LI GII THIU Trc vn bo v v chng nhim mi trng ang ngy cng c cp nhiu hin nay, vic thay th xng

xng pha ch, gy nhim mi trng, bng xng khng pha ch l xu hng chung ca nhiu quc gia trn th gii. tng tr s octan ca xng, ngi ta thay th s dng ph gia ch bi cc hp cht cha oxi c ch s octan cao v khng gy nhim mi trng. Nhng hp cht cha oxi thng c s dng l ru v ete nh Metanol, Etanol, v Metyl tert Butyl Ete (MTBE), Etyl tert Butyl Ete (ETBE),Tertamyl Metyl Ete (TAME),.. y l nhng hp cht c tr s octan rt cao v rt thch hp pha vi xng nhm lm tng tr s octan ca xng, ci thin cht lng xng. Hp cht oxi c s dng ch yu pha vo xng hin nay l Metyl tert Butyl Ete (MTBE). y l hp cht oxi c nhng tnh cht ni bt nh: c tr s octan cao, bay hi thp, bn oxi ho, c nhng tnh cht tng thch tt vi xng,.. v c bit l khng gy nhim mi trng. Cc quc gia pht trin hin nay u s dng xng c pha MTBE nh l: M, Anh, c, Nht, Canada,.. Nhu cu v MTBE trn ton th gii ang tng rt nhanh. Cc qu trnh cng ngh sn xut MTBE c thit k v lp t nhiu ni nhm p ng nhu cu MTBE ang tng ln ny. Hin nay, Vit Nam ang xy dng nh my lc du u tin ti Dung Qut, Qung Ngi, hn na trc sc p mi trng, chnh ph Vit Nam d tnh s loi b xng pha ch vo nm 2006. V vy vic tnh ton thit k quy trnh cng ngh sn xut MTBE cho xng l iu ht sc cn thit v quan trng. cng l l do chng ti thc hin bn n ny.

CHNG I: TNG QUAN L THUYT I.GII THIU CHUNG V MTBE I.1 Tnh hnh sn xut v s dng Metyl tert Butyl Ete (MTBE) l hp cht cha oxi c cha khi lng phn t l 88,15 v c cng thc cu to nh sau: CH3 CH3 - O - C - CH3 CH3 MTBE l mt trong nhng ete c vai tr quan trng i vi cng nghip sn xut xng. N ng dng lm cht ph gia cho xng nng cao tr s octan, nhm p ng c yu cu lm vic ca ng c xng cng nh m bo v yu cu v sinh mi trng v sc kho con ngi. Trc y vic nng cao tr s octan cho xng ngi ta dng cht ph gia l nc ch (CH3)4Pb, (C2H5)Pb. Tuy nhin loi ph gia ny bn cnh vic nng cao tr s octan, gim gi thnh sn phm nhng vn cn nhc im: nh hng n sc kho ca con ngi. nhim mi trng nh hng trc tip n ng c, khi ng c lm vic nhiu. Chnh v cc nhc im ny ca nc ch m mt s nc trn th gii ban lut cm v hn ch dng nc ch. Hin nay loi ph gia c dng thay th. Vic thay th ny ng ngha vi vic s c mt s thay i trong thnh phn xng khng ch, nhng ch yu l s khc nhau i vi ph gia nhm tng cng tr s octan. C mt s gii php hu hiu t ti tr s octan cao hn khi khng s dng ch: - Pha trn xng c tr s octan cao (nh xng alkyl ho, izome ho,..) vo nhin liu c tr s octan thp. - Nng cp v a thm cc thit b lc du sn xut hn hp xng c tr s octan cao.

- S dng cc cht ph gia khng cha ch, nh cc hp cht cha oxi: etanol, MTBE, MTBA, TAME,.. Trong s cc ph gia cha oxi ni trn th MTBE v etanol c s dng vi s lng nhiu nht. Chng hn nh M, MTBE c pha trn vi 15% th tch, etanol ti 10% th tch. Braxin pha trn ti 22% etanol vo xng trong nhiu nm. Bn cnh vic tng tr s octan, hn hp ca xng vi ph gia cha oxi gip thi hyrocacbon v CO t xe c s dng nhin liu. C th thy r tr s octan ca mt s cht cha oxi in hnh trong bng: Bng 1: tr s octan ca mt s cht cha oxi Ph gia cha oxi Metanol Etanol Tert-butanol (TBA) Metanol/TBA (50/50) Metyl tert-butyl ete(MTBE) Tert-amyl metyl ete(TAME) Etyl tert-butyl ete (ETBE) RON 127136 120135 104110 115123 115123 111116 110119 MON 99104 100106 9098 96104 98105 98103 95104

T ta thy, tr s RON ca MTBE vo khong 115123, do hn hp 15% MTBE trong xng c tr s octan gc l 87 s to nn mt hn hp c tr s RON nm trong khong 91 n 92, lm tng t 4 n 5 n v octan, tng ng vi hm lng ch t 0,1 n0,15g/l. Tng t, tr s octan ca etanol l 120135, do hn hp 10% ca etanol vi xng c tr s octan l 87 s to ra hn hp c tr s RON vo khong 9092. Nn nhim mi trng trn th gii trong nhng nm gn y gy nh hng nghim trng. Mt trong nhng nguyn nhn gy nn nn nhim mi trng l kh thi ca ng c c cha mt lng kh c hi nh: CO, NO, NO2,.. Lng kh ny gy nh hng trc tip n mi trng.

Do vy vn t ra u tin l phi gim lng kh thi lm cho nhin liu ca ng c v lm c iu ny ta phi lm cho nhin liu ca ng c sch hn, tc l phi sn xut xng sch, hm lng thm trong xng thp, hm lng benzen thp hn 1%. Mt khc c hiu sut ca ng c cao hn v tnh nng thot kh thi hon thin hn th ng c phi t s nn ln hn, tc l yu cu nhin liu phi c tr s octan cao, m xng chng ct trc tip th tr s octan cn thp, cha yu cu ca ng c. Do vy ngi ta s dng cc hp cht nng cao tr s octan pha vo xng, v ph gia u tin c s dng lm nhin liu cho xng l TEL (tetra etyl ch) v TML (tetra metyl ch) loi ph gia ny cho php nng cao ng tr s octan v lm cho gi thnh h. Loi ph gia ny do MDOLE ngi M tm ra vo thng 11-1921 Vo nm 1929, loi ph gia ny c mt trong xng thng phm ca M v c trong xng thng phm ca c trc chin tranh th gii th II khng xa. Tuy nc ch khi s dng pha vo xng b p c lng octan thiu ht v gi thnh xng kh r, song bn cnh vic to nn c cc u im th n cng li nhng tc hi nghim trng cho sc kho con ngi (v ch l cht c trch lu), cho mi trng v nh hng trc tip n tnh nng ca ng c nh: +Trong qu trnh chy to nn hp cht ch rn trong ng c. +Kch thch s nhim bn bugi, lm tng s mi mn xylanh v cc van. +Lm mt hot tnh ca xc tc trng hp x l kh thi, chnh v cn nhiu nhc im nn hu ht cc nc ban lut cm hay s dng nc ch lm cht mang tr s octan cho xng.

