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    13 views8 pages

    US20100137645A1

    Uploaded by

    Zhala

    Copyright:

    © All Rights Reserved
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    cu») United States cz) Patent Application Publication — co) Pub. No.: US 2010/0137645 Al oy (76) en (@y (66) Toth PROCESS FOR DECOMPOSING CYCLOHEXYLIYDROPERONIDE Imre Toth, Geleen (NL) Comespondence Address NIXON & VANDE 901 NORTH GI YE, PC EBE ROAD, 11TH FLOOR ARLINGTON, VA 22203 (US) Appl No, PCT Filed: PCTNo, $371 (0M), (2), Date: 117793,726 Dee. 16, 2008, PT#EPOS/L3822 Feb. 13, 2008 ‘US 2010013764541 (43) Pub, Date Jun. 3, 2010 G0) Foreign Application Priority Data Dee. 22,2004 (EP) 040784902 ication Classification G1) Inte Core 4983 2006.01) (52) US.CL s0ni342 on ABSTRACT The present invention relates to-a process for decomposing cyelohexylhyueoperoxide into eyelohexanone, said process comprising mixing an organic’ feed solution comprising cyelohexylhydroperoxide with an aqueous base soltion in the absence ofa transition metal catalyst resulting ia 8 mix- ture comprising () an aqueous phase and (i) an orgie phase comprising eyelohexanone and eyelohexanol. US 2010/0137645 Al PROCESS FOR DECOMPOSING. (CYCLOHEXYLHYDROPEROXIDE 10001} The present iveation relates ta process for decomposing eyelohexylhydroperoxide inte eyelohexanone. 10002] | Cyclobiexanone may be used for the production of ‘caprolactam and/or adipic acid, both nylon intermediates. For ‘caprolactam and adipic aid production, « known route for ‘eyclohexanone praduction involves oxidation ofeyelobexane ‘o yield a mixture containing cyelohexane, eyciohexanone, ‘yclobexanol, eyclohexylhydroperoxide and by-products, For the production of caprolactam, eyelohexanone is the ‘desired intermediate Por this purpose, eyelohexylhydroper- ‘oxide can fist be converted to eyelohexanone and cyelohex= ‘anol and he eyelobexanol ean be converted i evelohexanone ina separate step. 10003] Document EP-A:092867 describes a_process Wherein an organic feed solution comprising eyelohexylby- “dnoperonide is treated witha transition metal salt ike cobalt sulphate or chromium nite in the presence ofa aueous solution of an alkali metal hydroxide at « temperature of ‘We 15° C. to obtain a mixture containing an onganic phase ‘comprising cyclohexanone and eyclohexanol and an aghcous phase, EP=A.09,2867 deseribes that effecting svc a tau tion metal catalyzed, two-phase decomposition at tempera- tures of 70-115° C. resuls in improved selectivity to eyelo- hhexanone and cyclohexanol compared with effeting such ‘decomposition at higher temperatures. In such low tempera ture, two-phase decomposition processes, the molar rato of ‘eyclohexanone formed to eyelohexanol formed inthe organic Phase is usually at most 15. 0004} It has now sumprisingly been found thatthe molar ratio of cyclohexanone to cyclohexanol obtained in the ‘decomposition reaction of eyclobexylhydroperoxide (herein alter referred to as molar ratio of eyelohexanone formed (0 ‘eyclohexanol formed) i markesly increased by elfecting the ‘decomposition of eyelohexyliydroperoxide in the presence ‘ofan aqueous base solution, but inthe absence ofa transition metal catalyst. An increased molar ratio of cyclohexanone Tormed to cyclohexanol formed is advantageous in ease for ‘example caprolactam is theultimate desired product cause lor the production of caprolactam cyclohexanone is the ‘desired intermediate. In case for example caprolactam is the ultimate desired product, an increased molar ratio of eyelo- hhexanone formed to eyclohexanol formed is advantageous because less eyclobexanol needs tobe isolated from the mix- ture obtained after decomposition and less cyclohexanol needs to be converted t cyclohexanone. Thus the cyelohex- none recovery and purifiation ean be carried out easier 10005] Accordingly, the invention provides a process for “decomposing eyelohexylhydroperoxide into eyelohexanone, said process comprising, mixing. an organic feed solution ‘comprising eyclobexyihydroperoxide with an aqueous base solution in heabsence ofa transition metal eatayst resulting jn a mixture comprising (i) an aqueous phase and (i) an ‘organic phase comprising eyelohexanone and eyclobexana [0006] thas surprisingly been found tha withthe process ‘of the invention a mola ratio of eyelohexanone formed 10 ‘eyclohexanol formed in the organic phase comprising eelo- hhexanone and eyclobexanol higher than 2, even a mola ratio higher than 2.5 or even a molar esto higher than 3 can be ‘obtained. As used herein, the molar ratio of eyelohexanone Jun. 3, 2010 ormed to cyclohexanol formed in the omanie phase is efined 28 Morea semtilenat rman WHEN. Dayne ormee-voncentration of eyclohexanone in the organic phase ‘minis concentration of