure separators may be combined and fed to @ single intermediate pressure separator. Here again, any excess gas may be disposed of and unwanted gasses such as ‘methane may be removed to ensure that a reeyele of gasses does not rw in a undesirable build up of methane. “The pressure inthe intermediate presure separators typi- cally between $0 and 200 barg, preferably between 80 and 130 or 150 barg, preferably between 90 and 110 barg and we ‘have found that 100 bares parcularly useful. The reduction in the pressure releases the dissolved gasses, particularly ‘unreacted hydrogen and carbon monoxide, and methane, of ‘whieh a portion ean be sent othe oflgas reyele compressor system for subsequent recycle. The rests thea typically dis- posedofl asa purgestream Accordingly. offzas from both the high pressure separator and the intermediate pressure sepa- ‘ator ean be combined inthe offgas recycle eompressor sy {em fo produce the recycle materials when employed. The Flowsto the recycle compressor and the purge flows from igh ‘and intermediate pressure separators may be used 10 adjust the balance of the gasses, particularly the balance of hydeo- sen, carbon monoxide, carbon dioxide, nitrogen and methane that are fet the hydroformylation rectors forthe catalysed hydroformylation reaction with the olefin, Optionally the hydrogen content in hydroformylation may be adjusted by the incorporation of hydrogen oflgas from the hydrogenstion ‘unit ofthe present invention ‘When the offgasses from the high pressure and intermedi- ate pressure separators, optionally together with a hydrogen stream from the downstream hydrogenation reactor, are recycled, they may be fed tothe ecyele compressors and, if necessary, fresh hydrogen may be added 10 produce the stream for hydroformylation having the desired composition. Itisprefered that the reeyele compressor system comprises a series of gs compressors oF compressor stages in which the 8 pressure i gradually inereasod tothe pressure required in the liydrofomylation reaction. We particularly prefer ta use a recycle compressor system comprising thre gas compressors ‘or compressor stages in series. In such a system the olfgas {rom the high pressure separator and the intermediate pres- sre separator may be fed to the fist compressor which yp cally operate at a pressure between 50 and 60 barg. Hydro en as the offgas from the hydrogenation reactor (Which {ypically also contains carbon dioxide, some carbon monox- ‘de, plus nitrogen and methane) may also be fed to the frst ‘compressor. The gas mixture formed in this ist compressor ‘may then be fed to a second compressor where the presse ‘may be inereased to within the range 140 to 180 barg, pref terably 150 to 170 bars aad we have found that 160 bars is particularly convenient. The product ofthe sscond compres sormay then be passe the third compressor and aiional ‘2 fom the igh pressure separator may be introduced t0 ensure the desired composition ofthe recycle gas feed i the fist and second hydroformylation reactors, The pressure is then ised inthe thi compressor and the product from the third compressor foto the fest and second hydroforms ation reactors along with the olefin feed, hydeofoemylation catalyst And fresh gasses ‘The effective operation of the hydroformylation reaction therefore depends upon optimizing the combination of phy cal conditions such as temperatures, pressures, feed rates of ‘nw materials, space velocity inthe reactors and the chemical process conditions. The chemical conditions include in eachUS 7,586,017 B2 13 ‘of the reactors the nature of the olefin feed, relative propor. tions of olefin feed and other gasses incloding hydrogen ‘carbon monoxide and ineas such as aitrogen, methane and ‘carbon dioxideas wel as catalyst concentration, The amount ‘of offs that should be recycled and the amount of syngas fand olefin that shoul be fel tothe second and, optionally, subsequent reactors depends on many of these variables However by establishing the ofigas pressure from the high pressure separator and monitoring the composition of the ‘oflgas, which includes hydrogen, earbon monoxide and the various inert, the hydrogen and carbon