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TRUNG TM CNG NGH HA HC Th.s Trn Th Hng
GIO TRNH
TNG HP HU C HA DU
MC LC
mc Trang
MC LC .................................................................................................... 1 CHNG 1: NGUN NGUYN LIU . ...................................................... 4 1.1. Parafin........................................................................................... 4 1.2. Olefin............................................................................................. 7 1.3. Hyrocacbon thm ..................................................................... 18 1.4. Axetylen. ..................................................................................... 22 1.5. Kh tng hp ............................................................................... 24 CHNG 2: CC QU TRNH C BN CA TNG HP HU C .... 31 2.1. Qu trnh ankyl ha .................................................................... 31 2.2. Cc qu trnh ehydro ho v hydro ho ................................... 37 2.3. Qu trnh halogen ha ................................................................ 46 2.4. Qu trnh oxi ha ........................................................................ 57 2.5. Cc qu trnh thy phn, tch nc, este ha, amit ha ........... 72 2.6. Cc qu trnh sunfat ha, sunfo ha v nitro.............................. 83 CHNG 3: TNG HP T AXETYLEN ............................................... 93 3.1. Sn xut vinylclorua (VC) v polyvinylclorua (PVC) ................... 93 3.2. Tng hp vinyl axetat (VA), polyvinyl axetat (PVA).................... 95 CHNG 4: TNG HP T METAN V CC PARAFIN KHC. ......... 98 4.1. Tng hp hydrocianit t metan .................................................. 98 4.2. Tng hp amoniac...................................................................... 98 4.3. Tng hp metanol .................................................................... 103 4.4. Tng hp formanehit .............................................................. 106 4.5. O-ankyl ha bng olefin. Tng hp metyl tec-butyl ete (MTBE)109 4.6. N-ankyl ha. Tng hp amin t ru....................................... 110 4.7. Oxy ha naphta nh (C5 C8) .................................................. 113 4.8. Oxy ha parafin rn thnh axit bo tng hp ........................... 114 CHNG 5: TNG HP T ETYLEN ................................................. 118 5.1. Oxy ha etylen, tng hp oxit etylen, etylen glycol (EG).......... 119 5.2. Oxy ha etylen. Tng hp acetanehit, vinyl acetat, axit axetic123 5.3. Hyrat ha etylen. Tng hp etanol ......................................... 139 5.4. Halogen ha etylen. Tng hp vinyl clorua .............................. 141 CHNG 6: TNG HP T PROPYLEN V BUTEN.147 6.1. Oxy ha propylen. Tng hp acrolein, axit acrilic..................... 145 6.2. Halogen ha propylen. Tng hp allyl clorua. .......................... 150 6.3. Hydrat ha propylen. Tng hp iso-propyl ancol...................... 154 6.4. Oxy ha n buten. Tng hp anhyric maleic (AM). .............. 155 6.5. Oxy ha iso-buten. Tng hp metacrolein v axit metacrilic.... 156 2
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CHNG 7: TNG HP T BENZEN, TOLUEN, XYLEN (BTX)......... 158 7.1. Ankyl ha benzen thnh etyl v iso propyl benzen. .............. 158 7.2. ehydro ho cc hp cht ankyl thm. sn xut styren ......... 161 7.3. Oxy ha ankylbenzen. Tng hp phenol v aceton ................. 162 7.4. Oxy ha p-xylen. Tng hp axit terephtalic .............................. 167 7.5. Oxy ha metylbenzen. Tng hp dimetyl terephtalat ............... 172 CHNG 8: TNG HP CHT TY RA............................................ 176 8.1. Tng hp cht hot ng b mt dng ankylsunfat ................. 176 8.2. Tng hp cht hot ng b mt dng ankylarensunfonat...... 180 8.3. Phn loi cht hot ng b mt (HBM) ................................ 184 8.4. Nguyn liu sn xut cc cht ty ra ..................................... 186 8.5. C ch ty ra.......................................................................... 194 8.6. Mt s qui trnh cng ngh sn xut cht ty ra .................... 195 CHNG 9: TNG HP THUC TR SU ....................................... 203 9.1. Gii thiu .................................................................................. 203 9.2. Mt s cng ngh tng hp thuc tr su................................ 203 9.3. ng dng ca thuc tr su..................................................... 212 9.4. Phn loi thuc tr su............................................................. 216 TI LIU THAM KHO............................................................................ 229
