MTBE l cht lng khng mu, linh ng, nht thp, d chy, tan v hn trong cc dung mi hu c v hydrocacbon.

M U

MTBE l tn vit tt ca Metyl tert butyl ete l hp cht cha oxy c cng thc cu to:

MTBE c tng hp t TBA hoc tng hp t isobutylen vi metanol ( y l hai phng php chnh trong cng nghip). MTBE l cu t c tr s octan rt cao do vy c s dng ch yu pha vo xng nhm ci thin cht lng xng v gim nhim mi trng. MTBE c nhiu u im hn so vi ph gia Pb ch MTBE va c tc dng nng cao tr s ON ca xng va lm tng kh nng chy hon ton ca nhin liu, do gim kh thi gy nhim( kh CO ), khng lm tng p sut hi bo ho ca nhin liu, n nh tt c tnh tng thch khi pha chn vi nhin liu, tan tt trong nhin liu

Nhu cu tiu th MTBE ang tng nhanh, MTBE l mt trong nhng ho cht tng trng mnh nht trn th gii vi tc tng trng trung bnh 20% mi nm (1989--1994).D bo n nm 2010 nhu cu v MTBE trn ton th gii c th ln ti 29000 tn/nm. C nhiu cng ngh sn xut MTBE ca cc hng khc nhau trn th gii, v d nh qui trnh cng ngh sn xut MTBE ca Snamprogatti (M) s dng nguyn liu l hn hp kh C4 cha isobutylen. Qui trnh cng ngh sn xut MTBE ca Huls ( Cng ho lin bang c). qu trnh ca CD Tech dng nguyn liu C1 v C5 ( hn hp kh). Qu trnh ARCO vi nguyn liu t qu trnh ehydrat ho Tert Butyl Alcohol.CHNG I:TNG QUAN L THUYTA.GI THIU V MTBE :I.TNH CHT CA MTBE:[4,5,6]1.Tnh cht l hc: [5]MTBE l cht lng khng mu, linh ng, nht thp, d chy, tan v hn trong cc dung mi hu c v hydrocacbon.

Bng 1 Tnh cht vt l ca MTBEM88.15

t0s55.30C

Sc cng b mt20 mN/Kg.

Nhit dung ring ( 200C)2.18KJ/Kg.

Nhit ho hi 337KJ/Kg

Nhit chy-34.88 mJ/Kg

Im bc chy chy-280C

Gii hn n vi khng kh1.65-8.4 %V

Nhit ti hn2240C

Nhit t bc chy4600C

nht (g/s.cm)0,003-:- 0,004

T trng0,74044-:- 0,7478

tan ca MTBE trong nc48%

Nhit kt tinh-1090C

T trng bay hi tng i3,1

p sut ti hn3.43MPa

Bng 2 Cc hn hp ng ph ca MTBEHn hp ng pht0s, 0CHm lng MTBE, %Kl

MTBE - nc52.696

MTBE - Metanol51.686

MTBE- Metanol( 1.0MPa)13068

MTBE - Metanol(2.5 MPa)17554

2.Tnh cht ho hc: [5]

MTBE kh n nh di iu kin axit yu, mi trng kim hoc trung tnh, trong mi trng axit mnh c cn bng sau:

Tnh cht ho hc ca MTBE:

Nguyn t oxy O trong phn t MTBE c mt cp in t khng chia v cc nguyn t gc alkyl -CH3 v -C(CH3)3 c hiu ng cm ng dng (+I) to ra cho MTBE ( ete) mang c tnh ca mt baz. Do MTBE tham gia cc phn ng ho hc vi cc axit.

2.1.Phn ng vi cc axit v c mnh: MTBE phn ng vi cc axit v c mnh nh HCl, H2SO4 to ra mui . CH3OC4H9 + HCl [ CH3OC4H9]HCl

2.2.Phn ng vi HI:

MTBE phn ng vi HI , sn phm ca phn ng ph thuc vo nhit .

(-) iu kin nhit thng:

(-) iu kin nhit cao ( un nng)

2.3.Phn ng vi oxi:

(-) nhit thp to hp cht peroxyl khng bn, d gy n.

