Tng hp oxo sn xut butanol

MC LCA. GII THIU CHUNG2I. Lch s pht trin2II. Tng quan v butanol3II.1. n-butanol3n-butanol c cng thc phn t : C4H9OH, d chy hn du la v du diezen, nhng kh chy cc dung mi ha c khc.3n-butanol4II.2. iso-butanol5Iso-butanol : Isobutanol l hp cht hu c c cng thc (CH3)2CH-CH2OH, l cht lng khng mu, d chy, c mi c trng.5B.QU TRNH TNG HP OXO6I. S lc v qu trnh tng hp oxo (qu trnh hydroformyl ha)6II. C ch xc tc cho phn ng hydroformyl ha ca cacbonyl coban7III. Hydroformyl ha propylene10C. KT LUN16

A. GII THIU CHUNGI. Lch s pht trinQu trnh Oxo, chnh thc c gi nh hydroformylation, l tn gi chung cho mt phn ng ca mt olefin vi kh carbon monoxide v hydro cung cp cho mt aldehydesau hydro ha ca aldehyde dn n ru oxo.S pht trin t thi gian ca cng ngh oxo qu trnh ru c minh ha di y: 1938 - Oxo qu trnh pht hin bi Otto Roelen ca Ruhrchemie bng cch s dng mt cht xc tc cobalt. 1940s/1950s - Cc cng ty pht trin cc phin bn ring ca h v qu trnh oxo (v d nh, ICI, BASF, PCUK, Eastman). Nm 1960 - Shell pht trin mt qu trnh cobalt sa i, bng cch s dng cc ligand nh phosphines hoc phosphit ICI ci thin Quy trnh p cao Oxo ca n vi mt cht xc tc rhodium unliganded. Nm 1970 - Tng cng ty Union Carbide, Davy qu trnh cng ngh, v Johnson Matthey pht trin Oxo LP (sa i rhodium) qu trnh, bng cch s dng triphenylphosphine ligand (PPh3)Cc tnh nng chnh l thp hn nhiu p sut vn hnh bnh thng iso t l ttaldehyde c tch ra nh l hi ti ch kh ban u phin bn ca cc flowsheet. Nm 1980 - Rhne Poulenc / Ruhrchemie pht trin mt qu trnh hai giai on bng cch s dng sa i rhodium cht xc tc ha tan trong nc vi ligand sulfonate TPP. UCC v Davy pht trin mt bin th lng ti ch ca qu trnh Oxo LP cung cp li th hn kh ti ch i vi mt s tnh hung. BASF bt u mt qu trnh Oxo LP. Qu trnhu nhng nm 1990 - UCC v Davy. ci thin qu trnh Oxo LP c kh nng c propylene v c ci -2 ngun cp d liu, bao gm c dng butene hn hp thng mi, sn xut butanols, 2 EH v 2 PH-s dng mt sa i c hot tnh cao h thng cht xc tc rhodium v c mt "single-pass" chng trnh dng chy, m l n gin hn so vi kh sm hn hoc ti ch bin cht lng Oxo LP. Cui nhng nm 1990 - BASF bng sng ch butadien tuyn ng n n-butanol/n-butyraldehyde. Cc tnh nng chnh lu nm 2000 - Davy v Johnson Matthey giy php Johnson Matthey Oxo Cn Quy trnh ca h (trc y l Oxo ICI cao p Process) cho vic sn xut ru oxo cao hn (INA v IDA) t iso-octen v iso-noneneti thiu sn phm ph hnh thnh.II. Tng quan v butanol BUTANOL: Bao gm n-butanol, iso-butanol, tert-butanol. Trong phn tiu lun ch nghin cu qu trnh sn xut n-, iso- butanol. c bit l n-butanol, v n c rt nhiu ng dng.II.1. n-butanoln-butanol c cng thc phn t : C4H9OH, d chy hn du la v du diezen, nhng kh chy cc dung mi ha c khc.