eyclohexanone in the organi food soliton td, qa-Boncentration ofeyclohexanol nth ‘organi phase mis concentration of cyclohexanol ia the ‘onganie feed solution, All concentrations ae in mol per kg. [0007] Therefore the invention Ture provides a process Tor decomposing cyclohexylhydroperoxide into eyelolex- ‘anone, suid process comprising mixing an onze feed solt- ‘ion comprising eyclohexylhydroperoxide with an aqueous base solution in the absence of & transition metal catalyst resulting ina mixture containing (i) an aqueous phase and (i ‘an organic phase comprising cyclohexanone and eyelohex- Anal, wherein the molar ratio of cyclohexanone foemed 19 cyclohexanol formed in the onganie phase is higher than 2 Preferably, this molar rao js higher than 25 and even more preferably its higher han 3. [0008] _\ further advantage ofthe process aeconding to the invention is tht, compared with a process as for example described in EP-A-092867 a higher selectivity af the decom- position ofeyelohexylhydroperoxide ino eyclohexanoneand eyelohexanol ean be obiained. It has surprisingly been found that this hh seletivity can even be maintained at increased ‘temperatures, This was unexpected sinee the pri art relating to cYelohexylhydroperoxide decomposition inthe presence fof an aqueous base solution and a transition metal catalyst teaches that ineressed temperature results in decreased selec tivity. Anadditional advantage ofthe process according tothe ‘vention is that the base consumption ean be reduced, {009} In the process ofthe present invention, decompos- ing cyelobexylhydroperoxide present in the omzanic feed solution is eflected inthe absence ofa transition metal et Ist. This is done by mixing the organi feed solution com- prising eyclohexylhydroperoxide with the aqueous basesoh- ‘ion in the absence of transition metal catalyst. AS used herein, effecting the decomposition in the abseace ofa tran- sition metal catalyst implies thot no transition metal com- oui is prposely ade othe mixtre ta be decompose in an amount that notably catalyzes the decomposition. Alter- ‘atively transition metal catalyst presen in the organic feed solution is removed and/or deactivated before the onganie Teed solution enters the decomposition section to such aa extent that there is no catalytic activity inthe decomposition, Examples of transition metal compounds that notably cataly- ses the decomposition, even when present at small eoncen- ‘watons, are Cr salts and especially Co salts, Therefore, the process of the present insention especially elatesto effecting the decomposition without purposely adding a Co andlor Cr catalyst to the process of decomposing cyclohexylhydroper- oxide, In the framework of this invention, the entering of transition metal eompounds ino the mixture that is subjected {0 decomposition, due to corrosion of the reactor wall, is, however, not considered as purposely adding a transition ‘etal compound tothe mixture that is subjected to decom- position, [0010] “The eyelobexyhydroperoxide, which is decom- posed in the process of the invention, can be obtained with various known processes, [0011] Preferably, preparing the eyelohexylhyelroperoxide involves oxidizing eyelohexane with an oxygen containing {2 in the absence of substances promoting the decompo: tion of the eyelohexylhydroperoxide formed (hereinafter referred to as uncalalyzed oxidation) resulting inan oxidation reaction mixture comprising eyclohexane, cyclohexanone, US 2010/0137645 Al ‘xclohexano,eveloheryiydroperoxie, acid, ester, low boiling compounds, and high boiling compounds, With Low boiling compounds is mean organic compound heving @ boiling point lower thin cyclohexanone and bighee than ‘eyelobevane, Examples are butanol, Lpentanal,1-exan T-pentaol and epoxy-cyelobexane. With hgh bing om= pounds is meant organi compounds having w oiling pot Higher than eyelohexano. Examples are 2eycloexylidene ‘yelobexanone, -hexylidene cyclohexanone and 2-cycloe hexen-I-yeyelobexanone. The oxidation usally takes place in the liquid phase. As oxyget-contsining gas use an be mace for instanceof pure oxygen, ar rie or poorin oxygen, ‘oroxygen mined with aren or anober ine gs, Suitable ‘oxidation temperatures are between 120 and 200" C. Prefer ably an oxidtion temperature between 140 and 190° C. fs used Compared with the proces as for example described in EP.A.92867 the proces aoconlng tothe vention has the vantage that the ference between the oxidation tempera- ture andthe decomposition temperature can be decreed This is advantageous with espect to energy consumption as for example the degree of cooling of the reaction mite Jeaving the oxidation reactor before allowing the eyclohoxy~ lhydroperoide o decompone can be reduced. The oxidation reaction sully carried out fr minvts o 24 