Gii hn TEL cc i trong xng (g/l) nm 1998 mt s nc: Bng 2: Gii hn TEL cc i trong xng Nc M Canada , Php, B o Nha,TyBan Nha Cc nc khc 0,3040,840 Australia 0,151 o, Thu in, Phn Lan 0,301 Triu Tin 0,840 Venezuela 0,000 Nht Bn Xu hng hin nay l s dng hp cht cha oxi lm tng octan. Trong cc hp cht oxi c ng dng thc tin nht l cc ete: Metyl tert-Butyl ete (MTBE), Tert amyl-metyl ete (TAME), etyl tert butyl ete (ETBE). Khi thm hp cht cha oxi vo xng, ngoi vic lm tng octan, n cn lm gim lng kh thi CO. Khi cho MTBE vo trong xng th: +Khng cn bt c thay i no i vi ng c hin hnh. +p sut hi ca nhin liu gim do vy tn tht bay hi khi cp nhin liu v vn hnh gim. +Gim khi thi c bt l CO v cc hyro cacbon cha chy. +Thm 20% th tch MTBE vn khng c hi ti cng sut ng c cng nh tng s tiu tn nhin liu, trong iu kin lnh kh nng khi ng ng c cng d dng, ngn cn s ng bng trong b ch ho kh. +MTBE tan ln tt vi H2O nn im ng c ca nhin liu gim ng k. Lng TEL trong xng (g/l) 0,26 0,291 0,399 0,151

+Nhin liu trn MTBE tng thch vi tt c cc vt liu s dng sn xut t nh: m cao su, sn cc kim loi trong b ch ho kh, bm phun,.. +MTBE khng nh hng n h bi tit l thuc m yu. Metyl Tert Butyl Ete l hp cht cha oxi thuc loi hp cht alkyl tert butyl ete c cng thc cu to: CH3 | CH3 O C CH3 | CH3 MTBE c tng hp t metanol v isobuten vi xc tc l acid rn. Ngoi ra, MTBE cng c nhng ng dng khc trong cng nghip lc ho du nh: dng sn xut metaacrolein, metacylic acid, v isopren, sn xut isobuten (bng cch phn hu MTBE, tuy nhin y l bin php khng kinh t). 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 ti nm 2010 nhu cu MTBE s ln ti 29.000 nghn tn/nm. C nhiu qu trnh cng ngh sn xut MTBE cc hng trn th gii c pht minh v lp t sn xut MTBE. Qu trnh cng ngh sn xut MTBE ca Snamprogetti (M) s dng nguyn liu l hn hp kh C4 cha isobuten. Qu trnh Hiils (CHLB c) qu trnh ca CD Tech dng nguyn liu C4 v C5 (hn hp kh). Qu trnh ARCO vi nguyn liu t qu trnh hyrat ho Tert-Butyl Acolhol,.. Tng cng sut ca cc xng sn sut MTBE ang hot ng vo khong 25.275 nghn tn/nm.

I.2 Tnh cht ca MTBE : I.2.1 Tnh cht l hc : Metyl tert butyl ete trng thi bnh thng l cht lng, khng mu, linh ng, nht thp, d chy, tan v hn trong cc dung mi hu c v cc hydro cacbon. Mt s tnh cht vt l c trng ca MTBE c a di bng 3 [1] Bng 3: Tnh cht vt l ca MTBE Khi lng phn t, M Nhit si, ts Nhit nng chy Hng s in mi (20oC) nht (20oC) Sc cn b mt Nhit dung ring (20oC) Nhit ho hi Nhit chy Nhit chp chy Gii hn n vi khng kh p sut ti hn, Pc Nhit ti hn, tc 88,15 55,3oC -108,6oC 4,5 0,36 mPa.s 20 nN/m 2,18 KJ/kg. 337 KJ/kg -34,88 MJ/kg -280C 1,6584% th tch 3,43 MPa 224,0oC

T trng, p sut hi v ho tan trong nc ca MTBE theo nhit c cho bng 4 [1]

Bng 4: T trng, p sut hi bo ho v ho tan ca MTBE Nhit

o

p sut KPa 10,8 17,4

ho tan Nc trong MTBE, %KL 1,19 1,22 MTBE trong nc, % KL 7,3 5,0

T trng G/cm2 0,7613 0,7510 0,7489 0,7458

0 10 12 15 20 30 40

26,8 40,6 60,5

1,28 1,36 1,47

3,3 2,2 1,5

0,7407 0,7304

MTBE c th to hn hp ng ph vi nc, hoc vi Metanol. Bng 5: Hn hp ng ph ca MTBE [1] Hn hp ng ph MTBE - nc MTBE - Metanol MTBE - Metanol (1,0MPa) MTBE - Metanol (2,5MPa) Ts,o C 52,6 51,6 130 175 Hm lng MTBE, %KL 96 86 68 54

.MTBE khng c gii hn v tan ln vi cc dung mi thng thng. .MTBE rt n nh trong mi trng kim trung tnh v axit yu. .Trong mi trng axit mnh MTBE tch metanol v izo buten.

I.2.2 Tnh cht ho hc:

MTBE l cht kh n nh di iu kin acid yu, mi trng kim hoc trung tnh. Trong mi trng c cn bng: CH3 H+ CH3- O - C - CH3 CH3 (MTBE) CH3OH + CH2 = C CH3 (Iso butylen) CH3

(Metanol)

Trong iu kin phn ng mi trng acid, MTBE gn nh tr vi cc tc nhn khc nh buten-1, buten-2, n-buten, isobutan,.. iu ny lm gim cc sn phm ph v tng chn lc. Tuy vy do cn bng c th chuyn dch sang c th to thnh iso butylen v metanol nn c th gim chuyn ha. Do vy cn phi ly MTBE ra khi mi trng phn ng lin tc lm cn bng dch chuyn sang tri. I.2.3 Tnh cht ca MTBE nh hng n cng ngh: Vi cc tnh cht vt l nh trnh by, MTBE c th thu hi bng chng tch v nhit si ca MTBE l 55,3oC tc l ln hn hn hp ng ph ca metanol - hn hp cc hyrocacbon C4 (tos<30) v MTBE thu hi c y thp chng tch. Do cn bng ca MTBE trong acid ni trn nn tng chuyn ho to ra MTBE, trong cng ngh ngi ta s dng k thut phn ng chng tch trong cc thp chng tch v c t cc lp xc tc trong . y l k thut phn ng mi v rt thch hp sn xut MTBE.

