TNG QUAN V QUA TRNH ALKYL HOA

I-Gii thiu chung v qua trinh alkyl hoa : Qua trnh alkyl hoa la mt trong nhng qua trnh quan trong cua nha may loc du nhm san xut cac isoparafine ma chu yu la cac iso-octane cu t xng co ch s octane cao t olefine nhe va iso-butane. Alkylat nhn c la cu t tt nht pha ch tao xng cao cp v no co tr s octane cao va nhay be (RON>=96,MON>=94), ap sut hi thp, iu o cho phep ch tao c xng theo bt ky cng thc pha trn nao. Ngoai ra khi alkyl hoa benzen bng olefine nhe cung cho ta alkylbenzene co tr s octane cao dung san xut xng hoc tng hp hoa du va hoa hoc. Nh qua trnh nay trong tng lai cac nha may loc du se loai bo hoan toan ham lng ch va ham lng aromatique, nht la benzene trong xng. Mi y, My quyt nh loai bo tt ca ch va han ch ham lng cua mt vai cu t c xem la nguy him trong xng. Qua trnh tai tao xng la cn thit, nhng nhng rang buc chu yu phai ap ng nh sau: - Loai bo tt ca ch trong xng. - Giam ham lng benzene trong xng n gia tr nho hn 1% th tch. - Giam ham lng aromatique xung nho hn 25% th tch. -Ham lng olefin ln nht khoang 10% th tch. -Ham lng oxy ln hn 2% khi lng. -Ap sut hi khoang 0,46 - 0,56 bars. Alkylat la mt trong nhng thanh phn c ban cua nhin liu thoa man toan b nhng tiu chun cua xng tai tao. II-C s cua qua trnh alkyl hoa iso-butane bng olefine: 2.1-Nguyn liu: 2.1.1-Tnh cht cua iso-butane va olefine: a- isobutane: Iso-butane la hydrocarbure ho parafinique co cu truc mach nhanh, cng thc phn t C4H10 vi cng thc cu tao sau: CH3 CH 3 CH CH3 nhit thng iso-butane la cht kh trong sut, khng co mui, khi lng phn t la 58.2, khng tan trong

nc, rt t tan trong cac hp cht cha oxy va co cc noi chung. Mt s tnh cht ly hoa cua isobutane: Tnh cht Ga tr Nhit nong chay(0C) -159.44 Nhit si(0C) -11.57 3 Khi lng ring(g/cm ) 0,557 0 Nhit ti han( C) 135.1 Ap sut ti han (atm) 36.0 Th tch ti han (cm3/g mol) 263 Nhit nong chay (kj/g mol) 4.540 Nhit hoa hi (kj/g mol) 21.29 H s nen ti han 0.283 Gii han n vi khng kh cua iso-butane (% th tch ap sut kh quyn): -Gii han trn: 8.5% -Gii han di: 1.8% Tr s octane: RON=100, MON = 99 nhit thng iso-butane tr v mt hoa hoc, con nhit cao hoc co anh sang va s co mt cua xuc tac no co th co kha nng tham gia phan ng th. Trong nha may loc du th iso-butane thu c t cac qua trnh nh : ng phn hoa, cracking xuc tac, hydrocracking, cracking nhit... b-olefine nhe: Olefine la nhng hp cht hydrocarbure khng no, trong phn t co lin kt i, cng thc phn t tng quat la: CnH2n+2-2k trong qua trnh alkyl hoa, san xut iso-parafine thng s dung cac oleffine nh :C3H6,C4H8,C5H10 ... iu kin thng, propene va butene la cht kh khng mau, khng mui con pentene la cht long khng mau co nhit si thp. Tt ca cac olefine nay u tao vi khng kh mt hn hp n ht sc nguy him. Cac olefine nay tan kha tt trong nc c bit la hp cht co cc (do o hoa tan trong acid cua olefine ln hn nhiu so vi parafine). Mt s tnh cht ly hoa cua olefine nhe c cho bang sau: Olefine Tnc(0C TS(0C Tth(0C) Gii han n vi khng ) ) kh (% V) Propene -17.8 81.8 2.2 10 Butene-1 185.2 -6.3 146.2 1.6 9.4 Cis butene-2 13.5 151.0 1.6 9.4 Trans 185.3 10.9

butene-2 Iso_butene _pentene

138.9 140.8 163.2

-6.9 30.1

144.7

1.6 1,9 1.8 9.6 1.3 8.8

Olefine co th than gia cac phan ng sau: -Phan ng cng, v du nh cng H2 tao parafine: CnH2n+H2 CnH2n+2 Trong phan ng cng nu cng mt phn t bt i xng vao phn t olefine th phn mang in dng se tn cng vao nguyn t C mang nhiu hydro con phn in tch m se tn cng vao nguyn t C mang t hydro cha ni i. -Phan ng oxy hoa: cac olefine co kha nng tham gia phan ng oxy hoa vi ozone, nc KMnO4 trong mi trng kim. -Phan ng polyme hoa tao thanh cac phn t nng (phan ng trung hp), trong qua trnh alkyl hoa lam giam hiu sut va cht lng alkylat. 2.1.2-Cac ngun nguyn liu chnh: a- San phm cua qua trnh cracking xuc tac: Hiu sut thu hi kh cua qua trnh cracking xuc tac chim khoang 10-15% lng nguyn liu. Hiu sut nay phu thuc vao ban cht nguyn liu, iu kin tin hanh qua trnh. Nu cracking xuc tac iu kin nhit cao, tc nap liu nho, h s tun hoan ln, th hiu sut thu hi kh se cao va ngc lai. Thanh phn cua kh cracking xuc tac phu thuc vao ban cht cua nguyn liu c cho nh bang sau: Cu t C2H4 C3H8 C3H6 n-C4H10 i-C4H10 n-C4H8 n-C5H12 i-C5H12 Kh khac Nguyn liu nhe 2.40 11.70 10.75 5.30 23.40 1.00 6.30 15.70 23.45 Nguyn liu nng 7.00 10.85 13.30 8.75 19.75 18.55

Thanh phn cua phn oan kh cua qua trnh cracking xuc tac phu thuc vao ban cht xuc tac nh sau: Cu t Xuc tac Xuc tac Aluminosilicat Zeolithe C3H6 23.1 25.6 C3H8 7.0 5.7 n-C4H8 15.6 16.0 i-C4H8 6.7 10.0 n-C4H10 6.4 3.0 i-C4H10 28.1 15.2 Theo bang s liu trn th nu tin hanh qua trnh cracking cac phn oan nhe vi xuc tac Zeolithe th trong hn hp kh thu c iso-butane chim mt ham lng ln con vi butene th hiu sut thu hi trong trng hp dung phn oan va xuc tac aluminosilicat lai cao hn. b-San phm kh cua qua trnh hydrocracking: Trong cng nghip loc hoa du ngi ta s dung phn oan xng va gasoil lam nguyn liu cho qua trnh hydrocracking vi muc ch thu kh hyrocarbure cn thit va san phm dung lam nguyn liu cho qua trnh reforming. Nm 1967 Nht a thit k 4 nha may kiu iso-mark san xut propane va butane, cung vi xng co tr s octane cao C5, C6 t nguyn liu la xng chng ct trc tip co tr s ortane thp. Thanh phn nguyn liu va san phm cua mt qua trnh hydrocracking trong cng nghip nh bang di. T o ta thy ham lng iso-butane trong hn hp kh thu c chim mt gia tr ang k, y la ngun nguyn liu tt cho qua trnh alkyl hoa (chu yu la kh no). Thanh phn nguyn Phn oan 95liu 800C Parafine %k lng 77 Naphtene % klng 20 Aromatique % 3 klng Thanh phn san phm C1-C2 % klng 0.6 C3 % klng 13.2 i-C4 % klng 27.5 n-C4 % klng 10.7 i-C5 % klng 4.3 i-C6 % klng 12.4 n-C6 % klng 1.5 Phn oan 981400C 72 23.5 4.5