(-) nhit cao : phn ng chy: CH3 O C(CH3)3 + 15/2 O2 -----------> 5CO + 5CO2 + 6H2O +Q

Trong iu kin phn ng mi trng axit, MTBE gn nh tr vi cc tc nhn khc : buten,isobutylen,n-butan,isobutan. iu ny lm gim cc sn phm ph v tng chn lc. Tuy vy do cn bng c th chuyn dch sang phi to iso-butylen v metanol, dn ti lm gim chuyn ho. Do ta phi ly MTBE ra khi mi trng phn ng lin tc cn bng chuyn dch sang tri. MTBE c y tnh cht ho hc ca mt ete thng thng nh: phn ng vi cc axit v c mnh nh HCl, H2SO4,to mui ( hp cht oxoni). Phn ng vi HI, phn ng vi O2 ( nn d gy n) ; tham gia phn ng vi halogen ho vi Cl2, Br2 gc H- C.II. NG DNG CA MTBE:[1,5,4]

1/ ng dng lm ph gia cao octan trong xng nhin liu . Hin nay hn 90% MTBE sn xut c lm ph gia nhm tng tr s octan ca xng do MTBE c tr s octan cao : RON : 115 -:- 135

MON : 90 -:- 120

S pha trn t hiu qu cao nht khi MTBE trn vi xng du parafino v ngc la khi trn vi xng xng giu olefin th p xut hi bo ho ca xng gim . iu ny nh hng trc tip n kh nng pha trn Butan vo nhin liu do lm gim tnh kinh t ca n . Khi p xut bo ho gim xung th kh nng pha trn Butan vo xng tng ln , lm tng trin vng kinh t do Butan l cu t d tm , r tin v c tr s octan cao . Ngoi mc ch tng tr s octan cho xng . Khi thm MTBE vo xng s lm gim p xut hi bo ho ca xng do lm gim tnh bay hi ng thi khi chy to kh CO gim hm lng Hydrocacbon khng chy ht . Mc d MTBE c nhit chy thp hn mt cht so vi xng nhng khi trn khong 20%V th n khng lm gim cng sut ca ng c v mc tiu hao nhin liu . ng thi c tc dng lm khi ng ng c d dng lc nhit thp v ngn cn qu trnh to mui trong xilanh .

2/Nhng ng dng khc :

MTBE cng c s dng lm nguyn liu hoc cc hp cht trung gian trong cng nghip tng hp h c ho du . MTBE b b gy to Metanol . Ngoi ra MTBE cn c lm nguyn liu sn xut cc hp cht quan trng khc nh Metacrolein , axitMetacrylic , iso_pren , dng lm dung mi trong qu trnh phn tch v lm dung mi trit .

3/ Nhng u, nhc im ca MTBE khi s dng: u im :

+Tr s octan cao + bay hi thp +Kh nng pha trn vi xng tt +Gim to CO v chy ht Hydrocabon +Tnh kinh t khng ph thuc vo s tr gi +Sn phm c th thay th mt cht khc c gi tr tng ng +c chp nhn trn th trng .

Nhc im :

+ Nguyn liu isobutylen kh tm v t tin + c ht vi mi trng nc .

Tuy vy hin gi ph gia MTBE vn c nh gi l mt trong nhng ph gia c s dng rng nht trn th gii thay th cho ph gia ch.B. NGUYN LIU:I . METANOL:[2,5,8]Metanol ln u tin c tm ra vo nm 1661, c cng thc phn t l: CH3 OH Cng thc cu to:

Khi lng phn t: M =32.042 Metanol cn c gi l: Metyl ancol hay carbinol.

1. Tnh cht vt l :[5,8]

Metanol l mt cht lng khng mu, trung tnh, rt c tan v hn trong nc, tan nhiu trong ru,este v tan hu ht trong cc dung mi hu c, n ch tan t trong cht bo v du v metanol l hp cht c cc nn n ho tan c nhiu cht v c nh nhng mui