II. QU TRNH TNG HP

II.1 C s ha hc ca qu trnh ete ha: [1] CH3 | CH2 = C + CH3OH |

CH3

CH3 | CH3 - C - O - CH3 |

CH3

Qu trnh phn ng xy ra d dng iu kin nh nhng v trong pha lng (hoc pha lng - kh hn hp). Nhit phn ng trong khong 4090oC v p sut t 7-20at(p sut duy tr phn ng trng thi lng). y l phn ng to nhit nh, ( H = 37KJ / mol) thun nghch, c chn lc cao mc d c mt cc cu t C 4 khc (buten, n-butan, iso butan...) trong mi trng phn ng. Xc tc cho phn ng thch hp l xc tc acid rn. C th s dng xc tc acid rn nh bentonit nhng hay s dng nht l nha trao i ion cationit, gn y ngi ta nghin cu s dng xc tc zeolit. Phn ng tng hp l phn ng thun nghch, cn bng dch chuyn sang phi th ngi ta phi ly d lng metanol hn so vi h s t lng. Qu trnh tng hp MTBE l qu trnh d th E R II.1.2 ng hc v c ch phn ng: [4] Phn ng tng hp MTBE l phn ng thun nghch, xc tc acid, ng hc v c ch phn ng ph thuc vo mi trng phn ng, iu ny c ngha l ph thuc vo t l:

Isobuten (t mol) l Metanol C th xem l phn ng xy ra theo c ch ion vi s proton ho iso buten trc: R=
CH3 CH3

|
C = CH2

+H+

|
C+ - CH3

|
CH3

|
CH3

Sau ion cacboni s tng tc vi etanol: CH3 | CH3 - C+ + CH3OH | CH3 V cui cng: CH3 | CH3 - C - O - CH3 | | CH3 H CH3 | CH3 - C - O - CH3 + H+ | CH3 CH3 | CH3 -C - O+ - CH3 | | CH3 H

(2)

T l R<=0,7, khi lng metanol l ch yu trong mi trng phn ng, v vy metanol c xu hng hp ph ln xc tc nha trao i ion v do hu ht cc nhm Sulfomic ca nha b Solvat ho bi ru: R - SO3H + MeOH Me+OH2 + R - SO3S hp ph ca alken ln nha l rt nh. Do c th thy rng tin trnh phn ng tng hp MTBE s theo c ch Eley-Rideal (E-R), tc l phn ng xy ra trn b mt nha gia Isobuten t dung dch vi Metanol hp ph. Phn ng b mt l giai on quyt nh tc . MeOH + MTBE . MeOH . MTBE . + 2. MTBE + MeOH . + Iso buten + 2

V khi tc phn ng s c xc nh:

r=

K f .K M e (C IB C M e C MT /K) (1 + K M e .C M e + K MT .C MT ) 2

Trong : r: tc phn ng Kf: hng s tc phn ngthun KMe: hng s cn bng hp ph ca Metanol K: hng s cn bng nhit ng Ci: nng ca cu t i, mol/l i = Isobuten, Metanol, MTBE KMT: hng s cn bng hp ph Khi b hp ph Metanol c ni hyro theo 3 kchthc mng li ca 3 nhm SO3H v phn ng vi isobuten t dung dch trong cc mao qun v pha to gel. S hot ng ng tc dng ca c 3 nhm SO3H s to ra nhm tert-butyl c cu trc ging cation, v s trao i phi hp proton xy ra. Cng theo c ch ny c th xy ra s to thnh Metyl-sec butyl Ete ging nh to ra MTBE, song s to thnh ny mc nh bi v kh nng phn ng thp ca alken thng, Buten-1 hu nh khng hp ph R<0,7. Ngoi ra cng c s to thnh Dimetyl ete (DME) do phn ng ca 2 phn t Metanol hp ph trn 2 nhm SO3H cnh nhau. Khi 0,7< R <0,8, tc l CIB c gi trn ng k, khi c th thy rng c ch Lang muir-Hinshelwood (L-H) bt u c tc dng. Theo c ch ny, Metanol v Iso buten hp ph ln nha phn ng to MTBE: MeOH + IB + MTBE . MeOH . IB . MTBE . + 2 MTBE +

MeOH . + IB. +

Phn ng b mt cng quyt nh tc chung.

ng hc theo c ch ny s theo phng trnh:

r=

K f .K IB .K M e .(C IB .C M e C MT /K) (1 + K IB .C IB + K M e .C M e + K MT .C MT ) 2

Trn quan im phn t, c th suy ra rng s trao i phi hp proton m c lin quan n s hp ph isobuten l c tc dng. S hp ph isobuten dn n s gi c nh cu trc ging cation ca tert-Butyl vo nhm SO 3H, nhm m phn ng vi ni hyro ca Metanol vi SO3H bn cnh. S ng tc dng ca 3 nhm SO3H l cn thit n nh cu trc ca tert-Butyl v s trao i proton xy ra. MTBE c to ra v ni hyro vi nhm SO3H v lm gim tc phn ng, nu qu trnh phn ng khng lm cho cc ht nha co li c ch L-H c th xy ra nhanh hn c ch E-R v tc phn ng tng dn. Chm t R=0,7 v mn m khi R=1,7. Khi C IB cao, iso butylen trong dung dch, trong cc mao qun v trong cc th gel phn ng vi cc phn t iso butylen c n nh trn nha theo c ch E-R to ra di isobutylen (DIB), Metyl Sec-butyl Ete (MSBE) l cc sn phm ph. Khi R=1,7 th c s tng t ngt tc phn ng khi mo ca phn ng isome ho buten-1, iu ny c th l do gi tr ny hm lng mol butanol trong pha lng ln (khong 25%). Do s hp ph thun nghch buten-1 ln nha kh ln. Khi R=3,5, hm lng CH3OH trong pha lng cn t hn 15% mol trong khi hm lng iso buten l 50% (nu nguyn liu l phn on C4 t qu trnh Craking hi nc). CMe thp ny ht nha polime b co li v mng li SO3H dy c, c ch L-H bt u chim u th. Do lc ny phn ng tng hp MTBE xy ra ch yu theo c ch L-H. S to thnh DIB theo c ch L-H cng c tc dng. Khi R=10, lc ny phn ng ch xy ra theo c ch L-H cui cng khi tng hp MTBE t cn bng ho hc, mt c ch chuyn tip c th xy ra. R<=1 qu trnh phn ng ch yu xy ra theo c ch E-R v tc phn ng khi mo gim dn. R<1 tin hnh phn ng bt u theo c 2 c ch.

Trong qu trnh phn ng xy ra phn ng tng hp MTBE chuyn sang c ch L-H v tc phn ng tng dn v t cn bng ho hc. II.1.3 Xc tc cho phn ng: [5] Trong cng ngh sn xut cht oxy thng s dng xc tc l nha trao i ion dng cationt c mao qun ln. Nha cationt l 1 acid rn, l hp cht cao phn t gm matrix l hp cht trng hp ca styron v c thm divynyl benzen butadien hay cc hp cht khc ni i lin hp to thnh cu trc mng khng gian mc no khng tan trong nc v cc dung mi hu c nhng c cu trc xp h c kh nng trao i cc nhm chc nh l -SO3H c nh vo matrix polime ni trn (nh vo cc nhn thm) Matrix ca cation to thnh gia Styren v divinyl benzen c th biu din nh sau:

acid cng mnh th hot tnh xc tc cng cao. acid ph thuc vo kiu loi v s nhm acid trn nha v b nh hng bi ni ngang (lin kt ngang). hot ng ca xc tc nha ph thuc ch yu vo hnh thi ban u ca nha v vo tng tc ca n vi pha phn ng gm c dung mi v nhng cht khc trong h thng phn ng.

