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    Decomposition

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    Səkinə Əliyeva

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    ‘US 2015007: cu») United States TT9AL cz) Patent Application Publication co) Pub. No.: US 2015/0073179 Al Xiao (54) PROCESS FOR PREPARING CYCLOHEXANOL AND CYCLOHEXANONE BY CYCLOHEXANE OXIDATION (78) Inveator: Zaosheng Xiao, Suzhou (CN) (21) Appl.Nos — 1a4381,206 (2) PCT Filed: May 17,2012 (86) PCT No, §371 (00), (2), (4) Date POTICN 2012075632 Ag. 26,2014 G0) Foreign Application Prlority Data Mar. 31,2012 (CN) Publication Classification Gl me. C07 45/83 (2006.01) core 40700 (2005.01), core 29139 (2006.01), 2012100913665 (43) Pub, Date Mar. 12, 2015 (52) US. coc €U7C 48/53 (2013.01); €07C 29159 (2013.01); €07C 407/00 2013.01) spc 568/360: S68836 on ABSTRACT A process for preparing eyclohexanol and cyclohexanone by cyclohexane oxidation, ineludes steps of: fietly processing ‘uneatlyzedonidation on eyelohexane by molecular oxygen. in such a manner that an oxidized mixture with eyelobexy lhydrogen peroxide serving as a primary product is generate: thea decomposing the eyelohexyl hydrogen peroxide to pro- dace eyelohexanol and cyclohexanone; aad then distilling to ‘obiai a eyelohexanol product and a cyclohexanone product, ‘wherein the step decomposing the eyelohexy! hydrogen per oxide mtlizes three-step decomposition process including steps of: (1) performing the homogeneous catalytic decom- position by tlizing the bis{tert-butychromate a (Q) performing the heterozencous catalytic decomposition of the sodium hydroxide alkaline aqueous solution under low alkalinity: and (3) perlorming the heterogeacous catalytic decomposition of the sodium hydroxide alkaline aqueous solution under high alkalinity Patent Application Publication Mar, 12, 2015 US 2015/0073179 AI US 2015/0073179 Al PROCESS FOR PREPARING (CYCLOHEXANOL AND CYCLOHEXANONE, BY CYCLOHEXANE OXIDATION (CROSS REFERENCE OF RELATED "APPLICATION 10001] Thisisa US. National Stage under 35 U'S.C 371 of the Intemational Application PCT!CN2012/075632, filed May 17, 2012, which claims priority under3S U.S.C. 119(a- <4) 9 CN 2012100913655, fled Mar. 31, 2012 BACKGROUND OF THE PRESENT INVENTION 0002] 1. Field oFInvention [0003] The present invention relates toa process for pre paring eyelohexanol and eyelohexanone by eyclohexane oxi ‘ation, and more particularly to a process forpreparingcyelo- hexanol and evelohexanone by eyeloherane oxidation ‘comprising a three-step decomposition process for devon posing the cyelohexyl hydrogen peroxide 0003) 2. Description of Related Ars [0005] The conventional process for the preparation of ‘eyclohexanol and evelohexanone comprises: non-catalyicly ‘oxidizing cyclohexane with molecular oxygen to obtain ‘oxidized mixture containing eyelohexyl hydroperoxide (CHHP)asamain product; decomposing the CHHP to obtain ‘eyclohexanol and cyclohexanone; and rectifying to obtain, products of the eyelobexanol and the eyelohexanone Inter nationally the art of decomposing the CHHP to obtain the ‘eyclohexanol and the eyclohexanone comprises two man ners the homogeneous eatalytie decomposition by bis(ert- butyl chromate, disclosed by French Rhodia Company: and, the nonhomogeneous catalytic decomposition by cobalt acetate in the alkaline aqueous solution of sodium hydroxide, disclosed by Dutch DSM. Both of the two manners are improved low-temperate decomposition techniques based ‘onthe conventional homogeneous catalytic oxidation process ‘and the conventional saponification decomposition process ‘aqueous solution developed in the [0006] Though having 2 molar yield up t0 949% in the ‘decomposition process, the homogeneous catalytic devom- position of CHHP by the bis(tet-butyDehromate has two Serious defets Firstly, during decomposing, the scale forma- tion, mainly the chromium adipate, blocks equipments and Pipelines. Disclosed by Rhoda, the phosphoric acid octyl ‘ester is used asthe seale inhibitor, which fil to completely solve the scale fomation, The continaous production eyele ‘only