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CHNG 1: NGUN NGUYN LIU CA CNG NGH TNG HP HU C HA DU. Nguyn liu ch yu sn xut cc sn phm hu c l nhng cht hu c ha thch than , du m, kh thin nhin. T , ngi ta thu c hu ht cc loi nguyn liu ban u cho cc qu trnh tng hp hu c ha du: parafin, olefin, hyrocacbon thm, axetylen v kh tng hp. 1.1. Parafin Hyrocacbon no c chia ra thnh nhiu nhm sau: parafin thp phn t (C1 C5) dng ring l; parafin cao phn t (C10 C40) l hn hp lng v rn ca nhng ng ng vi s cacbon khc nhau. 1.1.1. Parafin thp phn t Gii thiu Metan l cht kh kh ha lng, nhng tt c cc parafin dng kh khc u ngng t khi lm lnh bng nc di tc dng ca p sut. Quan trng l s khc bit v nhit si ca n-butan vi iso-butan, ca n-pentan vi iso-pentan ln c th tch ra bng phng php chng ct phn an. Parafin thp phn t khng tan trong nc v cht lng phn cc, nhng b hp th bi nhng hyrocacbon khc v cc cht hp ph rn. Parafin thp phn t to vi khng kh nhng hn hp n nguy him. Ngun gc chnh ca parafin thp phn t l kh thin nhin v kh ng hnh, cng nh kh thu c t cc qu trnh ch bin du m c s tham gia ca hyro. tch kh du m, ngi ta c th dng cc phng php hp ph, ngng t, chng ct. Chng ct l phng php c dng nhiu nht. Tch parafin thp phn t Khi tch nhng kh kh ngng t phi dng p sut cao (2 4 MPa) v lm lnh su. Khi tch etan v metan khi nhng hyrocacbon khc bng phng php chng ct, ngi ta thng kt hp vi hp ph khng phi lm lnh su v kinh t hn.
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C 1 + C2
izo- C4 C4 C5 Izo-C5 2 1 5 6 7 8 9
4 kh C3 n-C4 C6 n-C5
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Hnh 1.1. S cng ngh phn tch hn hp parafin thp phn t. 1 My nn; 2, 5, 6, 7, 8, 9 Thp chng ct phn on; 3 - Thit b ngng t; 4 - Thit b un nng; 10 - Thit b iu chnh p sut.
Ngi ta nn kh trong b nn kh (1), lm lnh bng dng nc ri cho vo thp chng ct (2). Trong (2), C1 - C3 tch khi hyrocacbon nng hn. Ty vo p sut v hm lng phn on C1,C2 trong kh, lp phn hi lu trong thit b ngng t hi lu (3), ngi ta dng nc hoc propan lm lnh. Phn on nh c chng tch trong thp (5), lng hi lu c lm lnh bng propan. Sn phm pha trn ca thp ny l kh kh, sn phm y ca thp ct l propan lng. Phn on nng C4-C6 t thp (2) c iu tit n p sut 0,8Mpa. Trong thp (6), ngi ta tch phn on C4 v a chng qua thp (7) tch ring n- butan v izo-butan vi 98% hm lng sn phm chnh. Cht lng trong thp (6) c iu tit n 0,3MPa v c a qua thp (8). y, C5 c tch thnh n- pentan v izo-pentan vi 97% 98% sn phm chnh. Metan v etan trong kh kh, c th tch ra bng cch chng ct phn on nhit thp, lng hi lu c lm lnh bng propan, etan lng vi p sut 4,0 - 4,5MPa. Kh thin nhin c ti 96% - 97% CH4 nn c th dng trc tip nh metan k thut. 1.1.2. Parafin cao phn t Gii thiu Nhit nng chy ca parafin cao phn t tng dn theo chiu di mch cacbon, nhit nng chy ca parafin mch thng ln hn parafin phn nhnh tng ng. Mt im khc bit ca n-parafin l c
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kh nng to tinh th cng hp vi cacbamit v zeolit. Trong m bi trn, gasoil, du la c th cha n 30% n-parafin. tch chng, ngi ta dng mt s phng php tch: phng php kt tinh, tch bng cacbamit, tch bng zeolit. Tch parafin cao phn t Tch n-parafin bng zeolit y l phng php mi, tin b, c s dng nhiu. N dng cho bt c phn on no, cho tch n-parafin cao (80% 98%) v sch cao (98% 99.2%). Qu trnh gm 2 giai on chnh l hp ph nparafin v gii hp ph n-parafin. Chng c th thc hin pha lng hay pha kh nhit n 3000C 3500C v p sut khc nhau. Gii hp ph bng p sut thp, tng nhit y nhng cht khc ra (npentan, ammoniac) hoc kt hp nhng phng php ny. S cng ngh tch n-parafin bng zeolit c m t trn hnh 1.2.
