Tng hp oxo sn xut butanol

MC LC
A. GII THIU CHUNG ....................................................................................................................... 2 I. Lch s pht trin ............................................................................................................................. 2 II. Tng quan v butanol ..................................................................................................................... 3 II.1. n-butanol ................................................................................................................................ 3 n-butanol c cng thc phn t : C4H9OH, d chy hn du la v du diezen, nhng kh chy cc dung mi ha c khc. .............................................................................................................. 3 n-butanol ......................................................................................................................................... 4 II.2. iso-butanol .............................................................................................................................. 5 Iso-butanol : Isobutanol l hp cht hu c c cng thc (CH3)2CH-CH2OH, l cht lng khng mu, d chy, c mi c trng. .................................................................................................... 5 B.QU TRNH TNG HP OXO ........................................................................................................ 6 I. S lc v qu trnh tng hp oxo (qu trnh hydroformyl ha)..................................................... 6 II. C ch xc tc cho phn ng hydroformyl ha ca cacbonyl coban ............................................. 7 III. Hydroformyl ha propylene ........................................................................................................ 10 C. KT LUN .............................................................................................................................. 16

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A. GII THIU CHUNG

I. Lch s pht trin
Qu 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 aldehyde sau 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 tt aldehyde c tch ra nh l hi ti ch kh ban u phin bn ca cc flowsheet.

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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.
o

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 trnh u 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 nbutanol/n-butyraldehyde. Cc tnh nng chnh l u 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 isononene ti 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-butanol n-butanol c cng thc phn t : C4H9OH, d chy hn du la v du diezen, nhng kh chy cc dung mi ha c khc.

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n-butanol T nhng nm 1950, hu ht cc butanol trong Hoa K c sn xut thng mi t nhin liu ha thch . Qu trnh ph bin nht bt u vi propene (propylene), m l chy thng qua mt hydroformylation phn ng to thnh butanal , sau c gim vi hydro butanol-1 v / hoc 2 butanol. Tert butanol c ngun gc t isobutan nh mt sn phm hp tc sn 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.

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- 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 mt dung mi cho 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 lm sn mng hn v 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 ca thy lc v cc cht lng phanh . N cng c s dng nh mt c s cho nc hoa , nhng ngy ca ring mnh c mi thm rt c cn. Mui ca butanol l trung gian ha hc, v d nh kim loi kim mui ca tertbutanol l tert-butoxides . II.2. iso-butanol Iso-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

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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 OXO

I. 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, xeton Tng 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

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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 coban

Cc phn ng chnh nh sau: Olefin + CO + H2 andehit ru T 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 RCHO + H2 HCo(CO)4 + 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)4

2Co(OOC-R)2 + 3 H2 + 8 CO 2 HCo(CO)4 + 4RCOOH

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Dng tetracacbonylhydrit coban trng thi cn bng vi tricacbonyl hydrit coban. HCo(CO)4 HCo(CO)3 + CO Phc 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 C R-CH=Ch2 + HCo(CO)3 H

C R H

Co(CO)3 H

H C 2 C R

Co(CO)3 + H H

2CO

R-CH2-CH2-Co(CO)4 + R-CH-Co(CO)4 CH3

Bc 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 CO R Co CO CO CO Co CO R C CO O

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Axyltricacbonyl 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 R C CO Co CO CO + H2 H-H R C O CO S 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 Co CO CO O R C H + HCo(CO)3 +CO -CO O R - C - H + Co2(CO)8 O R - C - Co(CO)4 + HCo(CO)4

R-H + HCo(CO)4

Mt 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

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s dungjmootj cch thn trng to ra butanol t propylene qua butyraldehyt m khng cn phn lp aldehyt. O R-C + H2 H C 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 CH = CH2 H Co CO CO R P R R R CH2 = CH H - Co CO - PR3 HRh(CO)(PR3)3 + H2 O R - C - Rh(CO)(PR3)2 + CO R Rh(CO)(PR3)2 - RCHO +PR3 CH3 CH=CH2 H - Rh CO PR3 PR3 HRh(CO)(PR3)2 + PR3 + CH3-CH=CH2 CO P R R R HCo(CO)4 R-CH2-OH

III. Hydroformyl ha propylene Tng 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

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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

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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 isoaldehyt 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, butylpyrolidon v nc.

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*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.

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Cng ngh Ruhrchemie tng hp Oxo sn xut cc ru butanol Hydro 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.Isobutanol thu c ti nh thp .Sn phm y ca thit b tch iso-butanol c a

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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.

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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.

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TI LIU THAM KHO 1.http://en.wikipedia.org/wiki/Butanol 2. Cng ngh tng hp hu c ha du Phm Thanh Huyn, Nguyn Hng Lin

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