0.27 21.4 33.95 8.39 1.54 8.42

c-San phm cua qua trnh cracking nhit: Thanh phn cua kh cracking nhit bao gm cac parafine nh: CH4, C2H6, C3H8, n_C4 va i_C4 va cac olefine nh: C2H4, C3H6, C4H8. Ham lng cua chung co mt trong thanh phn khng phu thuc vao ban cht cua nguyn liu, ch cng ngh (Nhit , ap sut cua qua trnh)

Cu t CH4 C2H6 C3H8 n-C4H10 i-C4H10 C2H4 C3H6 n-C4H8

Cracking nhit P cao 37.0 18.0 16 4 2 4 9 4

Cracking nhit Pthp 27.0 22.0 2.5 1.0 _ 25.0 15.0 7.0

Theo bang s liu trn th kh cracking nhit co ham lng CH4 cao, con cac kh thuc phn oan C3-C4th co ham lng thp. d-Cac ngun thu khac: i vi iso-butane ngoai cac ngun thu trn ta con thu c t cac qua trnh ng phn hoa(isomere hoa). Qua trnh ng phn hoa thc hin s chuyn hoa cac nparafine thanh cac iso- parafine noi chung va n-butane thanh iso-butane noi ring dung lam nguyn liu cho qua trnh alkyl hoa. Con cac butene thu c t cac qua trnh dehydro hoa theo phan ng: C4H10 C4H8+ H2 2.1.3-X ly ngun nguyn liu: Nguyn liu cua qua trnh alkyl hoa cng nghip la phn oan butane, butylene, nhn c t qua trnh hp phu, phn tach kh cracking xuc tac la chu yu, phn oan nay cha 80-85% phn oan C4, phn con lai la C3 , C5 va cac tap cht nh: hp cht cua nit, lu huynh, oxy (cbit la H2O, mercaphtane, disulfure, methanol, dimethyl ether, MTBE), cac hp cht nay d tac dung vi xuc tac acide lam tng lng acide tiu hao trong qua trnh.

Anh hng cua tap cht n lng acide tiu thu trong qua trnh alkyl hoa nh bang sau:

Tap cht

Nc Butadiene Ethylene Mercaphtane(tnh bng kg S) Disulfure (tnh bng kg S) Methanol Dimethyl ether MTBE -Anh hng cua olefine trong nguyn liu: Trong nguyn liu cn cha t ethylene va nht la butadiene v khi tip xuc trc tip vi acide (c bit la acide sulfurique) chung se tao thanh cac polymere hoa tan trong acide lam giam nng acide do o lam giam hoat tnh xuc tac cua acide. x ly nguyn liu ta co th dung phng phap hydro hoa chon loc nhng lai khng kinh t i vi qua trnh s dung acide sulfurique. Ngc lai phng phap nay lai hiu qua hn vi qua trnh alkyl hoa bng acide fluorhydrique nu ng thi vi qua trnh hydro hoa butadiene ( cung iu kin) con co qua trnh isomere hoa v tr lin kt i : butene-1 butene-2. Qua trnh nay cho ta alkylat co im si cui thp (giam t 200 1750C va ch s octane cao (RON t 93 96, MON t 91.5 93.5). - Anh hng cua n-butane va propane : Mc du khng tham gia vao phan ng nhng propane va n-butane lai co anh hng n qua trnh v chung chim th tch vung phan ng, lam giam nng isobutane va lam giam nng xuc tac. cai thin iu kin alkyl hoa cn phai tach su hn cac n-parafine bng cac ct tach propane va butane. - Anh hng cua H2O:

Lng acid tiu thu (kg/kg tap cht) 10.6 13.4 30.6 17.6 12.8 26.8 11.1 17.3

Noi chung nguyn liu cua phn xng alkyl hoa bng acide sulfurique khng cn phai lam kh. Ngc lai nguyn liu cua phn xng alkyl hoa bng HF cn phai lam kh va ham lng nc rt nho (< 2 ppm). S co mt cua nc trong nguyn liu la do: Nc t qua trnh tach mui. Nc t qua trnh Ether hoa. -Anh hng cua hp cht cha oxi: S xut hin cua hp cht cha oxi trong nguyn liu cua qua trnh alkyl hoa la kt qua cua qua trnh san xut ether trc khi a vao phn xng alkyl hoa. Anh hng cua cac hp cht nay n mc tiu hao acide la rt ln nh a bit trong s liu bang trn. 2.2- San phm Alkylat: 2.2.1-Thanh phn alkylat: Nhng san phm u tin cua phan ng alkyl hoa isobutane bng olefine c cho bang sau: Olefine Propylene Iso-butene Butene-1 Butene-2 San phm Dimethyl-2,3 pentane Dimethyl-2,4 pentane Trimethyl-2,2,4 pentane Dimethyl-2,3 hexane Dimethyl- 2,4 hexane Trimethyl-2,2,3 pentane Trimethyl- 2,2,4 pentane Trimethyl- 2,3,4 pentane Trimethyl- 2,3,3 pentane MON 89 84 100 79 70 99.9 100 96 99 RON 91 83 100 71 65 109.6 100 103 106

Nhng s liu bang trn ch phan anh qua trnh alkyl hoa iso-butane bng olefine t 3 n 4 nguyn t carbone trong phn t. Qua trnh alkyl hoa iso-butane bng ethylene c bo qua. Ham lng ethylene trong nguyn liu la rt nho va olefine nay la cht co anh hng xu n lng xuc tac (HF va H2SO4) tiu thu. Thanh phn thc cua alkylat rt phc tap, no bao gm mt hn hp phc tap cua nhiu parafine t 5 n

12 va nhiu hn na s nguyn t carbone. Hai loai alkylat trong cng nghip thu c t qua trnh alkyl hoa isobutane bng phn oan C4 olefinique co thanh phn nh trang sau. y ta thy, phn oan C8 cua alkylat la san phm chnh cua phan ng, no chim khoang 62% th tch i vi xuc tac H2SO4 va 74% i vi xuc tac HF. Qua trnh alkyl hoa iso-butane bi butene la mt qua trnh phan ng san xut phn oan C8 (octane). Trong alkylat, t 6 n 18 isomere co th xut hin va chim khoang 90% th tch phn oan nay. Nhng isomere chnh la: Dimethyl-2,5 hexane; Dimethyl- 2,4 hexane; Dimethyl-2,3 hexane; Trimethyl-2,2,4 pentane. Trong san phm alkylat, cac cu t n nh nhit khng nhiu. nhit bnh thng cua qua trnh alkyl hoa nhng cu t nh: Methyl heptane, Dimethyl-3,5 hexane va Dimethyl-2,2 hexane chim 60% phn oan C8.