Hi Metanol to vi khng kh hoc oxi mt hn hp n khi bt la. Vi canxiclorua, Metanol to ra CaCl2.4CH3OH, v vy khng dng CaCl2 lm kh Metanol.Bng 5: Cc i lng vt l ca Metanol [5]T trng (101.3KPa), lng(g/cm3)00C150C250C300C500CGi tr0.810.796090.786640.782080.7637

p sut ti hn (MPa)8.097

Nhit ti hn( 0C )239.49

T trng ti hn0.2715

Th tch ti hn117.9

H s nn ti hn0.224

Nhit nng chy( 0C )-97.68

Nhit im ba-97.56

p sut im ba0.10768

Nhit si (101.3Kpa) ( 0C )64.7

nhit ho hi(101.3KPa)1128kj/mol

Nhit chy( lng, 250C ) (cal/mol)-173.65

nht (250C, mPa/S )lngHi0,5513m.pas9,6810m.pas

dn in (250C ),(2-:-7)10-9-1.cm-1

im chp chyCc h ( 0C )Cc kn( 0C )15,60C12,20C

Gii hn n

Nhit t bt chy5,5-:-44%V

Entanpyto thnh tiu chun(KJ/ mol) 250C(101.3KPa),hi 250C(101.3KPa),lng-200,94kj/mol-238,91kj/mol

Entanpy to thnh t do(KJ/mol) 250C(101.3KPa),hi 250C(101.3KPa),lng-162,24kj/mol-166,64kj/mol

Nhit dung ring(J/mol) 250C(101.3KPa),hi 250C(101.3KPa),lng44,06J.mol-1.K-181,08J.mol-1.K-1

Sc cng b mt trong k/c (250C), (mN/m)22,10mN/m

M mn lng cc5,7606.1090 C.m

Ch s khc x n20D1,32840

2. Tnh cht ho hc:[5]

Metanol c y tnh cht ca mt alcol no n chc. Cc phn ng ho hc c trng in hnh cho lp hp cht ny l kh nng phn ng ca nhm OH. Cc phn ng ho hc xy ra theo hng t tch cc lin kt C-O v O- H. Cc phn ng c trng l: 2.1. Tham gia phn ng este ho vi cc axit.

a, Vi axit hu c:

b,Vi axit v c:

2. 2,Tham gia phn ng ete ho : 2.3, Tham gia phn ng cng vi anken. :

2.4,Tham gia phn ng oxi ho vi O2.

2.5, Phn ng vi cc kim loi kim. :

2. 6, Tham gia phn ng Cacbony ho ( phn ng vi Ca(OH)2):

3/ .Sn xut v ng dng.Hin nay ph bin s dng qu tnh p sut thp v qu trnh ny c chi ph u t v chi ph sn xut thp. Do nng cao tin cy vn hnh thit b , d dng la chn qui m sn xut.Qu trnh sn xut Metanol c th chia lm 3 bc chnh: Bc 1: Sn xut kh tng hp. Bc 2: Tng hp Metanol. Bc 3: X l Metanol th c Metanol thng phm.Mtanol thng phm thng c tinh khit cao, khong 99% khi lng. y l mt im c li cho qu trnh tng hp sau ny.Hin nay ngun Metanol nguyn liu cung cp cho cng nghip sn xut MTBE khng c ln lm, b gii hn bi nhiu mt, mc d sn lng chung l khng nh. y l nhc im chnh ca qu trnh sn xut MTBE.II. ISOBUTYLEN :[8,16,17]

Isobutylen c cng thc phn t l C4H8 .Khi lng phn t M =56.1080Cng thc cu to ca isobutylen :

Isobutylen ( 2- metyl propene)1. Tnh cht vt l:[8,16,17]

Isobutylen l cht kh khng mu, c th chy nhit phng .

Isobutylen tan hon ton trong ru, ete v hydrocabon, nhng t tan trong nc.

Bng 6-Cc tnh cht vt l ca IsobutylenTnh chtn vGi tr

Nhit nng chy(101,3 KPa)0C-140

Nhit si0C-6,9

Nhit ti hn0C144,75

p sut ti hnMPa4,00

T trng ti hng/cm30,239

T trng( lng ,250C)g/cm30,5879

T trng( hi ,00C)g/cm32,582

p sut hi KPa

00CKPa130,3

200CKPa257,0

400CKPa462,8

600CKPa774,3

800CKPa1219,0

1000CKPa1824,7

Nhit ho hi p sut bo ho ti 250CTi im siJ/gJ/g366,9394,2

Nhit dung ring ng p 25oC khi ktclng 101,3 KPaJ.kg-1.K-1J.kg-1.K-115892336

Entanpy to thnh H0tKJ/mol-16,9

Entanpy t do G0t ( 25oC ; 101,3 KPa)KJ/mol58,11

Nhit chy( DIN 51794)oC465

Gii hn chy trong khng kh( 20o C; 101,3KPa)%V1,8 8,8

2. Tnh cht ho hc:Isobutylen c y tnh cht ho hc ca mt olefin thng thng. Ngoi ra isobutylen hot ng mnh hn so vi cc buten ng phn khc.a, Phn ng hydrat ho:

Hydrat ho isobutylen c ter-butyl alcohol (TBA), qu trnh phn ng c th c thc hin trong pha hi hoc pha lng, xc tc cho phn ng l axit H2SO4nng khong 45%( khi lng). Hoc xc tc nha trao i ion sunfonat styren-divinyl benren.

b,Phn ng ete ho Phn ng ca isobutylen vi metanol to thnh Metyltert butyl ether (hay MTBE), qu trnh phn ng thc hin trong pha lng, xc tc cho phn ng l xc tc loi nha trao i ion.

c, Tham gia phn ng cng hp:

Phn ng cng vi halogen, HX, Nc,

X : l halogen.d, Phn ng hydrofomyl ho:

Isobutylen tham gia phn ng hydrofomyl ho vi s c mt ca xc tc Co hoc Rh, ch to ra 3-methylbutanol. e, Phn ng Polyme ho v oligomer ho:

Phn ng ny thng c tin hnh trong dung mi tr, to= - 101000C

Phn ng oligome ho:

f, Phn ng vi (CO + H2O)

g, Phn ng oxi ho:

S oxi ho isobutylen trong khng kh trn hn hp xc tc oxit kim loi chuyn tip cho methacrolein ( nu tip tc oxi ho s to ra axit methacrylic), chn lc 70-80%, chuyn ho t khong 80%

h, Phn ng vi fomandehit:

Isobutylen phn ng vi formandehit, xc tc axit, to sn phm l isoputen. PHN 2 . CNG NGH

1. C s ho hc ca qu trnh sn xut MTBE:[1,8]MTBE c to thnh bi phn ng cng hp metyl alcohol(metanol) vo lin kt i hot ng ca isobutylen, phn ng nh sau:

Phn ng ny xy ra trong pha lng ti iu kin nhit 40 n 1000 v p sut 100 n150psi, y l phn ng to nhit nh H=-37KJ/Kmol. Xc tc l nha trao i ion mang tnh axit, phn ng xy ra nhanh hn rt nhiu theo s lng . y l phn ng thun nghch, phn ng c c cc cu t C4 khc nhau nh: buten, butan,isobutan,V y l phn ng thun nghch, do vy thu c chuyn ho cao (tc thu c nhiu MTBE) ta phi ly lng metanol hn so vi h s t lng , ng tm cch ly MTBE ra khi mi trng phn ng.Qu trnh tng hp MTBE l qu trnh d th Langmuri-Hinshel(L-R)2.ng hc v c ch ca phn ng tng hp MTBE [19,22]Phn ng tng hp MTBE l phn ng thun nghch, xc tc axit ng hc v c ch phn ng ph thuc vo mi trng phn ng . iu ny c ngha l ph thuc vo t l R=isobutylen /metanol

C th xem l phn ng xy ra theo c ch ion vi s proton ho Isobutylen trc:

Sau ion cacbon s tng tc vi metanol:

Sau :

3.Cc yu t nh hng n qu trnh tng hp MTBE:

a. Nhit phn ng:V phn ng tng hp MTBE l phn ng to nhit , do vy cn phi lm gim nhit ca qu trnh tng chuyn ho ca nguyn liu . Thc t thy rng :

Cc loi xc tc u c th cho chuyn ho, chn lc cao trong khong nhit to= 40 n100oC. Nhng nhit to= 80 oC l ti u nht.