n-butanolT nhng nm 1950, hu ht cc butanol trongHoa Kc sn xut thng mi tnhin liu ha thch.Qu trnh ph bin nht bt u vipropene(propylene), m l chy thng qua mt hydroformylationphn ng to thnhbutanal, sau c gim vihydro butanol-1 v / hoc 2 butanol.Tert butanol c ngun gc tisobutannh mt sn phm hp tcsn xutpropylen oxit.Butanol 85% c th c s dng trong xe hi c thit k cho xng du (xng du) m khng c bt k thay i ng c (khng ging nh 85% ethanol), v n cha nhiu nng lng hn cho mt khi lng hn ethanol v xng du gn nh l nhiu, do , mt chic xe s dng butanol s quay tr li mc tiu th nhin liu tng ng gi xng hn ethanol.Butanol cng c th c s dng nh mt ph gia pha trn nhin liu diesel gim pht thi b hng. Mt s tnh cht th hin s khc bit so vi etanol, butanol tr thnh mt nhin liu rt tt pha vo xng chy cho ng c.- Butanol c th vn hnh thun tin trong cc c s h tng dnh cho ch bin, lu tr du m k c vn chuyn bng ng ng.- Butanol c th trn c vi xng hoc du bt k t l no. V vy, n lm gim chi ph u t lin quan n vic lm mi li nh my hoc nhng thay i trong iu hnh.- Butanol khng ha tan hay hp th nc hoc cn bn trong ng, thng v cc dng c thit b khc.- Ch s octan v mt nng lng ca butanol gn vi xng v v th gi tr kinh t ca nhin liu ny s khng gy gim cp nh hn hp ethanol vi xng.- V p sut hi ca butanol thp hn xng nn nkhng lm tng p sut hi Reid (Reid vapor pressure- RVP) ca nhin liu. y l t tnh then cht cho xng thnh phm. T , cht lm tng ch s octan r tin hn nh butane c th c dng trong hn hp xng butanol trong ma nng.- Butanol c tnh tan thp trong nc v nc butanol lm gim thiu s r r v lan butanol vo nc ngm.Butanol thy s dng nh mtdung micho mt lot cc qu trnh ha hc v dt may, trong tng hp hu c v l mt ha cht trung gian.N cng c s dng lmsn mng hnv dung mi trong cc ng dng lp ph khc, ni n c s dng nh l mt tim n lm bay hi dung mi trong sn mi v men mi trng xung quanh-cha khi tng i chm.N tm thy s dng khc nh mt thnh phn cathy lcv cccht lng phanh. N cng c s dng nh mt c s chonc hoa, nhng ngy ca ring mnh c mi thm rt c cn.Muica butanol l trung gian ha hc, v d nhkim loi kimmui ca tert-butanol ltert-butoxides. II.2. iso-butanolIso-butanol : Isobutanol l hp cht hu c c cng thc (CH3)2CH-CH2OH, l cht lng khng mu, d chy, c mi c trng.