Nguyn liu 8 2 8 2 2
NH
N2
3 7
Hnh 1.2. S cng ngh tch nparafin v iso-parafin cao phn t bng phng php hp ph vi zeolit. 1,5 - Thit b un nng; 2 - Thit b hp ph v gii hp ph; 3,6 Sinh hn; 4,7 - Thit b tch; 8 - H thng thi kh.
Ngi ta trn vo phn on du vi kh mang (N2), gia nhit v ha hi trong khi thit b gia nhit (1). Hn hp hi kh thu c cho vo mt trong ba thit b hp ph (2) cha y zeolit. Ti y, xy ra
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qu trnh hp ph n-parafin. Lm lnh hn hp thot ra sau khi hp ph qua b lm lnh (3) ri tch phn ngng tch parafin ra khi kh mang trong b phn ly (4). Kh mang ny li em trn vi phn on ban u. Khi cht hp ph b parafin bo ha hon ton th chuyn hn hp kh mang vi phn on du vo b hp ph th hai, cn trong b th nht s xy ra qu trnh gii hp ph. Ngi ta cho vo b hp ph th nht nhng kh gii hp ph (NH3) lm nng s b b gia nhit (5). Sau khi gii hp ph, ngi ta lm lnh hn hp cht gii hp ph v parafin trong b lm lnh (6) v tch chng trong thit b phn ly (7). NH3 li quay vng vo gii hp ph. Mt trong ba thit b hp ph lm vic giai on hp ph, cn hai thit b cn li - gii hp ph, nh th qu trnh ng m cc dng chy u t ng. 1.2. Olefin Olefin l hyrocacbon nguyn liu quan trng, thng thng tn ti dng kh v lng, chng c sn xut bng nhiu phng php khc nhau 1.2.1. Phng php nhit phn v cracking nhit Nhit phn: l qu trnh thu nhit v lin h vi s lng sn xut nng lng, trong qu trnh tn dng nhit ca kh nng c ngha quan trng. Nhng s b phn phn ng hin hnh c chia theo kh nng cung cp nhit Cracking nhit: Cracking nhit parafin mm hoc cng dng trong cng nghip c sn phm olefin mch thng t 5 - 20 nguyn t cacbon. Cng ngh ca n rt ging vi nhit phn nhng sn phm du m. 1.2.2. Phng php cracking xc tc Cracking xc tc l qu trnh dng sn xut olefin C3 C4, trong c isoC4. Cho n ngy nay, qu trnh ngy cng c ci tin v hon thin, nhm mc ch nhn nhiu xng hn vi cht lng xng ngy cng cao v nhn c c nguyn liu c cht lng tt cho cng ngh tng hp ha du. Qu trnh cracking xc tc thng c tin hnh iu kin cng ngh nh sau: nhit khong 470 5500C, p sut trong vng lng ca l phn ng P = 0.27Mpa, tc khng gian th tch truyn nguyn liu, ty theo dy chuyn cng ngh m c th t t 1 120m3/h.m3(1 120h-1). Xc tc cracking ngy nay, thng dng ph bin l xc tc cha zeolit mang tnh axit. Sn phm ca qu trnh l mt hn hp phc tp ca hyrocacbon cc loi khc nhau m loi c s nguyn t cacbon t 3 tr ln vi cu trc mch nhnh chim ch yu. 1.2.3. Tch olefin Kh thu c t nhng qu trnh cracking v nhit phn khc nhau
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v thnh phn (theo s liu bng 1.1). Chng c th c chia ra lm ba nhm: Kh cracking nhit v xc tc cha nhiu hyrocacbon C3 v C4 nhng t etylen. T kh ny, tt nht nn tch propylen v buten, cn nhng cu t khc chuyn i nhit phn hoc dng cho mc ch khc. Kh khi nhit phn hyrocacbon dng kh cha t phn on cao. Nhng kh ny dng lm nguyn liu butan, t chng c th tch etylen v propylen. Khi nhit phn phn on du m lng thu c sn phm