Cu t ( % th tch ) Propane Iso- butane n-butane iso-pentane n-pentane Dimetyl-2,2 butane Dimethyl-2,3 butane Methyl-2 pentane Methyl-3 pentane n-hexane Dimethyl-2,2 pentane Dimethyl-2,4 pentane Trimethyl-2,2,3 butane Dimethyl-3,3 pentane Dimethyl-2,3 pentane Methyl-2 hexane Methyl-3 hexane

Qua trnh alkyl hoa vi xuc tac : H2SO4 HF 0.05 0.04 0.13 0.92 4.87 0.76 5.1 0.23 0.01 5.36 2.38 1.29 0.91 0.64 0.40 0.25 0.17 3.62 1.95 0.01 0.01 2.15 1.31 0.22 0.24 0.14 0.12 0.01 0.01

Ethyl-3 pentane n-heptane 24.2 38.02 Trimethyl-2,2,4 0.04 pentane 2.89 4.19 Dimethyl-2,2 hexane 4.69 3.57 Dimethyl-2,4 hexane 1.53 1.35 Dimethyl-2,5 hexane Trimethyl-2,2,3 13.15 9.63 pentane 3.41 4.90 Dimethyl-3,3 hexane Trimethyl-2,3,4 0.08 0.09 pentane 11.47 8.14 Dimethyl-2,3hexane 0.26 0.59 Methyl-4 heptane 0.23 3.20 Methyl-2 heptane 7.20 3.20 Trimethyl-2,3,3 6.90 5.52 pentane Dimethyl-3,4 hexane Methyl-3 heptane Trimethyl-2,2,5 hexane Hydrocarbure nng 2.2.2 San phm alkylat cua qua trnh alkyl hoa bng acide HF: a- Hiu sut va cht lng san phm: Anh hng cua nguyn liu olefine n hiu sut va cht lng san phm alkylat trong qua trnh alkyl hoa c cho bang sau: C3= 12i-C4= C3=+C C5= Nguyn liu
C4= C4=
= 4

1.7 1.78 1.29 1.6 7 1.28 1.28 3 1.1 95.9 93.7 1 4 93.4 90.8 91. 97. 5 8 90 94. 6 S tai sinh xuc tac c thc hin trong thit b chng ct n gian, s tiu thu xuc tac c biu th qua trnh alkyl hoa lng fluor mt mat trong cn goudron, lng nay nho hn1kg/tonne va no khng nhay cam i vi ban cht cua olefine . b-Thanh phn cua alkylat : Anh hng cua olefine n thanh phn cua alkylat thu c t qua trnh alkyl hoa bng xuc tac HF nh sau:

Hiu sut(VC5+/Volefine ) Mc tiu thu i-C4(ViC4/Volefine ) RON san phm MON san phm

1.7 6 1.3 6 92 90

8.7 3 1.1 94. 4 91. 6

Thanh phn alkylat Ban cht nguyn liu = (%khi lng) C3 2-C4= 1-C4= C3+C4 C5 4.8 2.2 2.7 3.7 C6 3.9 1.8 1.7 2.9 C7 45.8 2.8 2.7 25.5 TMPS 30.5 81.2 65.6 54.2 DMHS 3.5 9.2 20 7.2 + C9 11.5 2.8 7.3 6.5 + RON 90.6 97 94 93 TMPS-Trimethyl pentane. DMHS-Dimethyl hexane. Theo bang trn ta thy rng cht lng alkylat thu c khi qua trnh alkyl hoa iso-butane bng butene-1 la khng tt. Ham lng DMHS cao, hp cht nay co RON be, va cung co th sinh ra t qua trnh isomere hoa khng hoan toan butene-1 thanh butene-2 trc khi qua trnh alkyl hoa giai oan qua trnh alkyl hoa . 2.2.3- Alkylat i ra t qua trnh alkyl hoa bng acide sulfurique : a- Hiu sut va s tiu thu xuc tac: Anh hng cua nguyn liu olefine n hiu sut va s tiu thu xuc tac c cho bang sau:

Ban cht nguyn liu Propylene Butene Amylene + Hiu sut (ttch C5 /ttch 1.45-1.78 1.74 1.57 olefine ) 137-171 51-102 102-171 Lng acide tiu 1.27-1.32 1.24 1 + thu(kg/tonne C5 ) 88-90 92-94 88-90 Tiu thu i -C4(th tch/th 89-92 94-98 90-92 tch olefine ) MON RON T bang trn ta thy rng ban cht cua nguyn liu anh hng ln n lng acide tiu thu Mc tiu thu at n gia tr ln hn 100 kg/ tonne dalkylat C5+ i vi nguyn liu cha propylene hoc ham lng amylene cao. b-Thanh phn va cht lng alkylat :

Vi xuc tac la acide sulfurique, alkylat tt nht la nhn c t qua trnh alkyl hoa vi nguyn liu co ham lng n-butene cao. Nghin cu cht lng alkylat thu c t qua trnh alkyl hoa vi nguyn liu la iso-butane va amylene thy rng cht lng alkylat cung nh s tiu thu xuc tac phu thuc manh vao ham lng amylene, s tiu thu xuc tac tr nn ang k vi ham lng amylene vt qua 20% khi lng. Anh hng cua ham lng amylene trong nguyn liu olefine n ch s octane c biu th nh sau: Ch 98 s 96 ortane 92 90 88 86 liu. Fig.1. RON 94 MON 20 40 60 80 100 % amylene trong nguyn

Anh hng cua ham lng amylene trong nguyn liu n s tiu thu acide sulfurique nh sau: Lng 200 acide tiu 150 thu (kg/t C5+)100 50 20 100 40 60 80

Fig.2. % amylene trong nguyn liu 2.3-Nhit ng hoc cua phan ng:

Qua trnh alkyl hoa bao gm phan ng cua 1 mol isobutane va 1 mol olefine tao thanh 1mol iso-parafine .Trong trng hp olefine la butene th phan ng c vit nh sau: i-C4H10+C4H8 i-C8H18 (kh) (kh) (kh) : G = -18350 +39.1T 0 G < =0 khi T <=196 0C i-C4H10+C4H8 i-C8H18 (kh) (kh) (long) : G = 27100 +63.2T 0 G < =0 khi T <=156 0C Lng nhit toa ra cua phan ng phu thuc ban cht cua olefine phan ng alkyl hoa kem theo s toa nhit va giam s lng phn t cht tham gia phan ng do o phan ng thc hin thun li nhit thp va ap sut cao. Anh hng cua olefine n lng nhit toa ra cua phan ng : Olefine H ( kj/mol) Propylene -81.5 Butene-1 -89.4 Buten-2 cis -82.5 Butene- 2 trans -78.4 Pentene -74.9 2.4- C ch cua qua trnh alkyl hoa : Phan ng tng quat: i-C4 + olefine iso-parafine Cac phan ng alkyl hoa xay ra theo c ch gc, hp cht trung gian la Carbocation, qua trnh co xay ra phan ng phu va toan b qua trnh tao ra hai hn hp: - Iso-parafine goi la alkylat . -Polymere hoa tan trong acide huiles solubes. 4.1-C ch tao alkylat : 4.1.1-Phan ng chnh: Olefine (nh :butene-1, butene-2) b proton hoa sinh ra mt Carbocation trung gian: 2-C4=+H+X n-C4+X- (X-:HSO4- hoc F- ).(1) 1-C4= +H+X- n-C4+X- (2) Cac cu t n-C4+X- cn bng nhit ng vi hn hp cua butene-1 va butene-2 hoc butene-2 se chim u th: n-C4+X- 2-C4=+H+Xn-C4+X- cung co th phan ng vi iso-butane bng phan ng chuyn v hydrogene sinh ra butane mach thng va mtcation tertiobutylique: n-C4+X- + I-C4 i-C4+X- + n-C4 H (4) H Phan ng nay thng c goi la phan ng khi mao hay giai oan khi mao. Khi i-C4+X- at nng cao,