monoxide partial pressures atthe end ofthe hydroformylation reaction ean be ‘calculated and used 0 control the gas compositions in the upstream hydoformy/lation reactors. High hydrogen ane ear- ‘bon monoxide partial pressures enhance the stability ofthe ‘cobalt catalyst, and high hydrogen partial pressures assure a favorable hydroformylation reaction rate. Thesedesirs rein ‘conflict with the dese for higher level of inert buildup, hich enables mor effective gas purging and improvedver- all gas ulization, because less valuable hydrogen and carbon ‘monoxide need to be purged with the ners. This mst hom= ‘ever be balanced with the constraints imposed by a fixed ‘equipment design pressor, whic can result ina lower bydo= ten and carbon monoxide contentof the high pressure offgas and hence also in hydroformylation. The optimal control point therefore isa compromise between these counteracting preferences. Since the consumption of hydrogen in hydro- Jomylation i greater than the consumption of earbon mon- ‘oxide, where a series of hydroformylation reactors is used, hydrogen will be depleted relative to carbon monoxide inthe first reactor. Tie difficulty can he overcame by increasing the proportion of hydrogen inthe reeycle gas that i fed 10 the ccond andlor a subsequent hydeoformylation reactor. ‘Asa general puide we have found that the pressure atthe ‘end ofthe hydroformylation reaction should be kept above 170 bary. preferably above 190 or 200 bary, more preferably above 210 of 220 barg, most preferably above 240 bargin ‘ondertoavoid cobalt plating the hydrofoemyfation reactors, We have also fund thatthe carbon monoxide content ofthe ‘offgas from the high pressure separator should be such that the partial pressure of CO is above 75 harg. better above 77 barg, preferably above 84 bar, since if the partial pressure drops below these levels cobalt plating may occur in the hydroformylation reactors. Smiley the hydrogen content of the offgas from the high pressure separator should be such thatthe partial pressure of hydrogen is above 75 barg, better above 77 harg, preferably ahove 84 nnd more preferably above 91 burg, sinee ite partial pressure drops below this Jevel there isa drop in reaction rate. These issues may be ‘controlled by checking the syngas composition, the pressure ‘drop srossthe hydroformylation reaction and the proportion ‘of inerts inthe various streams and making the appropriate ‘adjustments. The use of at Jest two reactors in series and the separate adjustment ofthe feds othe eactrsby the reeyele ‘of gasses can make significant contribution to the eficiency and effective operation of the hydroformplaton reaction. “Another inmportant aspect of the hydroformslation reaction js thereationtemperature and temporatureconteol. The reac- tion i highly exothermic and the temperature generated ‘depends on the reativity ofthe olefins and the concentration ‘nd ratio ofthe reaetive materials, the catalyst concentration tnd the volume of inert material present. Accordingly the reeyele gasses ean be use to adjust the amount an ratios of the reactive materials present and the composition of the recycle gasses can be adjusted as a component of reaction temperature contr. The reactors are also provided with cool- ing systems. These an be internal cooling coils or piping, oF 0 o 14 ‘jacket around the reactor, oF a heat exchanger that is made part ofthe reactor, such avis disclosed in WO O1/29018. ‘combination of these cooling means may be employed. A heat ‘exchanger which is pan ofa loop reactor is typically located in the downward leg of the lop, preferably inthe lower part ofthe leg, and soften known as aconelitioner. The mteof heat transfer from the reacting fluid to the wall of any of such cooling system, and hence the reactor cooling, is improved ‘wheat the reacting fluid as higher velocity relative to the wall ofthe cooling system, In the preferred use of loop reactors, the circulation inthe loop reactor is important for the control of the degree of ‘mixing ofthe reactants and for an even temporatre distrib tion, We have found tha in order to obtain a well mixed reaction mixture the rate of eireulaton within the lop