hours. The pressure is usally between 0.1 and. $ MPa, preferbly betcen 0.2 and 25 MPa. Uncotalyzed eyelooxane oxida tin s preferred to catalyzed yclolexane oxidation because uneatalyzed eyelohexanconidation sults ia higher yells of ‘xcloeiiydroperoxide and Because there is 0 ned to Separate andor deactivate the transition metal exidation eat Iyst before decomposing the eyelobexyliyUrperoxde with the process according tothe invention. Asa rue the ection mist obtained in sch uneatalyzed eyelohexane oxidation ‘comprises 2 weight percentage of eyclobexylhydroperie that sat least comparable tothe weiaht percentages of eyelo- hexanope and eyelohexano. Oe, tneamount of exelhexy= Ihydroporoxie in the reaction mixture obwined in such uneatalyzed eyelobexane oxidation i a least two Sines as Jarge asthe amount of eylohexanove and eyelobexanol. 10012] Opvionlls, prior subjecting te eyeloexylydo- peroxide, presen! ia roction mixture obtained by oxidation ‘of eysfoexane with an oxygen containing gs, dacom- positon process acorn te inventon the reaction mix- ture aban by oxidation of eyloexane with an oxyeen- ‘onisining as can be concentrated by separating, pelerbly by flashing or distil ll or preferably part ofthe eyelo- hexane. Optionally. price wo decomposing eyelaxylivdo- peroxide, obiained by oxidation of eelohexane, according to the invention and prelenbly aller said concentrating Gf applied) the oxiatonreocton mixture maybe sted with water or preferably with an qucou laine solution, or ‘example deseribed in EP-A-4105, forthe purpose of neteal- $2ing cid formal inthe oxidation. When applying sch 9 neutralisation, the total hase consumption ea be reduced by ‘applying in the neutralisation atleast apart of the aqueous phase that canbe separated of from the reaction mixture afer the devomposing 10013], The eyelohexylhydroperoxide to be decomposed acconding othe invention my be present in any onganie feed Solution, The eyetohexyIhyoperDxie concentration inthe ‘organic feed solution i not ental. The eelobexy yop ‘eroxide may for example be present in an onan eed sot tion comprising betwen 0. an 20 we cyclohexyl do peroxide (relative tothe onuanie feed solution), In ease the Jun. 3, 2010 process according othe invention is applied for decomp jclohexyliydroperonide obtained By oxidizing eyelobes- fe, the organic feed solution comprising eyelaexylidro- peroxide usually also comprises otler ‘compound, for example (1)eyeloexane andor @ eyelohexanone andor 3) celohexanl The sun concentration of eyelobexanone and eelohexanol inthe organ feed soliton ot rica and is fr insiance between O and 20 wt (lative to the foal onic fed solution) [0014] thas further been found that in particular the tem- Pate at which the mixing feet the pH of the aque fm phase, the volume rao of the agusots phase othe npc phase andthe concentration ofearboxy ead sas in the aqueous base solution may father inuenee the molar Fao of yclohexanone forme to eyeloienanol ferme inthe mune phase {0015} Preferably, sid mixing is efected at temperature her than 70°C, more preerbly higher than 80°C more preferably higher than 90° C. and even mone preferably Siber than 100° C. lereasing the Temperature seus in inereave ofthe decomposition reaction velocity and hence lower residence times, It his surprisingly boon found tht Increasing the temperature doesnot significant impair the ‘molar ofeyelobexanonefomedieyctohexanl formed inthe organic phase and the selectivity of he decomposition of eyelohexyydroperoxie into eyelchexanone and eylo- hexanal. In ease the cyelobexyliydoperoxe fo be doco ined wil the process ofthe ivention is obtained by oxiiz- Ig cyclohexane, effecting, said. mixing at inrensd temperatures isin parila advantages, in patcular with respect to reduction of energy consumplion, because a Jneteased decomposition temperatures the degree of cooling ofthe reaction mixture leaving the oxidation reactor before atlowing the eylohexylhydoperoide to decompose can be reiced. Preferably, sid mixing is effected ata tempersture lower than 17 C. more preferably lower than 160" Cand even more pefraly lower than 150" Ct hts been found ‘hat effecting the decomposing st a temperature higher than 160" C. may reclt inw decrease ofthe mola ati of yclo- hexanone formed to eyeloexanol formed in the organic pine and may rst i a decrease ofthe teletvty ofthe {composition of eyeehexythydroperonide into eyelohen- fmone ad eytobexanol. This decrease may ever Be ore pronounced when the mixing is effect at 8 temperture her than 170°C: [0016] The mixing is preferably effected with such a quan- {ity of aqueous base solution that the pH of aqueous phase is Iigr tan 9, measured at 25° C. The pl ofthe aqucus phase is preferably higher than 10, more preferably higher than 11, more preferably higher