b. T l nguyn liu metanol/isobutylen :T l nguyn liu metanol/isobutylen khng ch trong khong l1,1. V nu d isobutylen th c th xy ra nhiu phn ng ph to dime, trime,TBAv isobutylen l olefin kh hot ng. T l ny nh hng ln ti hiu sut chuyn ho v chuyn ho ca xc tc vi Metanol l thp hn isobutylen.c. p sut: m bo qu trnh phn ng xy ra trong h lng p sut duy khong 1,5 MPa ( p sut t nh hng n qu trnh).d.Nng sn phm MTBE :V phn ng tng hp MTBE l phn ng thun nghch do vy nng sn phm cng cao th chuyn ho ca qu trnh cng gim . Chnh v vy m bo chuyn ho chung ca qu trnh tng hp MTBE t thay i ta phi tm cch ly sn phm ra khi vng phn ng . ly sn phm MTBE ra khi vng phn ng hin nay cc cng ngh mi thng dng thit b chng tch sn phm MTBE . e.S c mt ca nc :S c mt ca nc vi mt lng nh bng hoc t hn so vi hn hp ng ph vi Metanol khng lm nh hng lm n hng s cn bng ca qu trnh tng hp MTBE thm ch c th lm tng tc chuyn ho ca isobutylen . Ngai ra vi mt lng nc ln hn lng nc trong hn hp ng ph vi Metanol th cng nh hng n qu trnh tng hp MTBE v lm gim tc to ra MTBE . Nguyn nhn l do nc s tham gia vo phn ng to TBA vi isobutylen . V vy s c mt ca nc s dn n s to sn phm ph .f. Thit b phn ng: Thit b phn ng ng vai tr rt ln trong qu trnh tng hp MTBE , hiu sut ca qu trnh tng hp MTBE t hiu qu cao th cc thit b phn ng phi c cu to ph hp

g. Xc tc

Mtyutquantrngnacnhhngnhottnhvchnlccaxctclngknhcaccmaoquntnxctc. ngknhmao

qun phi ln chocacphntMetanol,isobutylen ,MTBE chuivov ra c.

Nhngnucclmaoqunc ngknhlnqu slmgimhottnhxctcngthicnglmgimchnlccaxctc.

Ccxcthngcsdnglxctc nha traoiion.NhatraoiionlpolimengtrnghpcnhmSO3H.Nhatraoiionctnhaxitmnh(dosnhmSO3Hquytnh)vckch thcmao qunln

Cu trc nha trao i cation

Mt s loi nha trao i cation

Sn xut MTBE

S chung

i t phn on C4 ca qu trnh cracking hi nc sau khi tch butadien

T C4 ca qu trnh FCC

4.1/Cng ngh ete ho ca hng CDTECH:[8]Cng ngh ete ho ca hng CDTECH l cng on ete ho Isobutylen bng Metanol to MTBE l cng on cui cng trong qu trnh sn xut MTBE ca cng ngh ABBLummusCrest.(*) I somer ho n_Butan

(*) Dehydro ho IsoButan (qu trnh Catofin )(*) Ete ho IsoButylen bng Metanol (qu trnh CDTech )Nguyn l hot ng ca dy chuyn :Nguyn liu u giu IsoButylen t thit b dehydro ho c kt hp vi lng Metanol mi t ngun d tr c nh kt hp vi Metanol tun hon t thit b thu hi Metanol trong dy chuyn tng hp MTBE . Hn hp ny c a vo thit b phn ng tng xc tc c nh u tin , y l thit b phn ng chnh ca dy chuyn sn xut MTBE .Qu trnh CDTech c thit k h thng thit b phn ng gm 2 thit b phn ng ni tip nhau . Gm mt thit b phn ng tng xc tc c nh v ni tip vi n l thit b phn ng chng luyn c dng xc tc .Thit b phn ng u tin c thit k iu khin sao cho mc phn ng l ln nht . Theo thit k nhit phn ng c tch mt phn bng qu trnh bay hi ca hn hp phn ng . Nhit ti a ca qu trnh phn ng c gii hn n nhit si ca hn hp phn ng , kt qu l vic iu khin nhit phn ng rt n gin v ng tin cy .