should be at least sx times the rate of fod oF materials the reactor, ‘We havealso found tat a temperature difference between the reactor outlet temperature and the conditioner inlet tempers- ture of greater than 20° C-ean indicate insulicienteircula- tion, Preferably tis temperature difference is lower than 20° such as not more than 16 or even 110° C., preferably not mon: than 5°C., however the prefered diference depends on the reactivity ofthe olefins being hyrofomylated and on the other operiting conditions. Cooling water or another medium such as an alkanol, for example methanol, is provided to the cooling system, if present. Such cooling system may comprise a jacket and a conditioner, for each reactor. The Mow rate of the cooling ‘water or medium is preferably substantially constant and high, in orer to enhance heat transfer, so the cooling system ‘may comprise » pumparoind setup for circulation over the jacket andor the conditioner. Ina loop reactor, the cooling ‘water ciculation is preferably in cotntercurent with the process fluid flow. Hot water liquid or vapor may be removed from this system and colder water may be introduces into ‘The colder water flow rate willbe selected according to the size of the reactor and the calelated heat generated by the reactor. For reactions to be performed in the temperatare range of 170° C.to 190° C. we prefer thatthe enoling water has a temperature in the range of 140-170" C., and the colder ‘water intmiced may havea temperatareaf 9 or 1000 125° CC. Ite feed oefin is Tow in reactivity, fr instance because itis of a high carbon number, the cooling system may be utlsed to supply heat into the reacting uid Tnorder to improve te selectivity of the hydeofomnylation action, water may be present inthe hydofomylationreae~ tors. We hive found that the injection of water reduces the formation of formate esters and heavy by-peodvers, When used, water should be injected into the frst restor, and may als be injected into the second an subsequent reactors, if they are used, but we have found that this is not abways essential. Ina gai reactor, the formation ofa significant Volume of @ slagnant Iroc Water phase in the bottom eat ‘become an impediment or even an obstruction to the eteula- ‘ion ofthe reactor Mid, Gas-lift reactors from which any free ‘water is continuously removed from the bottom have been eseribed in WO 01/14297. If there is no Water removal capability, the quantity of water that is introduced should preferably not exceed oe not exceed by more tha 10 ce 20% ‘he solubility ofthe water inthe evetion mixture, to avid the ormation ofa stagnant free water phase i the reactor, We have fond that no more than 2 wt % of water based on the ‘weight of olefin fed should be used in the fist reactor and ‘ypically from 1.0 % to 1.75 wi % particularly 1.5 91 % should be used. The weight th olefin feed being the weight ‘of unsaturated materials in the feed which is typically above 95 wt %of the feed and frequently about 9 wi % of the feeUS 7,586,017 B2 15, ‘Where waters injected into the second reator, similar siderations may apply depending on the design ofthe reactor Due tothe different liquid composition inthe second reactor, the water solubility may'be different inthis reactor, and we profer touse typically a total of 25 wt % water present based ‘onthe olefin feed, It needs to be understood that these water Jevels depend on the olefin type and alcohol prot that is processed, due to the diferent water solubility othe core- sponding process steams. It also needs to be understood that the dstibutionof the water injected depends on the sizeof the individual reactor stages, ‘We have found that the injection of water provides a sig nificant improvement in plant utilization as well as earbon ‘monoxide wilization, The water shouldbe injected ina man- ner that ensures good mixing of the water withthe reactants ‘and also prevents lage loctuations in the olefin to water feed ‘Accordingly: it is prefered that the water be injected into {ully operational reactor and when loop reactor is used i is preferod tht the materials are circulating ata velocity af at feast 0.6 meterssee when the water