phn ln l olefin C2 C4, chng c tch bng phng php chng ct hp th. Phng php ny i khi dng tch cc sn phm kh ca qu trnh nhit phn. Vi phng php chng ct nhit thp v c thc hin trong nhng thit b ln hin i, phn on olefin thu c sch hn v nng lng tiu tn cho cng on tch t hn. Chun b kh tch Trong kh cracking v nhit phn c nhiu tp cht cn phi lm sch s b. Mt s trong gy n mn thit b (H2S, CO2 ), s khc kt t li gy tt (H2O) ng ng v thit b, mt s khc c nhit si gn vi olefin v lm bn phn on thu c (axetylen, metylaxetylen). Ngoi ra, trong kh cn cha hi cht lng hyrocacbon m nhiu nht l benzen, penten. Khi lng c bn nhng hyrocacbon cao phn t v nc c tch ra t ngay giai on nn kh u tin. Sau , giai on nn kh bc hai v cui cng, kh c lm sch khi tp cht kt lng. Phng php lm sch kh khi H2S v CO2 c chn ty vo nng nhng tp cht ny. Nu nng H2S v CO2 khng ln lm, c th ra kh bng dung dch kim. Nu khi lng chng ln, ngi ta thng s dng phng php hp th bng etanolamin vi qu trnh trung ha hon ton tnh axit ca kh bng kim, trong thit b lc kh. Lm sch kh bng dung dch etanolamin da trn c s nhng baz hu c ny to vi CO2 nhng mui bn nhit thp v b phn ly khi gia nhit.
2HOCH2-CH2NH2 + H2S
20-400C 100-110 C
0
(HOCH2-CH2NH3)2S
Nh vy etanolamin trong thit b gii hp c th ti sinh v quay li hp th. Ngi ta sy kh ln cui bng dietylenglycol hoc kim rn, nhng cng c khi dng oxyt nhm hoc zeolit v chng hp ph tt nhng cht bn.
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Bng 1.1. Thnh phn sn phm cracking v nhit phn (% khi lng) Cracking Nhit phn Nhit phn Cu t xc tc hyrocacbon kh hyrocacbon lng CH4 6-7 16-18 15-20 C2H4 2,5-3,5 36-38 30-40 C2H6 6-7 26-28 5-8 C3H6 14-17 10-12 15-20 C3H8 13-15 5-6 1-3 C4H8 19-22 2-4 8-12 C4H10 20-32 1-3 C4H6 1-3 5-7 H2 0,7-0,9 1,5-2 0,9 -1,2 lm sch olefin ln axetylen, ngi ta dng phng php hyro ha chn lc trn cht xc tc khng ng nht, phn ng ny khng xy ra vi olefin: P d /A l2 O 3 C H + H C H
2 2 2 2 4
t mc ch ny, ngi ta cho xc tc paladi (trn cht mang) v cht xc crom coban niken lm vic nhit 1500C 2300C. Cng vi axetylen, mt s ien c kh nng phn ng b hyro ha, nu mun gi chng, ngi ta ch hyro ha etylen, sau khi tch phn on C4. Ngi ta thc hin vic lm sch ny trong phn on C2 C3 cn phi thm H2. Phn tch cc phn on sn phm ca cracking xc tc Tng qut dy chuyn cng ngh gm 3 phn chnh: - Phn ng - Ti sinh v tn dng nhit - Phn tch sn phm Hot ng ca dy chuyn nh sau: Nguyn liu mi t b cha nguyn liu (1), c cho qua thit b trao i nhit ng chm, nguyn liu mi c th c trn vi phn on tun hon HCO (2) v cn y (3), sau cho qua l t nguyn liu cracking (4). Nguyn liu sau khi ra khi (4) c tip xc vi dng xc tc nng ti sinh (6) y thit b phn ng (5) v xy ra phn ng cracking xc tc. Sau khi tch khi xc tc, dng hi sn phm (7) c chuyn n ct chng ct phn on (13). p sut trong thit b phn ng c khng ch bng b phn iu chnh p sut ca ct phn on. Xc tc lm vic c cho qua vng tch hi(cn gi l b phn ra xc tc) bng cch thi hi nc vo.