lst fr four months; washing and descaling after stall- ing the production devie are executed three times per your Secondly, the conversion rate is low, wherein the molar n= version rateis only around 92%; and around 5% of the CHHP stil remains in the decomposed materials. The remsining ‘CHIP is decomposed under the conditions of s high concen- tation of eyelofiexanol and eyelobexanone, high ait and high temperature inside the eyclohexane reeyeling columns the eyelohexanol and cyclohexanone product columns, sas manly produce acid compounds, Iikealipie acid and ‘ster compounds, mainly caprolactone; to speed up the con- ‘densationreaetion of fee radicals of the cyelohexanol andthe ‘eyelohexanone, and the esterification reaction of eyelohex= ‘anol: and to generate the high-boiling-point substances, and reduce the yield. Conventionally, the total molar yield of the ‘domestic and foreign devices thereofs oly around 80%. Mar. 12, 2015, 0007] ‘The non-homogencous eatalytie decomposition by cobalt acetate in the alkaline aquooss rolution of sodium hydroxide also has thre defects. Fry, the decomposition ‘causes the big secondary reaction, and hs a ow molar yield cof only 84%, Secondly, itis difficult ro completely separate the cyelohetane oil phase containing cyclohexanol and eyelohexanone from the alkaline aqueous phase containing the alkaline waste, The oil phase always contains a certain mount ofthe waste alkaline aqueous phase, in such a manner that the sales ofthe waste alkane ae aways formed i the rectification eolumas subsequently, which blocks ther ati columns aad the reboiles thereof, and results in the ‘continous production eyele of only six months. Thindy, the ‘decomposition bas a high alkali consumption and a lange sischarge capacity of alkali waste, A concentration of OF fon in the alkali waste mst be controlled around | mol. IF the concentration of OH— ion is over 1 mol/L, dtfculty of ‘combustion of alkaline waste is inereaseds if below I mol/L, «decomposition conversion rate is low, and pat of the eyelo- hhexy| drogen peroxide is decomposed continuously in aa cyelohexane recycling column and. eyelahexane and eyclo- hhexamone product columa in the subsequent process, and caprolactone and organie acids are mainly generated, which decreases the tot yield ofthe device and influences quality ff eyelohexanone products, Currently, the conventional industrial devices adopting the process have the total molar yield of only about 80%. [0008] Conventionally, the worldwide companies rspee- tively adopt one of the above two manners fo accomplish decomposing the CHHP at one step. The Chinese patents ‘ZL 9411039.9 and 21981127304, ied by the inventor this ‘pplication, disclose the two-step decomposition ar, At the fist step thereof, the alkalinity is lowered; the reeycling ‘amount ofthe alkaline aqueous phase is ineresed the tat ‘mixer is used, Industrial application results indicate tha, the ‘otal mola yield the device thereof really increases, bu the Separation ofthe eyelohexane oi phase from the waste alk Tineaqueous phase becomes more dilicult, The several setsof industrial production devives ofthe whole two-step decom- position art have a mola total yield of around 8236 ‘SUMMARY OF THE PRESENT INVENTION [0009] An object ofthe present invention is to provide a process for preparing eyelohexanol and eyclohexanone by cyclohexane oxidation, which has a high total yield, a long ‘continous prodiction eyee, a lw consumption and cost [0010] In order to solve the technical problems mentioned above the present invention provides a process fr preparing ‘yelohexanol and eyelobexanone by eyelobexane oxidation, ‘comprising stops of [0011] firstly processing uneatalyzed oxidation on eyclo~ hhexane by molecular oxygen, in such a manner that an oxi- ized mixture with eyelohexyl hydrogen peroxide serving as primary product is generated: [0012] then decomposing the eyclohenyl hydrogen perox- ide to produce cyclohexanol and eyelohexanone; and [0013] thea rectifying w obtain cyclohexanol product and ‘ oyclohexanone product [0014] wherein the step of decomposing the