butene-2 (cn bng vi n-C4 H) se phan ng vi nhng Carbocation i-C4+X- cho 2,2,3 TMP (Trimethyl- 2,2,3 pentane): 2-C4= + i-C4+X- 2,2,3TMP+X- (5) Phan ng cn bng (3) se dch chuyn sang phai. Nu vn tc phan ng (5) cao hn nhiu so vi phan ng (1) va (2) th co s thm vao trc tip olefine trn carbocation iC4+X, trong trng hp nay ban cht isomere i-C8+X- tao thanh phu thuc vao ban cht cua butene (2,2,3TMP hoc 2,2DMH). 2-C4= +i -C4+X- 2,2,3TMP+X- (6) 1-C4= +i -C4+X- 2,3 DMH (7) Khi xuc tac la H2XO4, phn ln butene-1 c isomere hoa thanh 2-C4= trc khi cng vao i-C4+X-. Khi xuc tac la HF qua trnh isomere hoa khng hoan toan (phan ng (2),(3) ). Qua trnh phn ly cac cu t TMP+X- va DMH+X- c thc hin bng phan ng chuyn v hydro : TMP+X- + i-C4 i-C4+ X- +TMP (8) H H + + DMH X + i-C4 i-C4 X + DMH (9) H H Nh vy Carbocation i-C4+ X- c tai tao. C ch trn c vit cho qua trnh alkyl hoa isobutane bi n-butene v qua trnh alkyl hoa bi propylene, isobutene, amylene rt phc tap v co nhiu phan ng phu. 4.1.2-Phan ng phu: S xut hin cua phan ng phu tao thanh cac phn oan nhe (t C5 n C7) va phn oan nng (t C9n C12) trong alkylat.Nhng phan ng phu chu yu nh sau: -Polyalkyl hoa: TMP+X- + C4= C12+XDMH+X- + C4= C12+XC12+X- + i-C4 H i-C12 H + i-C4+ X-cracking: C12+X- C6+X-+ C6= C6+X-+ i-C4 H C6 H + i-C4+ XC6= + H+X- C6+XC6+X- + i-C4 H C6 H + i-C4+ X-chuyn v hydro : C3= +2 i-C4 H C3 H + 2,2,4 TMP 2.4.2- C ch tao du hoa tan (hiules solubes): Cac phan ng tao du hoa tan co s tham gia cua hp cht olefine con iso-butane khng tham gia: 4 C4= + H+X- C16+ XC16+ X- + C4= n-C4 H + C16=+ XC16=+ X- + C4= n-C4 H + C16==+ XNhng phan ng tip theo chuyn i hydrogene dn n s tao thanh polymere khng no hoa tan trong xuc tac HF va H2SO4 lam giam hoat tnh xuc tac .

Vi s co mt cua acide sulfurique ,cac phan ng oxy hoa iso-parafine va olefine cung tao thanh du hoa tan, nc va sulfure dioxyde: i-C8 +4H2SO4 C16H28 + 4H2O + 2SO2 2.4.3-Cu truc va vai tro cua du hoa tan: Du hoa tan la hp cht khng no, no cha vong 5 nguyn t C, va co trung bnh khoang 10 20 nguyn t C trong phn t. Nhng polymere nay co th phan ng vi acide sulfurique tao thanh Ester. Ty s hydrogene/carbone thng khoang t 1,52 1.75 va co th giam nu cac polymere b oxi hoa bi acide sulfurique . Vai tro cua du hoa tan trong qua trnh alkyl hoa :phan ng alkyl hoa xay ra trn b mt tip xuc pha gia hydrocarbure va acide. Khi b mt tip xuc pha cang ln , th phan ng xay ra cang manh.Trong qua trnh alkyl hoa du hoa tan ong vai tro la cht hoat ng b mt lam tng b mt tip xuc pha gia hydrocarbureva acide (hydrocarbure khng co cc nhng acide co cc). C ch tao du hoa tan lam giam hiu sut cua phn oan C8 nhng no co vai tro tch cc lam tng b mt tip xuc gia hai pha. 2.5- Xuc tac : 2.5.1- Xuc tac acide long : Phan ng alkyl hoa iso-butane bi olefine co th c thc hin ma khng co mt cua xuc tac. Trong nhng iu kin nghim ngt :nhit ln cn 500 0C va ap sut t 200 400 bars. Khi co mt cua xuc tac acide, phan ng thc hin nhit thp hn (<500C) va ap sut thp hn (< 30 bars ). Co hai loai xuc tac c s dung trong phn xng alkyl hoa san xut alkylat o la acide fluorhydrique va acide sulfurique trang thai long . c trng ly hoa cua hai loai xuc tac c cho bang sau: c trng ly hoa Khi lng phn t Ty trong chun (d415) Nhit si (0C) Nhit nong chay (0C) nht (cP) acide Hammett ( -H0 ) hoa tan (% khi lng) : Acide fluorhydrique (HF) 20.01 0.99 19.4 -82.8 0.286 (00C) 10.0 2.7 Acide sulfurique (H2SO4) 98.08 1.84 290 10 33(150C) 11.1 -

i-C4H10 trong acide 99.5%(270C) i-C4H10 trong acide 100% (130C) HF trong i-C4H10 (270C) HF trong C3H8 (270C)

0.44 0.90

0.1 -

+Vi xuc tac H2SO4 th nng khoang 94 96 % khi lng nng acide m c hn th tnh cht oxi hoa manh va tnh cht nay lam phc tap thm qua trnh nh d tao nha, d tao SO2, SO3, va H2S lam giam hiu sut alkylat. Khi nng acide sulfurique thp qua, no d dang xuc tac cho qua trnh isomere hoa, d tao thanh cac hp cht alkyl sulfat tng ng va khi t nong chung b phn huy thanh cac cht n mon lam loang nhanh acide sulfurique. Acide sulfurique a c s dung trong cac dy chuyn hin ai thng c a vao tai sinh bng phng phap phn huy nhit cao. Hiu qua cua qua trnh alkyl hoa c tng ln khi thm vao xuc tac cac cht kch hoat c bit, no lam thay i sc cng b mt cua gii han phn chia hoc tao thanh nhu tng trong acide sulfurique. + Vi xuc tac la acide fluorhydrique ngi ta thng dung nng ln hn 87 % khi lng. Do co mt cua cac san phn nng (v polymere hoa ) va nc ma lam giam nng acide HF. Khi trong xuc tac ch cha lng nho H2O (<1.5% khi lng) va hydrocarbure nng (<12% khi lng) th hoat tnh xuc tac la tt nht. Khi nng acide fluorhydrique nho hn 87% no c a i tai sinh . Ngay nay UOP a phat minh ra c xuc tac HF dang acide rn va d th hoa xuc tac HF. Cai tin mi nay mang lai u im ni bt la: -Thay th c xuc tac HF dang long co tnh n mon manh va c hai do vy cac thao tac an toan hn va mi trng sach hn. -Hoat tnh tng ng vi dung xuc tac dang HF long -D tach san phm v a d th hoa xuc tac.

2.5.2. So sanh xuc tac HF va H2SO4. Trong nhng nm gn y cng nghip alkyl hoa dung xuc tac HF c nghin cu va phat trin cac hang ln nh: UOP, Phillips v qua trnh alkyl hoa nay co nhng u im ro rt hn so vi cng ngh dung xuc tac acide sulfurique nh :