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Hnh 1.3. S cng ngh cracking xc tc vi lp xc tc tng si (FCC) v phn tch cc phn on sn phm. 1- Bn nguyn liu; 2 Dng HCO tun hon; 3 Dng cn y; 4 L gia nhit; 5 - Thit b phn ng; 6 Dng xc tc ti sinh; 7 Dng sn phm hi; 8 Dng xc tc cc ha; 9 - Thit b ti sinh xc tc; 10 - Bung lng bi xc tc; 11 Thit b tn dng nhit; 12 - Lc in; 13 - Ct chng ct phn on; 14 - Thit b tch.
Xc tc c cha cc (8) c chuyn qua van iu khin v khng ch bi b kim tra mc xc tc trong l phn ng v sau i vo l ti sinh. Mc ch chnh ca ti sinh l t chy lp cc bm trn xc tc bng oxy ca khng kh. Xc tc ti sinh c chuyn vo ng phn ng ng sau khi c ui sch kh qua mt van l m s hot ng ca van ny c khng ch, iu khin t ng bi b phn iu chnh nhit ca reactor, ri sau xc tc c trnvi nguyn liu racking v hon thnh mt chu trnh.. ng thi ngi ta tho xc tc bn, gi ha ra v b sung xc tc mi m bo hot tnh n nh ca xc tc theo thi gian lm vic.
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Kh ca qu trnh chy cc v cc ht xc tc chuyn ng t pha c vo pha long ca nh l ti sinh, c qua 2 cp cyclon gi li cc ht xc tc v tch kh. Sau , khi kh c qua bung lng (10) tch tip bi xc tc ri qua b phn tn dng nhit (11), tip theo khi kh c lm sch khi bi xc tc bng lc in (12) ri i ra ngoi theo ng khi. Hi sn phm (7), c np vo ct chng ct phn on (13) tch chia thnh cc sn phm khc nhau.. Xng v phn nh hn c cho qua b phn ngng t ri vo thit b tch kh (14). Sau khi tch kh, ta nhn c phn on C1, C2 m chng c th dng lm kh nhin liu trong nh my. Phn on C3, C4 cha nhiu propylen v buten c tch ra v dng lm nguyn liu cho nh my ankyl ha v sn phm tip theo l xng kh butan T ct phn on chnh ta cn nhn c cc phn on sn phm nh naphta nng, LCO, v HCO. Phn HCO c th cho tun hon li thit b phn ng (4), v cui cng l phn on du cn c lm sch khi bn xc tc. Mt phn sn phm nh ca thit b tch bn xc tc cng c cho tun hon vi HCO. Tch kh t qu trnh nhit phn Bng phng php chng ct nhit thp, c th tch c metan, etan vi sch tng i cao. Qu trnh phn tch kh c thc hin p sut 3MPa - 4MPa. tch phn on metan, cn nhit t0 = -1000C, nhit ny c thit lp nh vng lm lnh etylen, n lm vic ch khi c propylen (hoc NH3), v propylen khi nn v lm lnh c kh nng ngng t v khi nn n p sut khc nhau c th cho nhit t 00C - 400C. nhit ny, kh nn etylen cng nh n p sut khc nhau m cho nhit t (-600C) (-1000C). Mt trong nhng s cng ngh phn chia kh khi nhit phn phn on hyrocacbon lng c m t trn hnh 1.4. Kh t thit b nhit phn c nn t t trong nm bc ca thit b nn kh tuabin (1) ( trn s ch c ba mc ), sau mi bc, kh c qua b lm lnh (2) v b phn ly (3), ti n c tch khi phn ngng t (nc v nhng cht hu c), tch nhng hyrocacbon nng nht, ngi ta ngn phn ngng t bc tip theo v cho quay li b lc bc trc (trn s ch c nn bc I v II). Nh hiu ng chng ct c thit lp v trong phn ngng sau bc I ca b nn kh l hyrocacbon lng iu kin thng. Chng c tch ra trong kh ha tan trong thp tch hi (4). Phn ngng t c chuyn qua phn ch bin, cn kh quay li ng ht bc I ca b nn kh.