Iso-butanol Iso - Butanol l mt dung mi quan trng trong cng nghip sn b mt, c tnh cht ho tan tt nhiu loi nha t nhin v nha tng hp nh : nha ureas, nha phenol, ethyl cellulose, polyvinyl butyral, cyclo pentandiene, c bay hi gia ethanol v n_ butanol , to ra lp sn nc mm do do c chy v dn u tt, tng kh nng chng c cho mng sn so vi cc alcohol mch ngn hn. Lng I_Butanol dng l 5-10%. N cng oc dng lm cht pha long cho sn cellulose nitrate. Iso - Butanol l mt dung mi thch hp cho sn acid curable v sn sy nha urea, melanine hoc nha phenol. Thng dng kt hp vi glycol ether, ethanol hoc hydrocacbon mch thng.Khi thm lng nh Iso_butanol vo sn alkyd s lm gim nht ca sn v n s ci thin c v lu lng sn. Nng I_butanol thp s ngn chn to mng si cho sn c nha ho tan trong cn v tc ng c li cho sn h nc. Iso - Butanol l ng dung mi vi Xylen hoc cc dung mi thm khc. N c dng trong h dung mi cho sn c nha amini hoc hn hp nha alkyd v nha amino, dng cho sn ethyl cellulose.B.QU TRNH TNG HP OXOI. S lc v qu trnh tng hp oxo (qu trnh hydroformyl ha)Tng hp Oxo l qu trnh phn ng ca cc hp cht hu c vi mono oxytcacbon c mt tc nhn nucleophil v xc tc thch hp to ra cc sn phm nh aldehyt, axit cacboxylic, este, xetonTng hp oxo hay hydroformyl ha l phn ng ca mt olefin vi cacbon mono oxyt v hydro. Bn cht ca qu trnh l l cng hp hydro vo nhm formyl (-CHO) vo lin kt i ca olefin khi hydrocacbon ny c x l bng hn hp Co v H2 c mt xc tc Coban. Vi olefin bt i xng, phn ng s dn n s hnh thnh hai aldehyt v c th oxy ha tip to ru tng ng. y l mt trong nhng qu trnh xc tc ng th quan trng nht hin nay vi khong nm triu tn sn phm oxo c sn xut hng nm.Hydroformyl ha l qu trnh xc tc ng th s dng phc phi tr ca coban vi olefin. Cht u to ra xc tc l mui coban c chuyn ha ngay ti ch, vi s c mt ca CO v hydro to thnh cc dng hot tnh coban tetracacbonyl hydrit cn bng cn bng vi coban tricacbonyl hydrit. Dng coban tricacbonyl hydrit c v tr phi tr trng, c kh nng to phc vi olefin. Olefin tham gia chuyn ha ha hc vi dng hp cht ny v to phn hai ng phn aldehyt, vi t l dng mch thng ln gp 4 ln mch nhnh. Trong trng hp nguyn liu l propylene, hai sn phm thu c l butyraldehyt v isobutylaldehyt.II. C ch xc tc cho phn ng hydroformyl ha ca cacbonyl cobanCc phn ng chnh nh sau:Olefin + CO + H2 andehit ruT l mch thng nhiu hn mch nhnh.p sut CO cn c duy tr mc cao m bo bn ca xc tc.Xc tc: thng l Co2(CO)8, HCo(Co)4, HRh(Co)4. 1/2Co2(CO)8 HCo(CO)4RCHO + H2 + olefin R-CO-Co(CO)4 R-Co(CO)4 Trong giai on u tin, dicoban octacacbonyl hoc cc mui coban khc c chun ha thnh tetra cacbonyl hydrit coban, l cht mang hot tnh xc tc.Co2(CO)8 + H2 2HCo(CO)42Co(OOC-R)2 + 3 H2 + 8 CO 2 HCo(CO)4 + 4RCOOHDng tetracacbonylhydrit coban trng thi cn bng vi tricacbonyl hydrit coban.HCo(CO)4 HCo(CO)3 + COPhc cha bo ha v tr phi tr ny to thnh phc vi olefin, dng hp cht trong mi trng CO s bin i thnh alkyl tetracacbonyl