eyclohexy! hydrogen peroxide utilizes a three-step decomposition peo- cess combining a homogeneous catalytic decomposition pro- cess of bis(tert-butyl)chromate with a heterogeneous ca Iytie decomposition process of sodium hydroxide alkaline ‘aqueous soliton, comprising steps of US 2015/0073179 Al 10015] (1) performing the homogeneous catalytic decor poslion by ulliag tn bist buyichronate as cay {tote} ©) petoming he heragnonan xc dace Psy hm rai ps hen Shee ow allt where tint cans a molar concenvaton of OT sat ange of G00 oa (0017) rei enti egg ohn nok high atin, where igi MholarsmcentaicnofoH coerce OA [0018] Further, in the step (1) of decor hexyl hydrogen peroxide, while performing the homoge- ‘neous catalytic decomposition by utilizing the bis(tert-butyl) romste the catalyst adding smooat ofthe estas is ‘Kelnt to ht mbs facto of hronsum in ele snc vidtion gu iat a ange of 1228 ppm. preferably 10 om 10019] Further, while performing the homogeneous cata- lytic decomposition by utilizing the bis(tert-buty!)chromate the coulyra decomposition tempers sa range of Go°C “160°C, adsomiton posure istarangeof003 MP3 MPa and racor etence tine sata ange of 2040 mints, nherin the decomposition pressure an ‘ote presse, 10020] Preferably, while performing the homogeneous {Static dosomposon byl doors GRRE reson Preseerend iereacorreiaeatt rime, and pete 2 mits 10021] Further, performing the homogeneous catalytic Aeonpostion ug te ser tu eromat a the stale for comprise ding Vhyaony sine ‘Sphooptncic nod (oct leser er erving as scale Whi toh ict ling sou ofthe yay ethene ‘Gpbosponic acd (pac enter is equa! to ag pnt of Chroma whch an acs component of the alt. {0023} Fuhr in the ep (2) of decomposing te ep fast hymen prone elo aan sary of Cages ee Sen nat jana este esidence ine at ns of 5-7 tte, aod petebly 6 it [o0zs) Paes, the step (3) for decomposing the eel hxst hydrogen prose under high aan, the molar Tyrone oyu sou’ sane of reactors tine ata of 2) mite, an preter 8 mites [0024] In the step (1) for decomposing the cyclohexyl fogen porxie the bister-uy eons opted as the exalt for perfoming the Homogeneous calc ‘cco copa ton i aly a ange iol ilo ‘Selcetnal ane cyl fod by the “tscmpston apabs fe RD (3) performing the heterogencous catalytic dacom- replace phosphoric ester for serving itor ‘which completely solves the problem of scale formation in, ‘yclahexy! hydrogen peroxide —homogencous catalytic “decomposition by bis(trt-butyehromate, in such a manner that production cyele ofthe homogencots catalytic docom- position reaches more than a Year. Mar. 12, 2015, {0026} Iie decomposition in the sodium hydroxide alkaline aqne- ‘us solution under low alkalinity, most of the eyelabexyl bydogen peroxide which isnot decomposed yet in the step (1) is processed with decomposition again to generate the the cyclohexanone, in sucha manner that of the tion of the eyclobexy] hhydogen peroxide rac articular, a concentration ‘of sodium hydroxide of alkali waste separated inthe step 2) ‘of the decomposition is low. A molarity of OF in the alkali ‘waste may be congolled to be at range of 0.520.2 moV/L ‘Therefore, a portion of alkali water is discharged as alk \naste, so asta decrease dist barge amount of the alkali waste, redice a consumption of soditim hydroxide, and facilitate ‘uring the alkali waste to reldce environmental polltion 0027} According o rules of Brown Lancaster, the reaction rate is dreily proportional to the eoneeatration of O17, ia the step (3) of performing the heterogeneous catalytic dscom- positon inthe sodium hydroxide alkaline aqueous solution ‘under the high alkalinity, the molarity of ON-in the soxinm hydroxide solution is controlled at a range of 1.50.5 mol/L in such @ manner that decomposition reaction is cared 0} {lly and completely, decomposition conversion of the eyelo- hex ‘and the decompos ti "Thus, theeyelohexy! hydrogen peroxides prevented from decomposing into acids and esters in subsequent rectifying columns, and the eyelo- boxy! hydrogen peronide is prevented from catalyring a con-

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