+ Tiu tn xuc tac t hn so vi khi dung xuc tac acide sulfurique :Khi dung xuc tac acide HF th lng xuc tac mt mat chu yu la trong cn goudron lng tiu hao nay nho hn 0.15 lb/thung alkylat. Trong khi o nu dung acide H2SO4 th lng tiu thu nay t 2530 lb/thung alkylat hoc ln hn tuy nguyn liu cha t hay nhiu olefine va ban cht cua olefine anh hng ln n lng acide tiu thu . + Ham lng iso-ortane trong alkylat cua qua trnh alkyl hoa bng HF cao hn so vi qua trnh alkyl hoa dung H 2SO4 iu o co ngha la cht lng alkylat tt hn + Xuc tac cua qua trnh alkyl hoa bng HF c tai sinh bng qua trnh chng n gian, trong khi o qua trnh alkyl hoa bi xuc tac acide sulfurique tai sinh xuc tac bng phng phap phn huy nhit cao. + V HF co kha nng hoa tan trong i-C4 cao hn so vi H2SO4 do o t tn cng khuy trn hn. Mt khac H2SO4 co nht ln hn nhiu do o nng lng tiu tn trong qua trnh vn chuyn va khuy trn ln hn nhiu. + Ga thanh cua HF nho hn so vi H2SO4. Chi ph cho xuc tac H2SO4 khoang 33% tng chi ph cua qua trnh alkyl hoa, con chi ph cho HF ch bng 5% tng chi ph cua qua trnh. + Do khng co tnh oxy hoa nn qua trnh thc hin nhit cao(10- 40 0C ) do o d dang lam lanh bng nc. Ngc lai qua trnh alkyl hoa bng acide sulfurique tin hanh nhit thp hn(0 10 0C, nu t0>100C th phan ng oxy hoa xay ra manh, con nu t 0<00C th nht cao ) do o vn lam lanh kho khn hn. + Thi gian phan ng nho hn (t 10 20 phut) thi gian phan ng cua qua trnh alkyl hoa bng H2SO4 ( t 20 30 phut ). Bn canh nhng u im trn HF con co nhc im so vi xuc tac H2SO4 la c, d bay hi nhit thng (t 0s =19.40C ). Do o khi qua trnh thc hin ap sut cao oi hoi thit b phai kn kht va chu ap. Acide HF rt c i vi con ngi, nu ro r ra ngoai th no se gy bong trm trong i vi da, mt va tuyn nhy. Ngoai ra acide HF co tnh n mon rt manh i vi thuy tinh, btng, va mt s kim loai c bit la li st va hp kim Silic. Bnh thng HF khng gy chay nhng khi co m th se d dang tao thanh hydrogene trong thung cha va ng ng d dang xay ra nguy c chay n khi co mt cua ngon la hay tia la in. iu nay dn n qua trnh alkyl hoa bng HF co dy chuyn cng ngh cng knh hn, phai b tr thit b chng chay n xung quanh bn cha HF va b trung hoa acide nu xay ra s c. Qua trnh lu tr phai gi

nhit nho hn 1000 F, nu ln hn 1250 F th phai co h thng lam lanh, do tnh c hai nh vy nn nhn cng lam vic trong phn xng phai c trang b dung cu cung nh trang phuc mt cach nghim ngt, xy dng h thng b thao va b trung hoa x ly khi co s c. H thng thit b, ng ng b cha phai c lam bng vt liu chng n mon manh. T nhng tiu chun la chon trn ta thy rng nu qua trnh alkyl hoa thc hin vi xuc tac HF th noi chung hiu qua kinh t cao hn so vi khi dung H2SO4. Trong qua trnh alkyl hoa bng xuc tac acide sulfurique th chi ph lam lanh va chi ph cho may nen la quan trong nht, chi ph hoat ng th ngc lai no quan trong i vi qua trnh s dung HF. V tng chi ph u t th ca hai loai qua trnh u co th xem la tng dng vi nhau ( nm 1985 , vi nng sut la 185000 tonne/ an th tng chi ph la 14.9 M$ i vi phn xng H2SO4 va 14.5 M$ i vi phn xng HF). 2.5.3- Xuc tac acide rn: thay th acide long ngi ta nghin cu a xuc tac rn vao lam xuc tac cho qua trnh alkyl hoa, nhiu hp cht c a vao th nghim nh: Zeolithe trao i, nha trao i ion (Amberlyst, Nafion ) acide rn (Alumine cloree, zircone sulfat ), acide hp phu trn cht rn (HFSbF5/Al2O3 , BF3/Zeolithe oxyde hoc nha) Anh hng cua xuc tac rn trong qua trnh alkyl hoa isobutane bng butene-2 nh bang sau: xuc tac Nhua Zeolithe ZrO2/SO4 2Nafion Beta Nhit (0C) 100 80 0 = i-C4/2-C4 (mol/mol) 10 10 100 = chuyn hoa C4 (%) 95 100 65 70 San phm : TMP/C5+ (% khi lng) 30 80 62 n nh (h) 20 50 75 Loai xuc tac u co n nh ln, loai th hai co n nh nho va ca hai lai co ty l TMP nho, thi gian phan ng ln. Loai con lai la zircone sulfat co th chp nhn c. Trong tt ca cac loai xuc tac rn t acide manh, trong tng lai c ha hen nhiu nht v mt chon loc va n nh nh: Silic tm CF3SO3H hoc FSO3H, Alumine tm BF3, Silic tm BF5.

Vi nhng loai xuc tac nay mt vai tp oan a s dung nh: TopSoe s dung thit b phan ng tng xuc tac c nh cha xuc tac Silic tm CF3SO3H hoc FSO3H. Catalytica vi Conoco va Neste Oil hoat ng nm 1993 s dung xuc tac BF3 trn Alumine. Chevron hoat ng nm 1994 s dung mt loai xuc tac treo trong thit b phan ng, tao thanh t BF5 ngng tu trn Alumine. IFP a phat trin nhiu loai xuc tac mi t Silic va mt pha acide tao thanh t acide sulfurique va mt cht phu gia (SO3, BO3H ...) 2.6.Cac ch tiu la chon CXT: Qua trnh la chon xuc tac da trn c s hiu qua kinh t, chi ph hoat ng, tng chi ph cho qua trnh lp t xy dng h thng thit b... Co 5 tiu chun chnh la chon xuc tac cho qua trnh alkyl hoa : Cht lng alkylat va ban cht cua nguyn liu . Gia cua xuc tac . Gia cua nguyn liu . Ch ph vn hanh va lam lanh . - Vn an toan trong vn hanh . 2.7-Cac thng s vn hanh cua qua trnh alkyl hoa : Qua trnh alkyl hoa thc hin trong tt ca cac iu kin ma chuyn hoa cua olefine trong nguyn liu la hoan toan. Cac thng s hoat ng c k n anh hng n cht lng alkylat va s tiu thu xuc tac, bao gm cac thng s sau : Thanh phn xuc tac ( ham lng nc va du hoa tan ) Nhit phan ng. Ty l mol gia iso-butane /olefine . Cng sut khuy trong phn xng alkyl hoa bng acide sulfurique cung co th xem nh mt thng s hoat ng, anh hng cua thng s nay n hiu qua cua qua trnh cho n nay t c nghin cu. 2.7.1- Thanh phn xuc tac : Thanh phn cua xuc tac long trong phn xng alkyl hoa la mt thng s quan trong chi phi cht lng alkylat . Nng acide dung khoang 88 98 % khi lng (tt nht la t 94 96 % khi lng ). iu nay quyt

nh n qua trnh tao san phm chnh la iso-ortane, cu t co NO cao. Nh a bit nu acide co nng qua cao phai y n tnh oxi hoa cua no, nu acide co nng thp th tc cua phan ng oxi hoa tng nhanh. V th h thng se at c kha nng phan ng cc ai khi ma nng cua olefine hoa tan trong acide ung bng lng ion carboni tao ra va tham gia phan ng alkyl hoa. Trong qua trnh do co tao cac san phm phu nh hydrocarbure nng, nc, du hoa tan nn lam giam nng acide. Do o trong qua trng phan ng nng acide giam dn, n mt luc nao o cn phai b sung vao mt lng xuc tac mi vi nng khoang 98 99.5%va rut bt xuc tac a s dung nng khoang 90 % khi lng, acide mi phai khng cha SO3 t do han ch nhng phan ng ng oxihoa tao thanh mt phn du hoa tan. Anh hng cua ham lng nc va du hoa tan trong acide sulfurique n cht lng alkylat nh a bit. Thanh phn ti u cua xuc tac tng ng vi ham lng nc khoang 1 % khi lng va ham lng du hoa tan khoang 4 8% khi lng. Anh hng cua thanh phn acide sulfurique n cht lng san phm alkylat c biu hin trn hnh ve Fig.2. Ham lng nc trong xuc tac HF la mt thng s quan trong, nu ham lng nc nho hn 1% thun li cho qua trnh alkyl hoa iso-butane bng phn oan C3-C4 olefinique, ngc lai ham lng nc qua cao (> 1% khi lng) keo theo s tao thanh fluorua cua isopropylene anh hng xu n qua trnh san xut alkylat cht lng alkylat tt nht tng ng vi ham lng nc khoang 2.8 % khi lng.
Ham lng Nc trong xuc tac(%)