coban cha ln kt . y l giai on quyt nh phn b ng phn ca sn phm v c hai dng phc mch thng v mch nhnh u c hnh thnh. H H C R-CH=Ch2 + HCo(CO)3 Co(CO)3 C H R H H H C 2 Co(CO)3 + 2CO R-CH2-CH2-Co(CO)4 + R-CH-Co(CO)4 C H CH3 R HBc tip theo l s hnh thnh ca phc axyl, hay thng c bit n nh l s nh nhm CO. Tuy nhin, trong thc t, n l phn ng di chuyn nhm alkyl nh c chng minh bng th nghim nh du ng v. CO O CO R C R Co CO CO Co CO CO COAxyltricacbonyl coban c to thnh ban u c th phn ng vi CO to thnh axyltracacbonyl hydrit coban tng i bn hoc phn ng vi hydro to ra aldehyt v tricacbonyl hydrit coban, hp cht khi u cho mt chu trnh xc tc mi. Th nghim t lng ch ra rng axyltetracacbonyl coban c th phn ng vi HCo(CO)4 to thnh aldehyt v actacacbonyl dicoban. Tuy nhin,gn y, ngi ta ch ra rng, di iu kin p sut v nhit cao ca cc qu trnh cng nghip, phn ng ca phc axyl vi hydro c vai tr tri hn trong qu trnh hnh thnh aldehyt. O O R C +CO R - C - Co(CO)4 CO -CO + HCo(CO)4 Co O CO R - C - H + Co2(CO)8 CO + H2 H-HR CO O C Co R C H + HCo(CO)3 O CO COS hnh thnh ca cc sn phm ph c th c gii thch xy ra cng vi cc phn ng trn. Qu trnh hydro ha olefin xy ra do phn ng ca phc alkyl vi hydro:R-Co(CO)4 + H2 R-H + HCo(CO)4Mt phn ng ph quan trng khc l qu trnh hydro ha axetaldehyt to thnh ru tng ng. Trong mt s qu trnh cng nghip, phn ng ph ny c s dungjmootj cch thn trng to ra butanol t propylene qua butyraldehyt m khng cn phn lp aldehyt. O HCo(CO)4 R-C + H2 R-CH2-OH HC ch phn ng trn cc xc tc khc cng tng t nh c ch ca Heck v Breslow. Sn phm mch thng c hnh thnh tri hn c th c gii thch nh s kt hp ca cc hiu ng in t v khng gian. Hiu ng khng gian c th c nhn thy d dng nh quan st s bin i t phc thnh phc alkyl, khi mt ligan phosphin c mt trong phc. R R R R CH = CH2 P R R H Co R CH2 = CH P CO CO H - Co R CO CO - PR3HRh(CO)(PR3)3 HRh(CO)(PR3)2 + PR3 + H2 - RCHO +PR3 + CH3-CH=CH2 O CH3 R - C - Rh(CO)(PR3)2 CH=CH2 PR3 + CO H - Rh R Rh(CO)(PR3)2 CO PR3III. Hydroformyl ha propyleneTng hp oxo vi nguyn liu propylene din ra cc iu kin sau: nhit 110 1800C, p sut 20 35 MPa, t l mol CO/H2 t 1/1 n 1/1.2, thi gian lu 1 5 pht, xc tc 0,2 1 % KL so vi propylene. Xc tc coban vn l loi s dng rng ri nht trong cng nghip cho qu trnh tng hp ny (BASF,ICI,PCUK, v Ruhrchemie). V dng aldehyt mch thng c th trng tiu th ln hn ng phn iso, cc iu kin cng ngh c iu chnh tng t l n-/iso-. iu ny phn no c th t c bng cch h nhit phn ng, tng p sut CO hoc bin tnh xc tc. tng t l n-/iso ln 9/1, hng shell s dng xc tc coban hydro-cacbonyl th bng photphin (HCo(CO)3P(n-C4H9)3). Phn ng c thc hin nhit 180 200oC v p sut 5 10 MPa. Tuy nhin, hot tnh ca h xc tc ny cn thp v c xu hng to iu kin thun li cho cc phn ng ph hydro ha olefin v aldehyt hn l xc tc thng thng.Coban cn c th c thay th bng rodi m hot tnh xc tc ca n ln hn 100 10000 ln, nhng do gi thnh cao nn phi tun hon li ton b xc