Sau khi phn ng trong thit b phn ng u tin , mt phn hn hp phn ng c lm lnh ti im bt v c bm ti ct chng ct phn ng xc tc m c kt hp c cc phn ng ht phn hn hp cha phn ng ht thit b phn ng tin v qu trnh chng ct phn on sn phm MTBE . Nh c ct phn ng ny m chuyn ho ca qu trnh tng hp MTBE c th t ti 99% tnh theo IsoButylen .Ct phn ng c vn hnh chnh xc cng ging nh cc ct chng ct thng thng , vi thit b gia nhit y v thit b ngng t tun hon nh .Metanol v hn hp C4 hnh thnh mt hn hp ng ph do n c nhit si thp hn nhit si ca MTBE t ta c th d dng tch c MTBE ra khi hn hp phn ng nh thp chng ct . MTBE c tch ra khi thit b phn ng nh l sn phm y cng vi mt lng nh sn phm ph ca phn ng . Tt c cc sn phm ph c hnh thnh trong phn ng tng hp MTBE u tng hp vi xng . cc sn phm ph bao gm TBA (c hnh thnh bi phn ng ca IsoButylen vi nc ) , diisoButylen (dc to thnh bi qu trnh ime ho IsoButylen) . Lng Metanol cn d c ly ra nh v i chng luyn cng vi C4 khng phn ng v c chuyn ti ct tch Metanol .Trong ct tch Metanol , Metanol c tch khi dng C4 nh qu trnh chit tch nh dng nc ngc v c ly ra nh l mt sn phm y gm Metanol v nc sau c dn ti y ca thp ti sinh Metanol. Ti ct tch metanol , pha Raffinat nh bao gm ch yu l Iso Butan v mt s tp cht l cc kh nh sau khi c cho qua thit b phn ng tch bt phn nh c tun hon tr li thit b phn ng dehydro ho .Metanol ti sinh ly ct ti sinh c tun hon quay tr li v c chn vi dng nguyn liu i vo thp tng hp MTBE u tin . Sn phm y ca ct ti sinh Metanol l nc c tun hon tr li ct tch Metanol.S cng ngh

2/ Cng ngh ete ho ca ETHERMAX(UOP) :[8]Cng ngh ete ho ca ETHERMAX l cng on ete ha IsoButylen bng Metanol to MTBE , l cng on cui cng trong qu trnh sn xut MTBE ca hng UOP.(*) I some ho n_Butan (*)Dehydro ho IsoButan v ti sinh xc tc dehydro (*) Ete ho IsoButylen bng Metanol 2.1 / Khi ct phn ng / C4 : Trong qu trnh phn ng IsoButylen phn ng chn lc vi Metanol to ra sn phm MTBE . Qu trnh xy ra trong pha lng , vi s c mt ca xc tc nha trao i ion . S qu trnh phn ng c biu din trn hnh 4 . Phn ng ca IsoButylen vi Metanol xy ra trong iu kin h s t lng ca Metanol ln hn so vi l thuyt mt cht . H thng vn hnh vi mt lng nh Metanol d s to iu kin phn ng tng hp MTBE xy ra hon ton hn v chn lc cng cao hn . C th l cc u im sau :(*) Cn bng chuyn dch theo hng to ra sn phm MTBE, chuyn ho ca qu trnh sn xut MTBE cao hn .(*) Ti a vic sn xut MTBE vi tr s Octan cao .(*) Nhit qu trnh c iu chnh hiu qu hn , an ton hn Nu Metanol khng d th phn ng dime ho IsoButylen s din ra mnh lit v pht nhit c th din ra mnh lit v xy ra rt nhanh . iu ny lm cho nhit trong khi xc tc tng t ngt lm hng xc tc v khng th ti sinh xc tc c na .Phn ng c chn lc xp x 100% ngoi tr nhng phn ng ph nh ca nhng tp cht c trong nguyn liu u . V vy s c mt ca nc trong nguyn liu u s gy ra mt lng tng ng TBA trong sn phm cng nh iso_amylene s thu c TAME trong sn phm. Nhng sn phm ph ny thng khng quan trng , chng c dng nh nhng hp cht pha trn vo xng v do n khng cn phi tch ra khi MTBE .Qu trnh ETHERMAX s dng thit b xc tc tng c nh theo cng ngh phn ng Koch EngineeringsRWD vi cng ngh chng luyn vt qua gii hn cn bng da trn cng ngh xc tc tng c nh thng thng . Trong thit b phn ng , qu trnh ngng t IsoBtylen v Metanol din ra di nhng iu kin thng thng . Mc d c th dng thit b phn ng dng ng nhng UOP chn thit b phn ng vi xc tc tng cht on nhit vi tc ln b tr sp xp vi cc thit b phn ng c bn ca qu trnh OLEFLEX . S tng nhit c iu khin bi s tun hon mt phn ca dng cht phn ng quay tr li np vo thit b phn ng chnh . Dng sn phm t thit b phn ng th nht s c i vo ct chng ct xc tc , ti y sn phm MTBE c tch ra khi hn hp Metanol v IsoButylen cha phn ng v cng din ra phn ng tng hp MTBE gia Metanol vi IsoButylen cha phn ng ht thit b phn ng th nht .Khu vc xc tc ca ct chng ct xc tc s dng kiu lp xc tc c nh tng cht vt qua nhng gii hn cn bng ca phn ng tng hp MTBE bng vic tch lin tc sn phm tch ra khi nhng cu t cha phn ng .c im chnh quan trng ca cng ngh ny l s phn phi lng v hi trong vng phn ng l ng ch , s phi hp hiu qu gia cc cht tham gia phn ng vi xc tc v s phn tch sn phm ra khi khi phn ng lun din ra . Tm li khi phn ng ny c hai chc nng chnh l : phn ng v chuyn khi . Vi cng ngh ny lm cho qu trnh truyn nhit v chuyn khi din ra c hiu qu gia pha hi , pha lng v xc tc rn vi cng mt cng sut ln .Sn phm MTBE c ly ra y ca ct chng tch v pha Raffinat C4 thu c nh thp , Metanol cn trong raffinat C4 c thu hi v ti sinh trong vi h thng nc ra . Raffinat C4 c qua thit b tch cc hydro cc bon nh to ra trong qu trnh OLEFLEX . S cng ngh:

SO SNH LA CHN CNG NGH

C th s dng cng ngh CDTech , cng ngh UOP, .. sn xut MTBE t ngun nguyn liu hn hp Raffinat C4 hoc t qu trnh FCC-BB t chuyn ho cao v n gin , hay c lp t trong cc nh my lc du . V kinh t y l cng ngh c vn u t thp khong 14,3 triu USD . Tuy nhin hin nay cng ngh sn xut m sn xut MTBE c trin vng l cng ngh sn xut MTBE i t kh Butan m . Song u t ban u cho dy chuyn cng ngh l kh tn km , nhng c th sn xut c vi mt cng xut ln . Cng ngh mi ca hng UOP gm cc qu trnh : qu trnh Butamer , Olefex , Ethermax , c nhiu u im hn cc qu trnh ABBLUMMUS v qu trnh ti sinh xc tc c tin hnh lin tc do xc tc lun c hot tnh cao . Hin nay vi qu trnh sn xut MTBE vi cng sut ln ch yu i theo cng ngh ny . V kinh t v vn u t cho cng ngh ny l khong 193 triu USD , gi thnh sn phm l 206USD/1tn MTBE .Sn xut MTBE theo cng ngh ARCO ca Texaco c vn u t l 67,8 triu USD , gi thnh sn xut 264 USD / 1tn MTBE , phng php ny cng c th sn xut vi cng sut ln song gi thnh sn xut t hn v phi kt hp vi qu trnh sn xut Propylen xit (PO).

Qua ta thy rng s dng cng ngh ca UOP t ra l c u vit hn c so vi cc cng ngh ca cc hng sn xut khc . Do vy ta chn cng ngh sn xut MTBE t kh isobutylen ca hng UOP.

Ta bit rng phn ng tng hp MTBE l phn ng to nhit , do phn ng xy ra vi chuyn ho cao ta phi ly nhit ca phn ng ra khi vng phn ng . tn dng nhit to ra t phn ng tng hp MTBE cho cc qu trnh khc trong dy chuyn nh : qu trnh dehydro ho isobutan thnh isobutylen ta chn thit b phn ng chnh l thit b on nhit . gim s lng cc thit b lm lnh ta chn thit b phn ng dng ng chm , xc tc t trong ng , nc lm lnh i bn ngoi ng .

Tm li vi ngun nguyn liu u l isobutan v Metanol ta chn thit b tng hp MTBE ca hng UOP vi thit b phn ng chnh l thit b on nhit dng ng chm . Ti liu tham kho