95 NOR 6 1 5 4 3 96 NOR 97 NOR 95 NOR 94 NOR

2 98 NOR Fig.3: Anh hng cua thanh phn acide sulfurique n cht 1 lng alkylat

2.7.2- Nhit phan 4.0 6.0 : ng 0. 0.0 2.0

8.0

10. 12 14 16 Ham lng du hoa tan (% khi lng )

Phan ng alkyl hoa la phan ng xay ra thun li nhit thp. Noi chung ch s RON cua alkylat tng mt n v khi giam nhit phan ng xung11 0 C. Trong thc t cac phn xng alkyl hoa bng acide sulfurique hoat ng nhit t 010 0C. Nu nhit nho hn 00C th nht cua acide rt cao lam tiu hao nng lng khuy trn va cht tai nhit trong trng hp nay cung kho tao thanh nhu tng tt thch hp cho qua trnh alkyl hoa, nu nhit ln hn 100C th cac phan ng oxi hoa, oligomere hoa, polymere hoa xay ra manh. Vi xuc tac HF do khng co tnh oxi hoa manh nn cac phan ng alkyl hoa co th thc hin nhit cao hn t 10 40 0C. Anh hng cua nhit phan ng dn hiu sut alkylat va ch s ortane RON cua qua trnh alkyl hoa bng xuc tac HF nh sau: (hiu sut =khi lng alkylat /khi lng butene chuyn hoa) T ( 0C) Hiu sut (%) RON -20 188 100.6 -10 201 99.4 0 175 96 10 127 92.6 Anh hng cua nhit n ch s ortane RON cua alkylat c biu th nh sau (vi xuc tac HF, nguyn liu la phn xng oan C4 cua qua trnh cracking xuc tac FCC ) c biu th nh hnh ve sau Fig.4:

98 97 96 95 94 93 92 91 Fig.4: 90

RON Clair

Nhit (0C)

15 20 25 30 35 40 45 2.7.3 - Ty l mol gia iso-butane /olefines: Nhit ,0C y la mt thng s quan trong nht v no khng ch lng tiu hao acide, hiu sut, cht lng san phm alkylat. Qua trnh s dung mt lng ln iso-butane

so vi olefine la cn thit han ch cac phan ng phu nh: polymere hoa olefine tao hp cht nng tng ng va tao du hoa tan. Ty l iso-butane/olefine lin quan ti nng iso-butane trong thit b phan ng . Anh hng cua nng nay n ch s octane moteur MON cua alkylat c biu th nh sau:

MON Cua Alkylat

9 4 9 3 9 2 9 1
90

_ _ Alkylat nhe (im si cui nho hn 1700C) __ Alkylat a tach butane

50 90

60 7080 Nng iso-butane trong thit b phan ng (%V)

S ch snng iso-butane trong thit b phan ng tng MON cua xng alkylat.. keo theo s cai thin ch s ortane moteur (MON ) ng thi lng acide sulfurique tiu thu giam xung, iu nay cch ra th sau: Lng Acide 80 sulfurique 70 tiuthu 3 (kg/m 60 alkylat )
50 40

Fig.5:

Nng iso-butane trong thit b phan ng n

30 40 50 60 70 80 90 Nng iso-butane trong thit b phan ng (% ttch) Fig.6: Anh hng cua nng i_C4 n lng tiu thu acid sulfurique

Vi nhng phn xng s dung HF lam xuc tac anh hng cua ty l iso-butane /olefine cung tng t :

Ch s octane

96 94 92 RON

MON

0 60

20

40

Ty l iso-butane /olefine (% ttch ) Fig.6: Anh hng cua ty l mol isobutane/olefines n NOR va MON cua alkylat.
2.5

Lng acide tiu thu (kg/m3olefin e)

1.5

0.5 0

2 10

8 Ty l iso-butane /olefine (% V)

Fig.7: Anh hng cua ty s ty isobutane/olefines Phn xng alkyl hoa s dung mol l mol iso-butane n lng tiu thu acide /olefine khoang t 5 8 cho xuc tac la acide sulfurique va 10 15 cho acide fluor hydrique. 2.6.4 - Thi gian phan ng :

Thi gian phan ng cua qua trnh alkyl hoa c xac nh bi hai yu t c ban : - Tc ly nhit khoi vung phan ng phai u gi nhit phan ng nh a chon. - Thi gian u iso-butane hoa tan vao pha acide (tao nhu tng tt), nh vy ma am bao tin trnh cac phan ng mong mun va han ch cac phan ng phu . Do cac thit b hoat ng theo dong lin tuc nn thi gian phan ng khng c khng ch qua ty l gia acide va hydrocarbure trong thit b phan ng. Ty l nay thng nm trong khoang t 1 2, trong khoang nay se cho cht lng alkylat tt nht . Trong thc t at hiu sut cc ai thi gian tip xuc trong thit b phan ng vi xuc tac la acide sulfurique khoang 20 40 phut, con vi xuc tac la HF th thi gian tip xuc khoang 10 20 phut. III. Cac s cng ngh Alkyl hoa: ng vi mi loai xuc tac khac nhau ta co co cac qui trnh cng ngh khac nhau: i vi loai xuc tac long: Cng ngh Stratco va Exxon-Kellog cho xuc tac acid H2SO4. Cng ngh UOP va Phillip cho xuc tac HF. i vi loai xuc tac rn: Cng ngh Akylene cua UOP. III.1 Cng ngh i vi xuc tac long: III.1.1 Cng ngh cho xuc tac H2SO4 III.1.1.1- Cng ngh Stratco : 1.S cng ngh cua qua trnh: Qua trnh nay thng goi la Effluent refrigeration process . S cua thit b phan ng Stratco c miu ta bng hnh sau: (Chen hnh) Thit b phan ng Stratco cho phep gii han thi gian tip xuc gia nguyn liu va xuc tac iu o lam han ch phan ng phu n mc ti thiu (V phan ng phu tao thanh du hoa tan, ty s hi lu acide cao cho phep am bao s pha loang olefine tt trong th tch phan ng va khng ch nhit cua nhu tng nho hn 10C.Thit b phan ng nm ngang, s trn ln hai pha c thc hin bng turbine, phan ng xay ra gn nh lp tc. Ngi ta thc hin ly nhit cua phan ng bng cach