tc. Tuy nhin qu trnh tng i kh thc hin. Hn na, t l n-/iso- khng cao v gim t 4/1 i vi coban khng bin tnh xung 1/1 vi loi xc tc ny. Tuy nhin, nh bin tnh cacbonyl rodi bng triphenylphosphin, hng Union Carbide thnh cng trong vic pht trin h xc tc ny v to ra t l sn phm mch thng ln hn nhiu (n-/iso- = 10/1) trong iu kin phn ng rt mm (nhit 60 120oC, p sut 0,1 5 MPa).Trong cng ngh Ruhchemie, propylene, xc tc tun hon v xc tc mi c a cng mt lc vi kh tng hp (H2 + CO) vo thit b phn ng. Thit b ny l dng a tng c lp v c lt bn trong bng thp hp kim cao, c trang b h thng khuy trn hiu qu v dng tch nhit sinh ra do phn ng(H0298 = -125 kJ/mol). Nhit ny c tn dng sn xut hi p sut thp. Dng sn phm c chuyn n thit b tch coban, ti y coban lng xung do x nhanh v ct nh. Kim loi c phn tch ra nh ly tm, h xc tc c ti sinh, ri tun hon tr li thit b phn ng. Dng sn phm khng cn ln xc tc cha 80 85%KL n- v iso- aldehyt vi t l 4/1, cc ru tng ng, butyl format v rt nhiu hp cht to thnh t cc phn ng ph nh ngng t aldol, axetal ha, hydro ha, c chuyn ti dy thp chng u tin tch cc cu t nng. Hn hp cc n- v iso- aldehyt c hydro ha thnh cc ru tng ng. Qu trnh tin hnh 5 10 MPa, 150 200oC, vi s c mt xc tc ng hoc niken. Sn phm hydro ha tip tc c chuyn ti dy thp chng th hai tch cc cu t nh v hai ru. tng cng hiu sut ru, cc sn phm nng c a vo mt thit b x l cracking hydro ha c bit.Mc d c nhng ci thin v t l n-/iso-, ng sn phm isobutyraldehyt c rt t ng dng vn gy nhng tr ngi v kinh t cho qu trnh. Do , Ruhrchemie ngh mt cng ngh c c phn xng cracking xc tc isobutyl-raldehyt v tun hon cc sn phm cracking (propylene, CO v H2).Nu hydro c thay th bng hi, c th thu c mt hn hp gm ch yu l cc butanol. y l cng ngh ca BASF (tng hp Reppe) hin ang c s dng ti mt nh my Nht Bn. N to ra dng sn phm c cha 88% n-butanol v 12% isobutanol. Phn ng chnh lin quan, l: CH3-CH=CH2 + 3 CO + 2 H2O C4H9OH + 2 CO2 H0298 = -240 kJ/mol H thng lm vic 100oC; 1,5 MPa, c mt xc tc pentacacbonyl st, butyl-pyrolidon v nc. *Cng ngh qu trnh tng hp OXO sn xut BUTANOL iu kin cng ngh Nhit phn ng 150oC, p sut 300 at, t l mol CO/H2 t 1/1 n 1/1,2, thi gian lu 15 pht, xc tc Coban chim t 0,2 1 % KL so vi propylene.Trong cng ngh Rhrchemie, nguyn liu bao gm: Propylen lng, kh tng hp, xc tc mi v xc tc tun hon c a cng mt lc vo thit b phn ng. Thit b ny l thit b a tng c lp v c lt bn trong bng thp hp kim cao, c trang b h thng khuy trn hiu qu v dng tch nhit do phn ng sinh ra. Nhit sinh ra do phn ng c tn dng sn xut hi nc p sut thp. Dng sn phm c lm lnh, ri chuyn n thit b x nhanh, ti nh thp kh d: CO, H2, kh propylenc tch ra. Hn hp sn phm y thit b x nhanh c a n thit b gia nhit, gia nhit n nhit cn thit. Sau c a n thit b chng ct nh, nhit c cung cp nh dng hi nc thi t di ln. nh thp thu c ch yu l cc kh CO, H2, propylene d, hi nc, v ln mt t cac sn phm lng nh. Hn hp kh tip tc c a n thit b gim p thu hi sn