Hnh thi ca nha trao i ion lin quan n cch tip cn ca cc phn t vo nhm Sulfonic. N c th b nh hng bi tng tc ca dung mi v nhng phn t hp ph vi nhm nh chc. Mt s loi xc tc nha trao i ion v tnh cht ca chng c a bng 7. Bng 6: Tnh cht ca mt s loi nha trao i ion [5] Tn mi thng acid C B mt ring theo BET, m2/g 41,5 25,0 42,0 34,0 29,0 25,0 6,2 48,1 31,0 29,0 35,0 220,1 151,2 163,8 156,9 165,7 B mt ring theo ISEC, m2/g Th tch mao qun, mL/g 0,67 0,52 0,36 0,28 0,33 0,30 0,16 0,38 0,47 0,48 0,33 n g knh mao qun, Ao 650 832 343 329 455 252 1148 342 597 662 386 Kch thc ht tb, nm 0,63 0,66 0,74 0,51 0,63 0,43 0,43 0,43 0,40 0,40 0,43

Bayer K2631 Bayer OC-1501 Ambalyst 15 Ambalyst 35 Dowex M32 PuroliteCT 151 PuroliteCT 165 PuroliteCT 169 PuroliteCT 175 PuroliteCT 179

4,83 5,47 4,75 5,32 4,78 5,40 5,00 4,90 4,98 5,25

PuroliteCT 171 4,94

II.1.4 Cc yu t nh hng n qu trnh cng ngh: II.1.4.1 nh hng ca t s Iso butene/Metanol n tc phn ng tng hp: Khi tng t s IB/MeOH tc l hm lng Iso butylen [6] trong hn hp phn ng tng s dn n vic gim hng s tc phn ng tng hp. iu

ny l do s n nh ca isobuten v phc hot ho, v do s tng ln nhiu cc proton hot ng. V vy trong cng ngh cn iu chnh t l ny ph hp trnh lm gim tc phn ng tng hp. II.1.4.2 nh hng ca nng MTBE to thnh n phn ng tng hp Khi nng MTBE tng dn n s tng hng s tc , hng s m khng ph thuc v nha trao i ion. C th thy rng s tng hm lng MTBE trong hn hp phn ng dn n nhng thay i, khng ph thuc vo nha, ca nhng thng s hot ho ( H v S), nhng thng s m dn n s thay i phc hot ho. V iu ny lm tng tc phn ng. [6] II.1.4.3 nh hng ca s c mt ca nc [7] S c mt ca nc vi mt lng nh, bng hoc t hn so vi trong hn hp ng ph vi metanol khng nh hng nhiu n hng s cn bng ca MTBE, thm ch c th lm tng chuyn ho iso buten. Nc vi mt lng nh cng c nh hng c ch v lm gim tc to ra MTBE, c bit l phn u (phn trn) ca thit b gin on hoc thit b ng chm. nh hng c ch s mt i khi nc b tiu th to ra TBA. TBA c to thnh rt nhanh. Cn bng TBA t c nhanh chng hn so vi ete. V vy s c mt ca nc s dn n s to ra phn ng ph. II.2 Cc phng php sn xut: T cc ngun iso-butan khc nhau m ta c hng sn xut MTBE khc nhau.
Hng 1:

i t phn on C4 ca qu trnh cracking hi nc sau khi tch butadien( Raffinat-1)

 Hng 2: t hn hp C4 ca qu trnh FCC

Hn hp C4 t pah Raffinat-1 ca qu trnh cracking hi nc v t qu trnh FCC l cc ngun nguyn liu truyn thng, c s dng kh ph bin trong cc phn xng sn xut MTBE trn th gii do gi thnh sn xut r, nguyn liu l sn phm th yu ca qu trnh lc du v c th s dng lm nguyn liu trc tip sn xut MTBE. Tuy vy, do s hn ch v k thut v d lng nguyn liu m phng php ny ang dn b thay th. Mt s cng ngh dng ngun nguyn liu ny l: + Cng ngh ca hng CD-Tech + Cng ngh ca hng Phillips + Cng ngh ca hng Snamprogetti + Cng ngh ca hng IPF, hng Hills Hng 3: T n-butan tch ra t kh t nhin

Trong thnh phn kh thu c t cc m kh thin nhin c cha mt lng kh butan kh ln. V th, ngi ta a ra phng php sn xut mi s dng nguyn liu l n-butan tch ra t kh t nhin vi tr lng

ln. Qu trnh ny gm 3 bc c bn vi nhiu cng ngh ca cc hng khc nhau : + Isome ha n-butan thnh iso-butan: Cng ngh ABB ca Lummus v cng ngh Butamer ca UOP + Dehydro ha iso-butan thnh iso-buten: Cng ngh Catofin ca Lummus, Cng ngh Oleflex ca UOP, cng ngh STAR ca Phillips, qu trnh FBD-4 ca Snamprogetti + Ete ha: Cng ngh CD-Tech ca Lummus, Ethermax ca UOP, Phillips Etherfication process ca Phillips. Hng 4: T tert butyl alcol (TBA)

II.3 Nguyn liu tng hp MTBE Nguyn liu tng hp MTBE l Metanol v Iso buten II.3.1 Metanol: [1] II.3.1.1 Tnh cht vt l: Metanol l cht lng khng mu, linh ng, d chy v tan nhiu trong nc, tan hu ht trong cc dung mi hu c, tan t trong cht bo v du, Metanol l cht phn cc v vy n tan nhiu trong cc cht v c phn cc v c bit l cc mui. Metanol to hn hp ng ph vi nhiu cht nh MTBE, Acrylonitrile, hyrocacbon (n-pentan, benzen, toluen...), Metyl acetat, Metyl metacrylat... Mt s tnh cht vt l quan trng ca Metanol c da vo bng 7.

Bng 7: Mt s tnh cht vt l ca Metanol

II.3.1.2 Tnh cht ha hc: Metanol l ru n gin nht, hot ng ca n c xc nh vi nhm chc OH. Phn ng ca Metanol xy ra qua s phn hu ca ni C-O hoc H-O v c trng vi s thay th H hoc nhm OH. Mt s phn ng c trng: Tc dng vi kim loi kim to mui ancolat Phn ng este ha Metanol tc dng axit v c, hu c to thnh este, phn ng thun nghch v xy ra trong mi trng axit H2SO4 c:

 Tc dng vi HX
Tc dng vi NH3

Metanol c th b oxy ha bi CuO hoc dung dch KMnO4 to thnh fomaldehyt:

Trong khng kh, metanol chy to thnh CO2 v H2O ng thi ta nhit: Khi cho hi metanol i qua ng nung 200 300 oC c mt xc tc Cu th xy ra phn ng dehydro ga to thnh formaldehyt:

II.3.2 Isobuten [8]. II.3.2.1 Tnh cht vt l: Isobuten l cht kh khng mu, c th chy nhit v p sut thng. N c th ho tan vi ru, ete v hyro cacbon, ch tan t trong nc. Mt s tnh cht vt l ca isobuten c da bng 8:

Bng 8: Mt s tnh cht vt l ca isobuten [8]

II.3.2.1 Tnh cht ha hc: Iso buten c cc tnh cht ca mt defin c trng vi nhng phn ng chnh nh phn ng cng, xc tc acid (phn ng cng ru to ete, phn ng cng cc halogen to cc dn xut halogenna, phn ng cng H2O to TBA, phn ng isome ho, phn ng polime ho to DIB, phn ng vi CO v H2O to ra axit cacbo xlic)(CH3)3C COOH, phn ng vi fomaldehyde to hp cht dng sn xut isopren. Phn ng cng: + Cng ru to ete

+ Cng nc to TBA

+ Cng hydro halogenua (HX)

Phn ng oxy ha

Phn ng polyme ha

III. CC QU TRNH CNG NGH Cc qu trnh sn xut MTBE khc nhau da trn cc ngun nguyn liu khc nhau.

III.1 Sn xut MTBE t hn hp kh C4 Raffinat-1 t phn xng etylen v t hn hp FCC-BB t qu trnh cracking xc tc. S khi ca qu trnh sn xut MTBE t kh C4 t xng etylen.