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Hnh 1.4. S cng ngh tch kh trong nhit phn hydrocacbon lng. 1 My nn kh; 2, 8, 11, 18 Sinh hn; 3,12 - Thit b tch; 4, 6 Thp to hi nc; 5 - Thit b ti; 7 - Thit b sy; 13, 14, 19, 20, 21 Thp chng ct phn on; 15 - Thit b trao i nhit; 16 - B phn cp nhit cho hi; 17 - Thit b lm sch; 22 Van chnh p.
Sau khi nn bc ba, kh chuyn qua lm sch khi tp cht axit. Lm sch bng dung dch kim hi luqua thit b lc m (5). Sau nn kh n p sut 3,5 4 MPa. Phn ngng to thnh c tch ra khi kh v sau khi qua thit b phn ly ca b nn kh bc IV, n chuyn qua thp tch hi (6). Ti y kh ha tan c tch ra v quay li b nn kh bc IV. Cht lng ca thp (6) gm hyrocacbon C4 C5 v tch chng, phn ct nh cho vo thp ct (21). Ngi ta cn cho vo y phn on tch c khi lm lnh su. Sau khi tch hyrocacbon cao, kh chuyn t thit b sy (7) cha y Al2O3 hoc zeolit v n b phn lm lnh su tch kh.
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tit kim, ngi ta lm sch s b kh tng bc nh cht lm lnh c lch nhit khc nhau. Kh i qua hai thit b lm lnh (8) v (9) nh vng propylen. trong b th nht, propylen ha hi khi t0 = -50C n -150C p sut cao, cn trong b th hai th p sut khng kh v nhit = -450C, iu tit kim c nng lng khi nn cht lm lnh. Lm lnh tip trong b lm lnh (10) nh qu trnh ha hi phn on etan thu c khi tch kh, v trong b lm lnh (11) nh cht lm lnh l phn on metan. V nhng phn on kh metan v etan thot ra t nhng b lm lnh ny c nhit thp nn ngi ta dng n lm lnh nhng phn khc (trn s c ch r). Mt phn cu t kh ngng t trong bung lm lnh s b. Kh c tch ra khi cht lng trong thit b phn ly (12),nhng dng ny chuyn n nhng a tng ng ca thp chng ct (13). Theo thnh phn hi v lng, thp ny c gi l thp tch metan. Nhim v ca n l tch phn on metan khi nhng hyrocacbon nng hn c thu li di thp. Metan l cht kh kh ha lng, ngoi ra n c lm long bi H2 nh th cng lm gim nhit ngng t ca n. Bi vy, lp lng hi lu trong thp tch metan cn phi lm lnh tht su.Do , vic lm lnh c thc hin nh qu trnh ha hi etylen lng t vng lnh p sut khng kh v nhit t0 = -1000C. thay i tng phn qu trnh lm lnh ny bng phn on metan thu c, ngi ta chn n p sut 0,5 0,6 MPa v dng n lm lnh pha trn ca thp. Cht lng di thp tch metan (13) gm hyrocacbon C2 C4. Mc tiu tip theo l tch C2 v C3 c thc hin trong thp chng ct (14), c gi l thp tch etan. p dng bnh thng trong thp l 2,5 MPa, cn nhit pha trn thp gn -100C. Bi vy, lp lng hi lu phi lm lnh nh vng lnh propylen, (propylen ha hi di p sut c kh nng m bo nhit cn thit do qu trnh ha hi ca n). Pha trn thp (14) thot ra l hn hp etylen v etan vi tp cht axetylen v khi lng khng ng k metan v propylen. Phn on ny n b phn lm sch hyro lm sch khi axetylen. Ngi ta gia nhit n trong b trao i nhit (15) nh nhit ca dng ngc v sau n b gia nhit hi (16). Sau , ngi ta thm vo mt lng nh H2 v hyro ha trong thit b lm sch hyro (7) trn xc tc khng ng nht. Lm sch phn on lm sch bng nc trong b lm lnh (18) v sau khi lm sch cho qua b trao i nhit (15), tip tc n c chuyn n thp chng ct (19) gi l thp etylen. Nhim v ca n l tch etylen v etan, v ng thi lm sch etylen khi metan v nhng dn sut khi lm sch hyro. Thp (19) thng lm vic p sut 2,0 2,3MPa v nhit pha trn l 300C n -350C. Do , lm lnh phn ngng hi lu phi