is injected, It 8 also prefered thatthe water and the olefin re continuously itro- ‘ced into the reactor atthe desired water to olefin ratio. The present invention is applicable to processes which ‘employ any liquid phase catalytic hydrogenation technique. Many of those employ heterogeneous catalysts in fixed bed reactorsorin slur circulating reator ystems. They may use ‘any’ of the conventionally used supported metal catalyst, such as Ni Pd or Pt supported ona variety of supports sch as granular carbon, silica, silia-alumina, zirconia, silicon bide, or copper chromite. Other wsefil catalysts include ‘cobalt compounds; nickel compounds which may contain smallamonnis of chromium or another promotor mixtures of ‘copper and nickel andor eiromiums and otber Group VILL metal catalysts, such as Pt, Pd, Rh and mixtures thereof, on supports, such as carbon sli, alumina or silica-alumina ‘The nickel compounds are generally deposited on support ‘materials sueh as alumina or kiezelgur. For example nickel based eatalystsmay be used saci as supports nickel sulphide ‘catalyst. The process may also involve the use of different, fetalysts in the series of hydrogenation reactors as is ‘described in US, Pat. No. 5,324,420. Other suitable catalysts and processes are disclosed in US. Pat. No. 4.982.011, US. Pat, No, 4,647,707, USS, Pat, No. 4,658,068, U.S, Pal No. 5,050,718, US. Pal No. 5.306.848, US. Pat. No.5324.420. US. Pat, No, 5,382,715, US. Pat, No, 5,399,793, US. Pat No. 5,663,388, US. Pat. No. 5,877,358, which uses interme- diate product reeyele, or US. Pat. No. 6,278,030. However, we prefer to use a cuprous ehrome hydmgens tion catalyst and particularly catalyst containing frm about 20% to 40% by weight of each of copper and chromium. ibased om the weight ofthe foal catalyst including any sup- Port, preferably Irom 25% to 32% of each of copper and ‘chromium, more preferably 29% to 31% of each of copper ‘and chromium. The remainder is typically barium, sifca and ‘carbon by way’of binders and supports. They may contain up to 10 wi % silica, Preferred catalysts comprise G 22 RS available from Sd-Chemie andl Cu 1155 T available from Engelbard. Cuprous chrome catalysts are preferred because they have alow tendency to cause reaction runaways. ‘Many of the hydrogenation catalysts, such as cuprous ‘chrom, are poisoned by sulphur species. Desuphurisation| may be performed optionally on the olefin fed tothe hydro- omslation, with echnigues known in thea, or as disclosed in US. Pat, No, 5324420, which uses massive nickel ‘catalyst containing some alumina and slicium, However, the presence of silicium together with alumina ean eause this 0 o 16 catalyst to show acidity, and therefore to cause olefin dimeri- sation. For certain ofthe olefin feeds, these dimers formed in esulfursation cause hydrocarbons to show up in the product leo! ater hydroformylation, hydrogenation and distill ‘ion. tis therefore important to use desulphurisation catalysts ‘witha low acilty level. Thisean be achieved by having either 4 high alumiaiumiilicium ito, approaching pure ali- ‘minum as the support or witha very low aluminiunsilicinm ratio, approaching a pure sliea support Inanother embodiment ofthe current invention, we prefer to te heterogencoue catalysts that are not poisoned By any sulphur species that may be present in the fod to hydroge- sation. This provides « more simple process for producing loos, because it avoids the nead to remove sulpur com pounds fom the olefin feed or from the synthesis gs fed to the hydrofomylation reaction or from the hydroformylation product, Suitable catalysts whose activity s not destroyed by sulphur impurities, may be monometallie catalyst eompos tions such as sulphided Mo oxide supported oa carbon, Fur ther examples are bimetallic catalyst compositions, such as stlphided Co oxide/Mo oxide supported on alumina, or se phided Ni oxide/Mo oxide supported on alumina, We have also found that redoced or partially evluced sulphides Ni/Mo ‘or Co/Mo, supported on alumina, is tolerant sulfur in the hhydrogenation feed, unlike reduced nickel supported onal ‘ming, Reference is made hereto copending application US. Ser. No. 