PGS.TS. inh Th Ng. Ho Hc Du M. Nh Xut bn Khoa hc v K thut H Ni, 2001.PGS.TS. Nguyn Th Minh Hin. Cng ngh ch bin kh t nhin v kh ng hnh. Nh Xut bn Khoa hc v K thut H Ni, 2002.PERP Report. Process Evaluation Research Planning-Methyl tertiary-Butyl Ether (MTBE) 94/95-4.Ullmanns Encyclopedia of Industrial Chemistry. Vol A16. p.465 p.486, p.543 p.550. VCH Verlagsgesellschaft mbH, D-6940 Weinheim. 1990.Ullmanns Encyclopedia of Industrial Chemistry. Vol A13. p.465 p.486, p.543 p.550. VCH Verlagsgesellschaft mbH, D-6940 Weinheim. 1990.Ullmanns Encyclopedia of Industrial Chemistry. Vol A4. p.544 p.549, .VCH Verlagsgesellschaft mbH, D-6940 Weinheim. 1990.Ullmanns Encyclopedia of Industrial Chemistry. Vol A7. p.216 p.220, .VCH Verlagsgesellschaft mbH, D-6940 Weinheim. 1990. UOP Report, January, 1998. MC LC Li gii thiu Phn : M u CHNG I : TNG QUAN V QU TRNH SN XUT MTBE

A . Gii thiu chung v MTBE I .Tnh cht ca MTBE 1.Tnh cht l hc ca MTBE 2. Tnh cht ho hc ca MTBE II. ng dng ca MTBE III. Nhu cu v sn lng ca MTBE trn th gii B . Nguyn liu

I. Metanol 1.Tnh cht vt l ca Metanol 2.Tnh cht ho hc II. Isobutylen Tnh cht vt l Tnh cht ho hc Sn xut v ng dng ca isobutylen Phn 2 Cng ngh sn xut MTBE

C s ho hc ca vic tng hp MTBE ng hc v c ch ca qu trnh tng hp MTBE Cc yu t nh hng Cng ngh CD Tech

5 Cng ngh ete ho ca Ethermax ca UOP 6. nh gi so snh v la chn cng ngh tng hp MTBE CH3

CH3 - O - C - CH3 CH3OH + CH2 = C CH3

CH3

CH3

CH3

H+

CH3

CH3

CH3

C

CH3

O

+ HI

CH3I

+

CH3

CH3

CH3

C

OH

CH3

CH3

CH3

C

CH3

O

+ 2HI

CH3I

+

(CH3)3CI ++

+ H2O

CH3

CH3

CH3

C

CH3

O

+ O2

CH3

CH3

CH3

C

O - OH

CH2

H

H HH

H

C

O - H

t0 1800 C

H2SO4

CH3OH + CH3COOH

CH3COOCH3 +H2O

t0 1800 C

H2SO4

CH3OH + HCl

CH3Cl +H2O

t0 = 1400 C

H2SO4

CH3OH

CH3-O -CH3 +H2O

xt

CH3

CH3

CH2

C

+

CH3OH

CH3

CH3

O CH3

C

CH3

(MTBE)

t0= 401000C

CH4O + 3/2 O2

2H2O + CO2

2CH3OH + O2

2CH2 = O + 2H2O

xt Cu

CH3OH + Na

CH3ONa + H2

CH3

CH3

CH2

C

H+

CH3

CH3

CH2

C

+

H2O

CH3

CH3

OH

C

CH3

Tert-butyl alcohol

(TBA)

xt

CH3

CH3

CH2

C

+

CH3OH

CH3

CH3

O CH3

C

CH3

(MTBE)

+ H2O

CH3

CH3

CH2

C

+

HX

CH3

CH3

CH3

CX

CH3

CH3

CH2

C

+

Cl2

CH3

CH3

CH2Cl

CCl

n

TH

CH3

CH3

CH2

C

- CH2

CH3

C

CH3

Poly isobutylen

CH3

CH3

CH2

C

+ CH3

CH3

CH2

C

CH3

CH3

CH

C

CH3

CH3

CH3

C

H+

CH3

CH3

CH2

C

+

H2O

(CH3)3CCOOH

Axit pivalic

+

CO

CH3

CH3

CH2

C

+

O2

Oxit kim

Loi chuyn tip

Methcrolein

xt

CH3

CH3

CH2

C

+

CH3OH

CH3

CH3

O CH3

C

CH3

(MTBE)

t0 = 401000C

CH3

CH3

CH2

C

+H+

CH3

CH3

CH3

+C

(1)

O

CH3

CH3

CH3

C +

+

CH3

H

CH3

CH3

CH3

C

O

CH3

H

+

(2)

CH3

CH3

CH3

C

O

CH3

H

+

CH3

CH3

CH3

C

O

CH3

+ H+

(3)

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