Nu ngun nguyn liu l isobuten t qu trnh cracking xc tc:

y l ngun nguyn liu truyn thng thng c s dng trong cc xng sn xut MTBE trn th gii. V vy qu trnh sn xut i t hn hp kh Raffinat-1 hoc FCC-BB l qu trnh sn xut MTBE ph bin trc y. u im ca n l gi thnh sn xut r, do nguyn liu l c sn gi thnh sn phm r v nguyn liu l cc sn phm th yu ca cc qu trnh lc du v c th s dng trc tip sn xut MTBE. Tuy vy do s hn ch v s lng nguyn liu m phng php ny ang dn b thay th. Mt s cng ngh dng ngun nguyn liu l hn hp Raffinal-1 hoc FCC-BB gm c: Cng ngh ca snamprogetti Cng ngh MTBE ca hiils Cng ngh CD-Tech Cng ngh ca phillip

III.1.1 S cng ngh ca snamprogetti

Hnh 1: S cng ngh sn xut MTBE ca hng snamprogetti 1. Thit b phn ng ng chm 3. Thp tch MTBE 5. Thp tch Metanol S cng ngh ny s dng nguyn liu l hn hp C 4 t qu trnh cracking hi nc hoc hn hp kh FCC-BB. Thit b phn ng th nht l thit b ng chm thc hin phn ng ng nhit, thit b th 2 thc hin on nhit. Xc tc c sp xp sao cho vic iu khin nhit l tt nht v chuyn ho t xp x 100%. Nguyn liu u gm metanol v hn hp kh C 4 giu iso-buten c a vo thit b phn ng ng chm (1). Thit b ny cho php tin hnh phn ng ch ng nhit. Sau , hn hp phn ng c a sang thit b (2) tip tc phn ng theo ch on nhit. Sn phm t y (2) c dn vo thp tch (3). MTBE ly ra y cn li l metanol v hn hp C4 cha phn ng c a qua thp hp th bng nc (4) tch hn hp C4 trn nh. Dung dch hp th metanol c a qua thp (5) thu hi metanol cho tun hon tr li cng dng nguyn liu u i vo thit b phn ng (1). 2. Thit b phn ng on nhit 4. Thp hp th Metanol

III.1.2 S cng ngh Hiils Qu trnh tng hp MTBE theo cng ngh ny chuyn ha iso-buten 99,9% mol.

Hnh 2: Cng ngh sn xut Hiils ( hai giai on) Giai on 1: 1. L phn ng dng ng (ng chm) 3. Thp chng ct C4 th nht Giai on 2: 5. L phn ng th cp 7. Thp hp th Metanol III.1.3 S cng ngh CD-Tech S ny c th s dng nguyn liu l hn hp l hyro cacbon C 4 hoc isobuten t qu trnh hyro ho isobutan. Cng ngh CD Tech s dng 2 thit b phn ng. Thit b th nht l thit b phn ng on nhit, cn thit b 2 l thit b phn ng chng tch, va thc hin phn ng va chng tch. Trong thp phn ng chng tch 2 ngi ta b tr nhng khong chng tch v nhng khong cha xc tc thc hin phn ng tng chuyn ho sn phm. y l cng ngh mi s dng k thut phn ng chng tch (3) l ct tch MTBE kkhi Metanol, (4) l ct 6. Thp chng ct C4 th 2 8. Thp tch Metanol 2. L phn ng on nhit 4. Thp chng ct hn hp ng ph

tch Metanol - nc, Cng ngh cho ta chuyn ha iso-buten ti 99,9% mol. Nhit mang vo ct chng tch c tit kim nh nhit t thit b phn ng th nht.

Hnh 3: S cng ngh ca hng CD-tech 1. Thit b phn ng c lp xc tc c nh 2. Thit b phn ng chng tch xc tc 3. Thp hp th Metanol 4. Thp chng ct Metanol

III.1.4 S cng ngh ca hng Phillip

Hnh 4: S cng ngh ca hng Phillip 1,2 Thit b phn ng 4. Thp hp th Metanol 3. Thp tch MTBE 5. Thp ti sinh Metanol

Qu trnh ny c tin hnh nh sau: Iso-buten cng vi metanol nguyn liu v metanol tun hon c lm giu ti b phn l phn ng (1,2) cha ng nha trao i ion axit. thit b (1) di xc tc c nh (gian on 1) c lm lnh bn ngoi. Cng ngh ny cho php cht xc tc d thay i m khng ngng hot ng v ng thi cho sn phm MTBE cht lng cao. MTBE t y thp RWD c lm lnh trc khi vo b cha. Phn lng ra khi nh c cha C4S. Metanol d v hydrocacbon nh khc c bay hi qua van tit lu sao i vo thp ra bng nc, ti y Metanol c tch ra theo nc vo thp chng ct thu Metanol hi lu li qu trnh ete ha cn nc quay tr li ra kh. Phn kh ra khi thp ra c x l hi lu li iso-buten ti nh my dehydro ha.

III.2 Sn xut MTBE t kh butan t m kh [9], [10], [2]. y l xu hng sn xut mi s dng nguyn liu l phn butan tch t kh t nhin vi tr lng ln. S qu trnh sn xut MTBE t kh n-butan nh sau: Metanol

Qu trnh bao gm 3 giai on: + Isome ho kh m n-butan to thnh isobutan, qu trnh isome ho xy ra nhit thp (150-200oC) v p sut l 200-400psig trong pha hi. Xc tc cho qu trnh l Pt hoc Al2O3 hoc Pt/Al2O3 c tm mt lng hp cht hu c dn xut clo. Kh n-butan a vo s chuyn ho thnh isobutan gn im cn bng. Mt s qu trnh isome ho thc hin isome n-butan to thnh isobutan l: qu trnh isome ho ca Lummus (hnh 6), qu trnh Butamer (UOP) (hnh 7)

Hnh 6: Qu trnh isome ha ca Lummus

1.Thp tch iso-butan 2.Thp sy 3,4.L phn ng 6. Thp n nh 7.Thp ra kh 5.Thit b chng tch 8.My nn

Hnh 7: Qu trnh isome ha butamer ca UOP 1. Thp tch 5,6. Thit b sy I. Nguyn liu butan III. Nhin liu kh 2,7,9. Thit b lng 8. Thit b chng tch II. Iso-butan IV. Na2CO3 3,4. L phn ng 10. Thp ra

+Qu trnh hyro ho isobutan thnh isobuten: Qu trnh hyro ho ny c thc hin t=540760oC v p sut thp. Xc tc phn ng c th l Cr/Al2O3 hoc Pt. Sn phm thu c cha 7585% iso buten v isobutan. Cc qu trnh hyro ho hin nay sn xut iso buten l: qu trnh Catofin (Lummus) hnh 8, qu trnh oleflex ca UOP (hnh9), qu trnh STAR ca Phillip, qu trnh FBD-4 ca Snamprogetti (hnh10 v 11).