trang b h thng chum ng trao i nhit bn trong thit b phan ng . Thit b phan ng Stratco co cac c trng sau : Th tch thit b khoang 34 m3 . Nng sut x ly khoang 0.39 0.44 m3 alkylat /m3TBP .h . Ty s th tch acide / hydrocarbon thng >= 1 . Ap sut trong thit b phan ng u gi hai pha trang thai long ( khoang 3kg/cm3) Nhit :7 100C . Ty l iso-butane /olefine : 810 Tiu hao acide :30 50 kg/m3 alkylat (khi nguyn liu la butene) S chi tit cua qua trnh alkyl hoa theo cng ngh Stratco: (Chen hnh) 2. Miu ta qua trnh : (thm vao!!!). III.1.1.2- Qua trnh Exxon /Kellogg : 1. S cng ngh: Qua trnh c ng dung bi hang Exxon, trong o s dung thit b phan ng bay hi ng thi di dang mt thung nm ngang.Trong thit b phan ng, nhit phan ng c tach ra bng qua trnh bc hi cua mt phn iso-butane.Acide sulfurique c a vao thit b va chay tran t ngn nay sang ngn khac. Nguyn liu iso-butane c chia lam nhiu phn va no c dn ng thi vao cac ngn. Nhit khac nhau cua cac ngn c khng ch bng s bc hi cua iso-butane, vn tc phan ng cua olefine rt nhanh va pha hi khng cha olefine. Cac ngn khac nhau lam vic nhng ap sut c la chon tuy thuc nhit trong lo (2 120C), ham lng iso-butane rt cao trong ngn u tin va y ap sut rt ln ( 1.4 1.75 bars ), ap sut tng cui cung la rt thp (0.35 0.84 bars). Thi gian lu trong vung lng gan khoang 30 50 phut, hu nh tt ca acide t vung lng gan c hi lu v ngn u tin cua thit b phan ng. Nng sut cua thit b phan ng Exxon khoang 0.15- 0.18 m3alkylat /m3TBP .h -1 . Ty l th tch acide/hydrocarbure nho hn 1. Nhit :4 100C. Ap sut : 1 3 kg/cm3.

So vi qua trnh Stratco qua trnh nay co nhng u im sau : Co s hoa hi trc tip cua iso-butane trong thit b phan ng do o khng cn trang b h thng ng trao i nhit do o c cu bn trong thit b khuy va thit b phan ng rt n gian iu nay dn n gia thanh cua thit b phan ng thp . S bc hi tai ch cua iso-butane cho phep qua trnh thc hin nhit thp hn nhiu so vi qua trnh Stratco va tranh s vn chuyn cht tai nhit va tht thoat cht tai nhit trong qua trnh lam lanh. Iso-butane bc hi trong thit b phan ng c nen, lam lanh va ngng tu. Propane c loai ra nh cua thit b Depropaniseur. Iso-butane c a hi lu tr lai thit b phan ng pha hydrocarbon long i ra t vung lng gan sau khi c x ly bng KOH se c a n thap tach iso-butane /n-butane/alkylat . Do nhng u in trn nn y chon qua trnh cng ngh cua Exxon. 2- Miu ta qua trnh : S n gian cua Exxon Research and Engineering c miu ta nh hnh ve Fig.9: Nguyn liu olefine u tin c lam lanh trc va c chia thanh 5 dong co lu lng bng nhau va c a vao 5 ngn cua thit b phan ng .Hai dong iso-butane va acide hi lu c a vao thit b phan ng ngn th nht.Vi s co mt cua thit b khuy trn th s tip xuc cua cac cht tham gia phan ng va xuc tac tt hn. Di tac dung cua acide sulfurique th iso-butane va olefine phan ng vi nhau rt nhanh, tao alkylat va toa nhit. Vi h thng lam lanh t ng, nhit phan ng c tach loai bng cach cho bay hi iso-butane t hn hp phan ng. Hi nay i t thit b phan ng n vung lam lanh trao i nhit vi iso-butane tun hoan sau o chung c nen lai, dong hi i ra sau may nen c trn ln vi dong san phm nh i ra t thit b tach isobutane (Deisobitanizer) sau o c cho qua trnh alkyl hoa trao i nhit vi dong alkylat i ra t thap tach n-Butane i vao thap tach propane. Propane i ra t nh thit b tach, san phm ay cha a s la iso-butane, sau o c lam lanh va quay lai thit b phan ng. Qua trnh tach propane nhm muc ch tranh s tng nng cua no trong thit b phan ng. San phm sau khi ra khoi thit b phan ng c a vao thit b lng gan (Settler), o pha acide c tach ra

khoi pha hydrocarbon va c a quay tr lai thit bi phan ng. San phm cua phan ng alkylat cha iso-butane, n-butane va mt lng nho cac cu t nhe cha bc hi ht trong thit b phan ng c a qua thit b x ly bng KOH, thit b ra bng nc tach loai cac cu t acide trc khi a vao thit b deisobutanizer tai y iso-butane i ra t nh thap c a qua trn ln vi dong i ra t may nen va qua thit b trao i nhit vi dong alkylat noi trn trc khi vao thap tach propane san phm nh la propane c a v lu tr , san phm ay la iso-butane c a i lam lanh va sau o quay tr lai thit b phan ng. San phm ay la alkylat cha nbutane c a qua thit b tach butane, sau thit b nay ta thu c n-butane nh va alkylat ay, cac san phm c a i thu hi nhit va vao bn cha. Trong thit b phan ng mt phn olefine cua nguyn liu se b polime hoa tao du hoa tan trong acide lam giam hoat tnh xuc tac cua acide sulfurique. Nh a cp phn trn, tap cht trong nguyn liu cung lam tng xu hng nay. V vy qua trnh lam sach acide sau khi s dung phai bt u t phn xng tach loai du nay, acide mi c a vao thay th cho lng acide em i tai sinh va duy tr nng cua acide u cao gi nguyn hoat tnh cua xuc tac. Qua trnh tai sinh xuc tac la nhim vu kho khn i vi qua trnh alkyl hoa bng acide sulfurique. My a tai sinh acide a s dung bng phng phap lp t thm phn xng san xut acide sulfurique. Tuy nhin cac nc khac nh Nht Ban co qua trnh san xut alkylat vi xuc tac acide sulfurique vi nng sut tng i nho, v vy qua trnh iu hanh thit b alkyl hoa co lp t thit b tai sinh acide d dang, vic thao tac i vi nhng thit b nay tng i n gian nhng lai tng ngun u t. 3.2.3.2 - H thng lam lanh : Hai h thng lam lanh c s dung trong cng ngh alkyl hoa bng xuc tac la acide sulfurique cua ER& E nh hnh ve sau Fig.10: ER & E s dung h thng t lam lanh ly nhit phan ng t thit b phan ng, trong s cua ER & E olefine nguyn liu c a vao cac ngn cua thit b phan ng o ngun nng lng trn ln phai hp ly tao s tip xuc tt gia hydrocarbon va acide nh vy chon loc cua phan ng tt hn, phan ng ng thc hin ap sut thp khoang 10 lb/in2 (tc la 70.3 g/cm3) duy tr nhit phan ng khoang 400F (khoang 4.5 0C). Hi hydrocarbon giau iso-butane c a ra t pha trn cua