phm lng, ri a n thit b ti sinh xc tc. Ti y thit b chng ct nh thu c hn hp cc sn phm v xc tc. c a n thit b ti sinh xc tc. Xc tc c phn tch nh ly tm, h xc tc c ti sinh v xc tc mi c b sung, ri tun hon li thit b phn ng. Dng sn phm khng cn ln xc tc cha 80 85%KL n- v iso-aldehyt vi t l 4/1, cc ru tng ng, butyl fromat v rt nhiu hp cht to thnh t cc phn ng ph nh ngng t andol, axetal ha, hydro ha, c chuyn n thit b chng tch cu t nng. Ti nh thp thu c ch yu l n- v iso- butanal, sau c lm lnh, qua thng hi lu, mt phn c bm tr li hi lu. Sn phm nh tip tc c ua qua thit b hydro ha t trn xung. y thit b tch aldehyt ta thu c ch yu l cc phm nng ca cc qu trnh ngng t andol, axetal ha v ln t mt phn butanal. Sn phm nng tip tc c a qua thit b lng, phn y l cc sn phm nng c a ra ngoi v phn trn l sn phm nh c a qua thit b hydro ha. Cng ngh Ruhrchemie tng hp Oxo sn xut cc ru butanolHydro c a qua thit thit b gim p cng vi butanal v mt phn hydro d tun hon c a vo thit b huydro ha. Hn hp cc n- v iso- aldehyt c hydro ha thnh cc ru tng ng. Qu trnh c tin hnh 5 10 MPa, 150 200oC, vi s c mt ca xc tc ng hoc niken.Hn hp sn phm c a qua thit b lm lnh sau a qua thit b x kh nhanh tch kh d hydro, hi nc c thi ra ngoi t nh thp .Hn hp sn phm lng a qua thit b tch sn phm nh,ti nh thp tch cc kh nh cn ln li:hydro,hi nc.Sn phm y ca thp tch sn phm nh c lm lnh ri a qua thit b tch iso-butanol.Iso-butanol thu c ti nh thp .Sn phm y ca thit b tch iso-butanol c a qua thit b tch n-butanol.n-butanol thu c ti nh thp cn y thp l cc sn phm nng:2-etylhexanol...u im: S cng ngh n gin, d vn hnh. c ng nhiu trong cng nghip. Sn phm thu c t yu cu.Nhc im:T l n-/iso- butanol cha cao khong 70% Nhiu sn phm ph to thnh trong qu trnh phn ng nh hng n hiu sut ca qu trnh. Xc tc v sn phm u l pha lng, do qu trnh tch xc tc rt kh.

C. KT LUN Vit Nam,ngnh cng nghip du kh ngy cng pht trin to ra ngun nguyn liu di do cho cc ngnh cng nghip khc, c bit l ngnh cng nghip tng hp hu c, cng nh nghnh cng nghip tng hp cc hp cht trung gian, t tng hp c v s cc sn phm nhm phc v cho x hi. Trong cng ngh tng hp oxo sn xut butanol gp phn khng nh, sn xut ra mt lng butanol nhm p ng c nhu cu x hi. c bit pha vo xng lm nhin liu cho ng c. Cng ngh ny n gin, d vn hnh, nhng t hiu sut cao. Nn quy trnh cng ngh ny c s dng nhiu ni trn th gii nn vic vn hnh cng nh khc phc s c d dng v c c kinh nghim ca ngi i trc.Chng em mong rng thng qua bi vit ny mi ngi s c ci nhn khch quan hn trong cng nghip nc nh ni chung v ngnh cng nghip tng hp hu c ni ring. Do hn hp v kin thc cng nh cha c nhiu kinh nghim nn bi vit khng khi gp phi nhng thiu st. Chng em mong c s gp ca c, c nhng hiu bit thm, cng nh kinh nghim. Chng em xin chn thnh cm n.

TI LIU THAM KHO1.http://en.wikipedia.org/wiki/Butanol2. Cng ngh tng hp hu c ha du Phm Thanh Huyn, Nguyn Hng Lin

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