Hnh 8: Qu trnh Catofin ca Lummus

1. Trao i nhit 8. Thit b lm lnh I. Parafin C3-C5 2. L thi 9. PSA 3. L hi 7. Thp sy kh 10. un nng s b IV. Kh thi 4. L gia nhit 5. My nn sn phm 6. Ni chng

II. Sn phm III. Kh nhin liu

Qu trnh ny s dng xc tc Crom oxit, nhit cp cho phn ng bng cch t chy ci to thnh xc tc nh dng khng kh nng.

Hnh 9: Qu trnh Oleflex

1. Thit b phn ng 4. Thp sy 2. Thit b gia nhit 5. Tuabin gin n kh 3. L ti sinh xc tc 6. Thp tch hydro

7. Thp ct phn sn phm nh I. Nguyn liu iso-butan k thut v tun hon II. Kh thi IV. Phn ct sn phm nh III. Sn phm iso-buten V. Hydro tun hon

Hnh 10: Qu trnh STAR ca Phillip

1. L phn ng 6. Thp sy kh 8. Thp tch sn phm I. Kh nhin liu 2. ng khi 9. My nn III. BFW 3,4,5. Thp chng 7. Thit b lm lnh II. Nguyn liu iso-butan

Hnh 11: Cng ngh dehydro ha ca hng snamprogetti (FBD-4)

1.Dng trao i nguyn liu 2.L phn ng ti sinh 3.Thit b phn tch 4.Thp tch sn phm 7.Thit b lm lnh 10. B phn lc I. Iso-butan IV. Kh nh II. Kh thi V. Sn phm III. Khng kh 5.ng khi 8.Thp sy kh 6.Lc kh nhin liu 9.My nn

+ Qu trnh ete ho isobuten thnh MTBE: qu trnh ny c tin hnh to=40-90oC v p sut t 7-29 at, xc tc l nha trao i ion. Phn ng thc hin trong qua lng. Cng ngh qu trnh ete ho ca mt s hng nh qu trnh CD Tech (Lummus), Ether max (UOP), Phillip, Etherfication Process (Phillip)...

Hnh 12: Cng ngh Ethermax ca UOP

1.Thit b phn ng 3.Thp ra kh bng nc I. Iso-buten III. MTBE 2.Thp chng ct 4.Thp chng ct ru nc II. Metanol IV. Raffinat C4

III.3 Sn xut MTBE t Tert Butyl Alcohol: y l qu trnh sn xut MTBE i t nguyn liu iso buten ca qu trnh hyrat ho TBA. TBA thu c l ng sn phm trong qu trnh sn xut propylen oxit. S qu trnh:

Qu trnh sn xut MTBE t TBA do hng Texaco thc hin c s nh sau:

Hnh 13: Cng ngh sn xut MTBE t TBA ca Texaco 1. L t 3. Thit b phn ng on nhit 5. Thp hp th Metanol I. Nguyn liu Metanol III. Hn hp Raffinat C4 V. Nguyn liu Metanol VII. Sn phm MTBE 2. Thit b phn ng 4. Thit b phn ng chng ct 6. Thp ti sinh Metanol II. Nhin liu IV. Metanol ti sinh VI. Iso-buten

CHNG 3 : TNH TON THIT B

I.TNH TON CN BNG VT CHT: Dy truyn sn xut MTBE t nguyn liu kh isobutan vi cng sut 50.000 tn/nm. Dy chuyn sn xut 24h/ngy v mt nm lm vic 330 ngy cn 35 ngy ngh sa cha, bo dng nh k. *Cc ch tiu sn xut: Nng sut MTBE: 50.000 tn/nm Nh vy nng sut dy chuyn tnh theo gi l:

50.000.000 = 6313,13kg/ h 330.24

Tnh theo Kmol/h:

6313,13 = 71,74Kmol/ h 88
(khi lng phn t ca MTBE l 88) Nng sn phm: MTBE chim 99% (khi lng) Metanol chim 0,5% Cn li l Dime ca i-Butylen, ru, TBA, nc... Nguyn liu l kh iso-butan tiu chun c cho bng 12 (theo TY38.101492-79) Loi B

Bng 12: Thnh phn kh iso-butan nguyn liu Thnh phn Iso butan Propan Tng Buten n-butan
+ C5

% th tch 90 4,5 0,5 6 0,5 0,005 0

Cc cht khc H2S v Mercaptan H2O v kim

Metanol nguyn liu l metanol thng phm vi thnh phn: Metanol Nc Tng aceton v aldehyd Tng acid Phn cn I.1 Tnh cn bng vt cht chung Qu trnh sn xut MTBE qua 2 giai on: giai on hyro ha isobutan v giai on tng hp MTBE. Ta tnh cn bng vt cht tng giai on: Giai on tng hp MTBE: Cn bng: khi lng vo = khi lng ra - Cc dng khi lng i vo phn tng hp MTBE gm c: + Hn hp C4 lng i ra t phn hyro ha: G1, kg/h + Dng nguyn liu Metanol : GMeOH , kg/h - Cc dng sn phm i ra khi phn tng hp MTBE gm c: 99,9% (khi lng) 0,1% < 30 mg/kg < 30 mg/kg < 10 mg/kg.

+ Hn hp kh C4 cha phn ng + Sn phm MTBE

: GC 4 chaphnng , kg/h : GMTBE , kg/h

H2 O do trong nguyn liu Metanol cha 0,1% (W). y on gin ta coi rng trong qa trnh hp th Metanol v qa trnh chng tch thu hi Metanol v nc, lng H2O s dng khng b mt mt v c tun hon li cho qa trnh hp th Metanol v lng H 2O ly ra bng lng nc a vo dy chuyn do c trong nguyn liu Metanol v bng GH 2 O, kg/h Tnh ton cc khi lng G1, GMEOH , GC 4
cha phn ng

, GMTBE , nh sau:

+ Khi lng sn phm MTBE i ra phi l nng sut quy nh ca ton dy chuyn sn xut v bng 6313,13 kg/h. Vy GMTBE = 6313,13 kg/h + giai on tng hp, phn ng tng hp nh sau: Iso-buten + MeOH MTBE y l phn ng thun nghch, tuy vy khi qua thp phn ng chng ct (thp CD) theo cng ngh CD Tech th chuyn ha chung t 99%, chn lc t 100% (tnh theo iso buten). Vy to ra MTBE t nng sut yu cu l 71,74 kmol/h th lng iso buten cn to ra t phn hyro ha tiu th cho phn ng tng hp l:
71,74 = 72,46kmol/h 0,99

(0,99 l chuyn ha ca phn ng tng hp theo iso buten) y n gin trong tnh ton ta coi chn lc MTBE t 100% v iso buten khng tiu th cho phn ng ph to ra TBA v DIB. Vy GIB =72,46 . 56 = 4057,76 kg/h (MIB = 56) + Khi lng Metanol a vo thit b phn ng MTBE theo t l:

Metanol = 1,1 (t l mol). iso buten

Vy lng Metanol a vo l: 72,46 . 1,1 = 79,706 kmol/h Hay 79,706 . 32 = 255,60 kg/h Lng Metanol a vo thit b = lng metanol (99,9% W) mi a vo + lng metanol tun hon. Trong : Lng Metanol tun hon = lng Metanol cn li sau phn ng- lng Metanol trong sn phm MTBE. Lng Metanol cn li sau phn ng = Lng Metanol a vo Metanol tiu th cho phn ng. Lng Metanol tiu hao cho phn ng cng bng s kmol MTBE to ra (theo phn ng tng hp) v bng 71,74 kmol/h. Vy lng Metanol cn li sau phn ng l: 79,76 -71,74 = 7,966 kmol/h Hay 7,17. 32 = 254,91 kg/h. Ta coi cc sn phm ph khc trong MTBE sn phm ch gm c Metanol v khng cha DIB, TBA... Lng Me cn li trong sn phm MTBE chim 1% khi lng tc l bng: 0,01. 6313.13 = 63,13 kg/h. Coi rng Metanol c thu hi theo dng sn phm chnh ra khi thp phn ng 2 l 100%. Nh vy lng Metanol tun hon l: 254,91. 63.13 = 191.78 kg/h. Lng Metanol (100% W) mi cn a vo l: 2550,60 - 191,78 = 2358,82 kg/h. Lng Metanol (99,9%) mi cn a vo dy chuyn l:

2358,82 = 2361,18 kg/h 0,999

Vy lng nc a vo dy chuyn l: GH 2 O = 2361,18 - 2358,82 = 2,36 kg/h. Cn bng ta c: G1 + GMeOH (99,9%) = GC 4 Hay G1 + 2361,18 = GC 4
cha phn ng cha phn ng

+ GMTBE + GMeOH trong MTBE + GH 2 O + 6313,13 + 63,13 + 2,36

tnh G1 v G c + ta tnh cn bng vt cht cho giai on hyro ha. 4 * Cn bng vt cht giai on hyro ha: Khi cn bng: khi lng vo = khi lng ra. - Cc dng vt cht i vo phn hyro ha gm: + Hn hp C4 lng iso butan nguyn liu: Giso- C 4 H10 , kg/h - Cc dng vt cht i ra gm: + Hn hp lng C4 sn phm c cha iso buten: Giso- C 4 H10 , kg/h + Hn hp kh thi giu H2: Gkh thi , kg/h Vy cn bng ta c: Giso- C 4 H 10 nguyn liu = Giso- C 4 H8 + Giso- C 4 H 8
sn phm

+ Gkh thi

Tnh ton cc khi lng nh sau:

nguyn liu

Ta c phn ng: iso-C4H10 iso-C4H8 + H2 (*) Lng iso-C4H8 cn to ra giai on hyro ha tng hp c 6313,13 kg
MTBE h

nh ta tnh: 72,46 kmol/h.

Phn ng hyro ha (*) thc hin trong dy chuyn t chuyn ha 40%, v chuyn ha t 92% mol [2]

Nh vy lng iso-C4H10 cn hyro ha cn l:

72,46 = 78,46 kmol/h. 0,92

V chuyn ha ca (*) t 40%, vy lng iso-C4H10 nguyn cht cn a vo dy chuyn l:

78,46 = 196,90 kmol/h. 0,4

Trong 72,46 kmol/h iso-C4H10 s tiu hao cho phn ng chnh (*) to ra 72,46 kmol/h iso-C4H8 v 78,76 - 72,46 = 6,3 kmol/h s tham gia phn ng ph iso-C4H10. Gi s iso-C4H10 ch tham gia cc phn ng ph cracking: iso-C4H10 C2H6 + C2H4 x (kmol/h) x (kmol/h) x x x (2) x iso-C4H10 CH4 + C3H6 (1)

n gin ta gi s cc phn ng (1) v (2) xy ra vi tc nh nhau, tiu th lng iso-C4H10 nh nhau, cc phn ng c hiu sut nh nhau v bng 100%. Vy lng iso-C4H10 tiu th cho mi phn ng l:
x= 6,3 = 3,15kmol/h. 2

Lng iso-C4H10 cn li khng chuyn ha l: 196,90 - 78,76 = 118,14 kmol/h. V khi lng nguyn liu iso-C4H10 cn cha cc thnh phn kh khc nh propan, n-butan, buten... v iso-C4H10 ch chim 90% th tch. Vy lng kh iso-C4H10 nguyn liu cn a vo l: Giso- C 4 H 10 nguyn liu = 0,9 = 218,78 kmol/h
196,90

Vy thnh phn v khi lng kh iso-C4H10 nguyn liu a vo nh sau: Bng 13: Thnh phn v khi lng kh iso-C4H10 nguyn liu a vo:
STT 1 2 3 4 5 6 Tn cu t iso-C4H10 Propan n- C4H10 Tng n- C4H8 C
+ 5

% 90 3 6 0,5 0,495 0,005

kmol/h 196,90 0,03. 218.78 = 6,56 0,06. 218,78 = 13,127 0,005. 218 78 = 1,09 0,495. 10-2.218,78 = 1,08 0,005 . 10-2.218,78 = 0,01 = 218,78

kg/h 196,90. 58 = 11420,2 6,56. 44 = 288,79 13,127. 58 = 761,35 1,09. 56 = 61,26 1,08. 72 = 77,97 0,01. MTB = 0,45

H2Sv Meroaptan Tng

100

Vi

MTB

M H 2 S + M C H 3S H 3 4 + 4 8 = = 41 2 2

Vy Giso- C 4 H 1 0

nguyn liu

= 11420,2 + 288,79 + 761,35

+31,26 +77,97 +0,45 = 12610,02 kg/h. Gi s ch c cc phn ng hyro ha v cc phn ng no cng chuyn ha 40%. C3H8 6,56 n-C4H10 13,127 C3H6 + H2 2,62 (4) 5,25 (3) 2,62 5,25

n-C4H8 + H2

Lng C3H8 tham gia phn ng (3) l: 0,4. 6,56 = 2,62 kmol/h. Lng n-C4H8 tham gia phn ng (4) l: 13,127. 0,4 = 5,25 kmol/h. + Giso-sn phm
:

Dng vt cht i ra khi thit b hyro ha s c ngng t cc cu t t C3 tr ln s ngng khi b nn p sut. Cc cu t C2 tr xung s khng ngng v i ra khi dy chuyn th kh (kh thi). Vy hn hp lng Iso- C4H8 sn phm i ra khi phn hyro ha c khi lng v thnh phn nh sau: Iso- C4H8: l lng Iso- C4H8 to ra: 72,46 kmol/h = 405,76 kg/h Iso- C4H10: bng lng Iso- C4H10 cn li cha chuyn ha v bng: 196,90 - 78,76 = 118,14 kmol/h = 6852,12 kg/h n-C4H10 : bng lng c ban u - lng tham gia phn ng v bng: 13,127 - 5 25 = 7 88 kmol/h = 456,87 kg/h. n-C4H8 : bng lng c ban u trong nguyn liu + lng to ra phn ng (4): 1,09 + 5 25 = 6 34 kmol/h = 355,04 kg/h. C3H8 : bng lng c ban u trong nguyn liu - lng phn ng theo (3): 6,56 - 2,62 = 3,94 kmol/h = 177,36 kg/h. C3H6 : bng tng lng to ra do phn ng (2) v (3): 3,16 + 2,62 = 5,77 kmol/h = 242,34 kg/h.
+ C 5 : bng lng c ban u:

1,08 kmol/h = 77,97 kg/h. Vy Giso- C 4 H 8 +Gkh

thi

sn phm

= 12215,46 kg/h.