thit b phan ng va a n may nen va sau o c lam lanh, v vy khng co s khac nhau v nhit gia nhu tng trong thit b phan ng va cht lam lanh. Qua trnh khuy trn cn mt nng lng u tao ra s tip xuc tt gia acide va hydrocarbure. VAPEUR Ngc lai trong h thng lam lanh gian tip (qua HYDROCARBURE trnh cua Stratco) th cn phai ha thp nhit cua cht DECANTEUR lam lanh nho hn nhit cua nhu tng trong thit b phan ng tao ra s chnh lch nhit tao iu kin thun li cho qua trnh trao i nhit qua chum ng. iu nay dn n hiu qua lam tng nng lng cn ACIDE thit cua may nen. Trong h thng nay cn mt nng lng khuy trn cao v nng lng nay nhm khc phuc tn tht ap sut tao ra khi lu lng cua nhu RECYCLE tng trong thit b phan ng cao, ma lu lng nay cn ACIDE thit cho vic tao ra mt h s trao i nhit u ln cho qua trnh trao i nhit. Chnh hai yu t nay lam cho h thng lam lanh trc tip t tn kem hn, hiu qua hn h thng lam lanh M gian tip va co chi ph hoat ng thp hn. 3.2.3.3- Qua trnh tai sinh xuc tac a s dung : Co nhiu phng phap tai sinh acide c nghin cu trong thc t, REACTEUR nhng c s dung nhiu nht trong thc t la qua trnh phn huy acide sulfurique a s dung nhit cao, acide a s dung cha khoang 3% nc, VERS DEISOBUTANISEUR 67% du o, qua trnh tai sinh xuc tac acide sulfurique CHARGE thc hin qua trnh alkyl hoa nhiu giai oan: ISO-BUTANE c RECYCLEE Qua trnh phn huy bng cach t bng khng INDIRECT EFFLUENT REFRIGRATION kh cac hp cht xut hin trong acide thanh SO 2, H2O, CO2 va N2. VAPEUR HYDROCARBURE FIG 10: Chuyn hoa SO2 thanh SO3. Hp nc SO3 thu c acide sulfurique co ISO-BUTANE RECYCLE nng khoang 9899% . M M M M M Qua trnh tai sinh xuc tac acide a s dungVERS DEISOBUTANISEUR la rt phc tap, no khng kinh t khi nng sut ln.

ACIDE

ACIDE RECYCLEE

CHARGE AUTO REFRIGERATION

III.2. Cng ngh Alkyl vi xuc tac rn: III.2.1 Gii thiu ve cng ngh: Phn xng Alkyl hoa ang chim mt v tr quan trong trong nha may loc du, trc y no c san xut bng xuc tac acide long HF va H2SO4, hng mi ang c ng dung la san xut alkylat co cht lng cao vi gia phu hp bng cach s dung xuc tac rn goi la cng ngh ankylene. u im cua cng ngh nay la co an toan cao, tin li khi vn chuyn xuc tac va co chon loc, nng sut cao III.2.2 Phan ng va cac thng s hoat ng cua qua trnh.

Cac phan ng cua qua trnh alkyl c m ta mt cach tng quat nh sau: Qua trnh alkyl hoa xay ra bi phan ng gia iC4 va cac

olefine nhe trn b mt xuc tac rn.C ch phan ng tao thanh cacbocation tng t nh qua trnh dung xuc tac long. u tin C4+ c tao thanh bi H+ cua olefefine nhe trn b mt xuc tac rn sau o C4+ phan ng vi olefine tao thanh C8+ ,tip tuc co s tach H t iC4 khac tao san phm C8. Ngi ta cho tun hoan lai chuyn hoa ht olefine. Trong qua trnh alkyl co dung xuc tac long cac bc phan ng c xay ra bi s tip xuc ring re vi hyrocacbon tng ng vi t l iC4/Olefin (I/O). Cac thng s anh hng n qua trnh Alkylen gm :Nhit phan ng, t l I/O, thi gian phan ng va t l xuc tac trn Olefin (C/O). Nhit : Ch s c tan tng khi nhit phan ng giam va qua trnh lam lanh thng oi hoi ti u hoa trong iu kin phan ng. Nhit ti u c chon bng cach cn bng gia s tng ch s c tan vi vic giam chi ph u t cho qua trnh lam lanh T l I/O: T s nay cang cao th cht lng san phm tng v phan ng polyme hoa Olefin c giam ti thiu .T l I/O ti u c chon da trn vic cn bng gia vic tng cht lng san phm va chi ph u t vn hanh Thi gian phan ng

Thi gian tip xuc gia cht phan ng va xuc tac co anh hng trc tip n cht lng san phm bi v phan ng phu Isomer hoa va Cracking, lam giam cht lng san phm, xut hin khi thi gian tip xuc dai. T l xuc tac trn Olefin: T l cua cac tm xuc tac hoat ng trn Olefin la mt thng s chnh lin quan n n nh va hoat tnh cua xuc tac. T l C/O cang cao th hoat tnh cua xuc tac giam v vy vic ti u hoa t l C/O oi hoi phai cn bng gia chi ph tng lng xuc tac vi vic tng n nh cua xuc tac III.2.3. S phat trin cua Alkylen S phat trin cua qua trnh oi hoi phai tao ra mt cng ngh s dung xuc tac mi III.2.4.M ta qua trnh Alkylen Cng ngh Alkylen c chia lam 3 khu vc - Khu vc x ly nguyn liu - Khu vc phan ng - Khu vc phn tach

1. Vung x ly nguyn liu : Vic x ly nguyn liu rt cn thit v xuc tac cua qua trnh d mt hoat tnh bi mt s cht nh di-Olefin, sulfure, oxygen va cac hp cht cua Nit. Nhng cht ng c nay lam giam hoat tnh va cung co th lam mt hoat tnh vnh vin cua xuc tac. Khu vc tin x ly nay s dung cng ngh ging nh trong qua trnh Alkyl hoa bng HF va mt s cac qua trnh loc du khac . 2. Khu vc phan ng

Hai yu t c ban chi phi qua trnh Alkylen la: + T l I/O cn phai c duy tr thu c san phm co cht lng cao. + Thi gian tip xuc gia cht phan ng va xuc tac phai c ti u hoa at c s chuyn hoa Olefin cao ng thi giam ti u phan ng phu. Vic hi lu iC4 cha phan ng t vung phn tach iu khin t l I/O. Chi ph vn hanh khu vc phn tach ty l vi ty s I/O. Thit b phan ng pha long, dong oolefine sach c trn vi dong iC4 tun hoan t vung phn tach sau o c phun vao ng Riser thng ng. Xuc tac mi cua qua trnh c a vao t di ay ng riser, o co s tip xuc cua hn hp iC4 va olefine. Cac cht phan ng va xuc tac chuyn ng nhanh trong ng riser, xay ra phan ng ankyl hoa . Tai u ra cua ng riser xuc tac va HC c tach nhanh bi trong lc iu khin thi gian tip xuc gia HC va acide. Dong san phm se i ra nh cua thit b va i vao b phn phn tach sau o xuc tac c a vao khu vc phan ng lanh. Xuc tac i ra khoi ng riser i vao tng cha ni cht xuc tac c hoat tnh lai bi dong hydro a bao hoa iC4.Xuc tac a mt hoat tnh mt phn bi lng nho hyrocarbon nng va cha no a hp phu trn b mt xuc tac. Hydroge, c hoa tan trong dong iC4 tun hoan ,bao hoa nhng hyrocabon nay,cho phep giai hp d dang t b mt cht xuc tac. Ngun hyrocacbon c ly chu yu t phn xng reforming. Xuc tac sau khi c hoat tnh se chuyn ng xung pha di ng nh trong lc va sau o c tun hoan tr lai. Dong HC nng a bao hoa c thu hi vi san phm vung phn tach. Mc du cac HC nng a c tach nhit thp vung phan ng, mt lng nho cac cht nay kho co th tach iu kin nhit thp cua phan ng. iu cn thit la x ly cht xuc tac nh ky vi nhit cao hn nhit cua phan ng am bao no c hoat tnh lai hoan toan. V vy mt thit b tai sinh phn tach c lp t bn canh tht b phan ng loai bo nhng vt HC nng tch tu trn b mt cht xuc tac. Trong giai oan tai sinh ln hai nay, mt lung cht xuc tac chay vao thit b tai sinh, ni no c tip xuc trong thi gian dai iu kn nhit cao, vi s lu thng cua dong cht tai sinh hyrogen. Vung tai sinh nhit cao nay c thit k ban lin tuc hay gian oan. Sau giai oan tai sinh, cht xuc tac di chuyn xung di ay cua thit b tai sinh ri tr lai ay cua ng riser.

Cht xuc tac cua qua trnh Alkylen, HAL-100 co bn vt ly cao va a c phat trin bi hang UOP