than 12. more preferably higher than 13 and even more preferably higher than 13.3, ‘meamined at 25° C. By increasing the pH ofthe aqucus Phrse, the decomposition reaction velocity is increased. By Increasing the pif ofthe aqueots phase, the molar rai of cyeloexanoneformed%o cyelohexanlfomedin the organic phase may be furlierinreased. AGiGonaly, an intend PHtofthe aqueous phase may resuitinan iene selectivity Of the decomposition reaction wo eylohexanone and eyelo- hexanol.On the other hand an increased pH ofthe uous riuve results in an increas Base consumption In ease the {loherylhydroperoxie to be decomposed wit the process ofthe invention fs obtained by oxidizing cyclohexane, the rising is advantageously effected a high temperate and relatively high pi of the aqueous pase, becuse this results US 2010/0137645 Al ‘na high selectivity to eyelohexanone and eyelobexanol and ‘thigh molar ratio of cyclohexanone formed to cyelohex- ‘anol formed and a the same time in decreased energy con: sumption, 10017] In the process ofthe invention, the volume ratio of the aqueous phase to the organie phase is preferably higher than 0.02, more preferably higher than 0.1 and even more preferably higherthan0.15. Increasing the volume ratio ofthe aqueous phase to the organic phase results in increased ‘decomposition eacton velocity. Ithas also been found that increasing the volume ratio of the aqueous phase to the ‘organic pliase may result ia a increased selectivity of the ‘decomposition of eyclohexyihydroperoxide into eyelohex= ‘anone and eyelobexanol and in an increased molar ratio of ‘eyelohexanone formed to eyelobexano formed inthe organic phase, Tere is no specific upper limit forthe volume ratio of the agueos phase to the organie phase. From an economical point of view, however, the volume rato of the aqueous phase fo the organic phase is preferably lower than 5 [0018] -Thopressuee, at which mixing the organic feed solu- tion comprising cyelohexylhydmperoxide withthe aqueous base solution is effected, is not eritical and may be Varied ‘within wide anges. The pressure employed is for example between 0.1 and 5 MPa and advantageously depends on the temperature used 10019] The process of the invention involves mixing the ‘organic feed solution comprising eyclobexyliydroperoxide with the agueous hase solution. ‘The aqueous base solution may be added to the onan feed solution in any suitable manner. Mixing the organic feed solution withthe aqueous base solution muy be elected by any’ suitable method, for ‘example by using @ packed! column, a flow or Fine mixer, 3 pump, a static mixer, an agitated vessel or combinations thereat: Mixing may also involve injcting the organic feed Solution into the aqueous base solution, or vie vers, [0020] | Aswscd herein, anaqueous hase solution refers oa aqueous Solution comprising dissolved bases). Preferably, the base isan cath alkali metal hydroxide andor one of more salts of an earth alkali metal or the base is an alkali metal hydroxide and/or one or more salts of an alkali metal. Hence preferably, the aqueous base solution is an aqueous solution ‘comprising an earth alkali metal hydroxide andlor one oF ‘more salts of an earth alkali metal oF the aquoous base solu- tion is an aqueous solution comprising an alkali metal hydroxide and/or one of more salts ofan alkali metal, More preferably, the aqueous base solution is an aqueous solution ‘comprising an kali metal hydroxide and/or oneormore sats fof an alkali metal. Suitable (earth) alkali metal salts are (earth) alkali metal phosphates, (earth) alkali metal earbon- tes and (carth) alkali metal bicarbonates. Preferred (earth) alkali metal salts are (cath) alkali metal carbonates and (arth) alkali metal hicarbonates. A prefered earth alkali ‘tals magnesium. The alkali metal is preferably potassinm ‘or sodium, more preferably sodium. Ina prefered embodi- rent, the aqueous base solution further comprises carboxylic ids alts It fs been Found thatthe presence ofearboxslic salts results in an increased reaetion velocity for decom posing cyelohexythydroperoxide into the desired products ‘gyelohexanone and eyelohexanol. [thas further been found that the presence of carboxylic aeid salts may result in an jnereased molar ratio ofeyclohexanone formed t eyclohex- ‘anol formed in the organic phase. Salts of mono- and poly ‘carboxylic acid in which the carboxylic eid moc prefer- ably comprises 1-24 C-atoms are suitable, more preferably Jun. 3, 2010 tne carboxylic aid moiety. comprises I-12 C- Examples of suitable carboxylic aids in the sll are fo aeid, dee acid, propionie acd, butyric aid, apie acid, Ihexanoie oi, heplani acid, penanoic acid, propane car boxylic acid, gre acid, hexane dicarhoxylic acid, hoptane

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