: kh thi gm c H2, CH4, C2H4, C2H6, H2S v

Mercaptan khi lng v thnh phn hn hp kh thi nh sau:

H2 l tng lng kh thi to ra do cc phn ng

(*), (3) v (4) bng: 72,46 + 2,62 + 5,25 = 80,33 kmol/h = 160,66 kg/h.

CH4: l lng to ra do phn ng (2) l: 3,15 kmol/h =50,4 kg/h. C2H4: l lng C2H4 to ra do phn ng (1): 3,15 kmol/h = 88,2 kg/h. C2H6: l lng C2H6 to ra do phn ng (1): 3,15 kmol/h = 94,5 kg/h H2S: l lng H2S c ban u: 0,01 kmol/h = 0,45 kg/h.

Vy Gkh thi = 394,21 kg/h. Vy cn bng : Giso- nguyn liu = Giso- sn phm + Gkh thi 12610,02 2610,02 Hn hp C (iso-C4H8) sn phm i ra khi phn hyro ha c khi lng Giso- C 4 H 8 G1 = 12215,46 kg/h Trong thnh phn v khi lng nh trong bng 14. Bng 14: Thnh phn v khi lng kh ra khi phn hyro ha: Thnh phn iso-C4H8 iso-C4H10 n-C4H10 % 33,6 54,8 3,7 Kmol/h 72,46 118,14 7,88 Kg/h 4057,76 6582,12 456,87
sn phm

12215,46 + 394,21

v cng l G1:

n-C4H8 C3H8 C3H6 C5

+

2,9 1,8 2,7 0,5

6,34 3,94 5,77 1,08 215,61

355,04 173,36 242,34 77,97 12215,46

Tng

100

Hn hp ny l dng nguyn liu i vo phn tng hp MTBE. By gii ta thay G1 = 12215,46 kg/h vo phng trnh cn bng vt cht cho giai on tng hp MTBE ta c: G1 + GMeOH (99,9%) = G
O

C4

cha phn ng

+ GMTBE + GMeOH trong MTBE + GH 2

G1 = 12215,46 kg/h GMeOH (99,9%) = 2361,18 kg/h GMTBE = 6313,13 kg/h GMeOH trong MTBE = 63,16 kg/h GH 2 O =2,36 kg/h Ta c G C 4 Phn ng: Iso- C4H8 71,74 + MeOH 71,74 MTBE 71,74 (kmol/h).
+

cha phn ng

= 8198,02 kg/h

Xc nh thnh phn v khi lng dng C4 cha phn ng:

Nu coi rng phn ng t chuyn ha 90% mol (theo iso-C4H8) v chn lc t 100% th lng MTBE to ra 71,74 kmol/h. Lng iso-C4H8 cn to ra lng 71,74 kmol/h MTBE l:

71,74 = 72,46kmol/h 0,99

Lng iso-C4H8 cha chuyn ha l: 72,74 - 71,74 = 0,72 kmol/h. Ngoi ra cc cu t khc trong hn hp l tr khng phn ng. Vy thnh phn v khi lng ca kh C 4 cha phn ng theo bng 15 sau:
+

Bng 15: Thnh phn v khi lng ca kh C 4 cha phn ng. Thnh phn iso-C4H8 iso-C4H10 n-C4H10 n-C4H8 C3H8 C3H6 C5
+

% 0,5 82,1 5,5 4,4 2,7 4,0 0,8 100

Kmol/h 0,72 118,14 7,88 6,34 3,94 5,77 1,08 143,87

Kg/h 40,32 6852,12 456,87 355,04 173,36 242,34 77,97 8198,02

Tng

Tm li ta c bng cn bng vt cht chung cho ton b phn xng bng sau: Bng 16: Cc dng vt cht cho ton phn xng. Cc dng vt cht i vo (kg/h) Giso- C 4 H1 0 nguyn liu = 12610,02 GMeOH (99,9%) = 2361,18 Cc dng vt cht i ra (kg/h) GMTBE = 6313,13 G
C4
+

cha phn ng

= 8198,02

GMeOH trong MTBE = 63,13 GH 2 O =2,36 Gkh thi = 394,21 Tng = 14971,20 Tng = 14970,85 *Tnh lng nguyn liu mi cn thit a vo dy chuyn: Kh Raffinat-2 sau khi thu hi c em x l loi cc cu t cha oxi nh: Metanol, MTBE, H2O (vi lng nh), loi Propan v Propylen... t tiu chun nh kh iso-butan nguyn liu ri c tun hon trn vi nguyn liu mi. Ta c: Dng iso-C4H10 + lng iso-C4H10 tun hon = lng iso-C4H10 i vo dy chuyn. Tnh theo cu t iso-butan ta c: 196,90- 118,14 = 78,76 (kmol/h). V trong Iso-butan nguyn liu th isobutan ch chim 90% th tch. Vy trong isobutan nguyn liu mi cn a vo dy chuyn l:
78,76 = 87,51 kmol/h 0,9

Bng 17: Lng iso-butan nguyn liu mi cn a vo dy chuyn. Thnh phn iso-C4H10 % 90 Kmol/h 78,76 Kg/h 4568,08

Propan n-C4H10 Tng n-C4H8 C5

+

3 6 0,5 0,495 0,005 100

0,03. 87,51= 2,63 0,06. 87,51= 5,25 0,005. 87,51= 0,44 0,495. 10-2. 87,51= 0,43 0,005. 10-2. 87,51= 4,4.10-3 87,51

2,63. 44= 115,51 5,25. 58= 304,54 0,44. 56= 24,50 0,43. 72= 31,19 4,4.10-3. 41= 0,18 5044

H2S v Mercaptan Tng

Giso- C 4 H 1 0 nguyn liu mi = 5044 kg/h. Isobutan tun hon c thnh phn ging nh nguyn liu mi v khi lng nh sau:

Bng 18: Thnh phn v khi lng ca dng tun hon. Thnh phn iso-C4H10 Propan n-C4H10 Tng n-C4H8 C5
+

% 90 3 6 0,5 0,49 5 0,00 5 100 0,03. 0,06.

Kmol/h 118,14
118,14 0,9 118,14 0,9

Kg/h 6852,12 3,94. 44 = 137,27 7,88. 58 = 456.81 0,66. 46 = 36,75 0,65. 72 = 46,78 0,0066. 41= 0,27 7566

= 3,94 = 7,88

0,005. 0,9 = 0,66 0,495. 10-2. 0,005. 10-2.

118 ,14 0,9

118,14

= 0,65

H2S v Mercaptan Tng

118 ,14 0,9

= 0,0066

131,28

Cn bng ta c: Lng iso-C4H10 mi vo + lng iso-C4H10 tun hon = lng iso-C4H10 vo dy chuyn. 5044 + 7566 = 12610,02 = 12160,02 12160,00