601504,543, filed on Sep. 19, 2003. However, we ‘have found that catalyst compositions which comprise one or ‘more active metals on aeiie supports ean demonstrate exees- sive by-produet formation when used for th hydrogenation ofaldehydes. Such acide supports may be alumina (AL,O,). silica-alumina, or carbonaceous supports that may be treated to make them acidic. Iisa farther embodiment of our invention that these sup- ports can be modified to reduce their acidity under process conditions, When used, the modifies are materials of abasic ature, ie. are providing basicity, under process conditions, thereby reducing overall substrate acidity by counteracting the acidity inberent to the support without the modifier. The modifiers may be any ofthe members of Group IA or TA of the Periogic Table ofthe Elemeats. In particular, eompounds that may be used ean be magnesium compounds oF compo- rents thereof, but calcium, sodium and potassium may be used as well, These modifiers are typically added as fully ‘oxidized material during catalyst formation, An alternative or rducing the acidity of the eatalyst support during aper- tion is by adding a small umount of base to the feed to be hydrogenated, similar to what is disclosed in WO 01/87809 {English equivalent US 20030114720 Al). ‘An alternative process for hydrogenating aldehyde con- taining streams to corresponding alcohols according to the reset iventio uses bi-phasic catalysis involving ionic lige bids as a separate liguid phase, Ione liquids are non-coord- ating solvents fora wide ange of transition mictal catalysts. They are immiscible with » number of organi solvents and hnydrocarbons, and therefore provide a suitable environment {0 carry out biphasic catalysis. Examples of suitable ionic Tiquids may be the following combiUS 7,586,017 B2 " Ow QO aaa k lesa csmayra ‘wherein emiin|*{BE,}" stands for 1-thy,3-methylimmeda- zolium tetrafluoroborate, and [NBuPy|"[BF,) stands for '-butylpyriiniam tetraflzroborate. Other examples may be 1-Butyl3-methytimmedazotium (shortened to [bmim]")tetrafiuornborat, its bexafluoraphos- phate, any of its halides (X), or is iflate (CP3COO}-, Bocoing tothe following forma Owe Be NFS Me tain] = a1 [Pel (CECOOY or x) a (on ano Tio where Xia It should be understood that the two alky] substituents oo the immedazolium cycle can be any one independently selected from methyl, ethyl, - and isopropyl, or any of the possible butyl isomers. Aso, any qustemary ammonium eat- ‘ons along with the above anions may be used. Examples are ‘of the formula [RH.N}, wherein R-methyl, ethyl, propyl ‘any ofthe butyl isomers, and may be 1 or above, and 4¥4 ‘Other anions may be [PP [SbF el Therefore a futher embodiment of this invention is 2 hydrogenation process sing. a suitable transition metal hydrogenation catalyst, sueh as Ni, Co, Cu, Cr, Ror Rh but ‘lhers are also known, dissolved in an onic Higuid which may be contained ina pumparound system enhance mixing. The hydrogenation feed is then introduced into the reactor system appropriate temperature and hydrogen paral pressure, and themixture of hydrogen containing gas and the two Tiquid is Jntocuced into a hydrogenation reactor. The product fom the reactor is then pasted on toa setlr, optionally afte cooling andr separation of any excess gas if use. Inthe setter the ‘organic hydrogenation produetypicaly forms.an upper ayer that can be withdrawn for funkier processing, and the ionic Tiguid comprising the catalyst separates as the bottom layer, ‘which may be reeyeled to the hydrogenation reactor in the reactor system, optionally after cooling, Alternatively, the reactor itself may be provided with a cooling system, In @ Jurther embodiment, the hydropenation reactor system using the ionic liquid may use a gs itor a loop reactor optionally with a cooler as part of te reactor loop, ‘Such an ionic liquid based hydrogenation reactor system ‘may be used in series with another ionic liquid based hyro- nation reactor system, of with a conventional hydrogens tion reactor containing # heterzencoss hydrogenation c Jyst. The current invention is applicable toa hydrogenatir process using hydrogenation reactors in series, wherein one ‘the hydrogenation actors is using a metal hydrogenation ‘catalyst dissolved in anionic liquid In preparation forthe hydrogenation phase ofthe process ‘ofthe present invention the product from hydroformylations preferably cooled, pasted toa decobalting ordemetalling and ‘washing unit (though the cooling ean also be performed after 0 o 18 fon what process for demetalling is selected) filtered to further remove remaining cobalt species. ‘The use of pumice filters is particularly prefered for the removal of cobalt. At this stage the water content of the hhydroformylation producti typically between 0 S.and3 w1% water, which may he dissolved andlorin the form of entrain ‘droplets. Depending onthe hydroformylation andor demet- alling proces, suc water droplets may be very small and be present asa metastable haze that can take 24 hours or more t0 lear. Typiclly sucha haze represents fro0.1 90.4 wt%OE {re water relative to the oruanie phase, more typically about (02-0.3% wi, These amounts Fre waler ae sulficiealy lows sueh that after preheating t the desired entry temperatire of the hydrogenation reaction, this fee water becomes totally issolved in he organic phase, ani no free water enters the hydrogenation reactor itself. I the hydroformylation i using cobalt catalyst, and the decobaltng is using a ase, there may also be small ainounts of base present in the organic andor ia the free water droplets or haze. The temperature ofthe pro ‘ct a this stage is ypicully between 40° C. and 80" C, more ‘ypically between 50" Cand 70°C. and especially 60°C. The products then fed (without any further water addition) tothe fist hydrogenation reactor where itis hydrogenated over a catalyst bed, preferably a cuprous chrome catalyst at a tem- perature inthe range 170 0 190° C. and a hydrogen pressnre ‘F400 60 bar, Alternatively the hydrogenation is performed ‘ver sulpided, alumina supported Co and Mo oxide eat Ist ata temperature in the range of 200 to 230° C. and a Fydrogen pressure up to 175 barg, or over a sulphided, al ‘mina supported Ni and Mo oxide eatalyst ata temperatre range of 145 to 185°C. and a hydrogen pressure upto 50 oF even as high as 125 barg, wherein the higher pressure is preferred hecaaseof suppressing side reaction, an effect that an be noticed up to 4 pressure of about 125 barg. Ifthe catalyst particle size is sufliciently large to aveid the risk of ed lifting, itis prefered thatthe produet pass in an upward direction through the first hylrogenation reactor since this results in an inereased liquid holdup in the reactor and in improved heat transfer tothe actor jacket, if present, orto the reactor shll side in case ofa shell and tube type tubular reactor. Adiabatic reactors may also he employed in the hydrogenation process. Muibed chamber reactors may also be employed, and temperature control may be eflected by injection of cooled liquid or ga, preferably reeyeled from point dowastream in the process ow. “Alternatively with low pressure hydeofoemylation, option- ally followed by aldol condensation, the Feed for hydrogena- ‘ion consists primarily of aldehydes, which may contain also ‘ carbon-carton double hond as result of the aldaisation, ‘when use, including dehydration. Other compounds present say be alcohols, furher aldehyde condensation products such as aldoxanes, acids, esters, ettrs, which are possibly cyclic, laciones, hemi-acetas,giyeols or eyelicaldols. They ‘ay be formed by side reations such as the Cannizzaro or the Tishchenko resetions during the hydroformylation or the aldolisation process. The feed for hydrogenation may also contain trices ofthe ligand that is used in the low pressure hhydroformylation process. Optionally, the feed for hylroge- ‘ation may be distilled before itis passe on tothe hydroge- ‘ation process, for removing lights andlor heavy by-products andor the Figand tees or derivatives thereo! "The aldalisation process may be catalysed, and a dite alkaline solution is typically prefered as the catalyst, more preferably 2% wt solution of sodium hydroxide or soinm carbonate. The aldolisston produet may optionally be passed fn fo a water wash step fo femave trices ofthe aldolisation catalyst