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nh qu trnh ha hi ca propylen lng t vng lnh. H2 cng tp cht metan v etylen thot ra t pha trn th, c cho quay li giai on nn kh ban u tng ng. Etylen lng t mt trong nhng a pha trn thp (19) c thu li. i khi n c gi li trng thi lng v khi chuyn n ni bo qun hoc xitec vn chuyn. Thng n dng dng kh v c th yu cu nhng p sut khc nhau ( v d: tng t nh phn on etan). Phn phn on etan lng t li thp (19) b chn li v s dng lnh ca n nh m t trn. Cht lng trong thp tch etan (14) chuyn n thp tch propan (20). Trong thp (20), di p sut ~20 Mpa, phn on propan, propylen c chng ct. Ngi ta lm lnh phn ngng hi lubng nc. Ngi ta thu v bo qun phn on ny dng lng, nhng ty vo p sut yu cu trong giai on tng hp tip theo m ngi ta ngn v s dng lnh ca n cho nhu cu ny hoc khc. Phn on C4 + C5 c thu hi di thp tch propan v a qua tch thm thnh phn on buten v penten trong thp (21). C c v tch phn on olefin - Phn on olefin thu c khi tch kh nhit phn thng cha n 2 3% mentan v etan, cn nu khng lm lnh khi axetylen th c n 1 2% hyrocacbon ny. Trong nhng thit b hin i, cht lng etylen tng ng k v polyme ha n thnh polyetylen cn phi t tinh khit ln hn 99,9%. - Ty thuc vo ngun thu m c th thu c propylen v propan vi t l khc nhau. Khi tch n t kh cracking, hm lng propylen ch t 30 - 40%(v); cn khi nhit phn hyrocacbon lng, hm lng propylen t 90 - 95%(v) propylen. Nhng cu t khc l hyrocacbon C2 0,2 - 2,0%(v). Cn khi khng lm sch bng hyro th c 0,5 2,0%(v) metylaxetylen v propaien. Thng ngi ta dng phn on propylen tng hp, khng cn phi lm sch thm. i vi cc qu trnh tng hp cn hm lng propylen cao hn, tt hn l tin hnh c c, ng thi tch mt khi lng propan bng chng ct. Khi chng ct, trong propan c c metylaxetylen cng propaien. ngi ta thu propylen c sch cao (99,9%) cn thit sn xut polypropylen. - Phn on buten: Cng ty vo ngun gc thu m c th chia ra khng ch theo hm lng tng i ca buten v butan m cn theo t l ca nhng ng phn khc nhau ca chng, bao gm c butaien1,3. Bng 1.2. Thnh phn cc cu t ca phn on C4 (% khi lng) Izo-C4H8 C4H6 Qu trnh n-C4H10 Izo-C4H10 n-C4H8 Cracking 10 - 20 35 - 50 25 - 40 5 - 10 xc tc Nhit phn 5 - 7 1-3 20 - 25 30 - 35 30 - 40
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Vic tch phn on C4 bng chng ct bnh thng khng th c v ha hi ca cc cu t trong phn on rt gn nhau. V vy phi dng nhng phng php c bit da trn c s chng ct chit tch v qu trnh hp ph ha hc. Khi ch bin phn on C4 ca nhit phn, tch butaien-1,3, phng php thng dng l hp ph ha hc bng dung dch ammoniac-acetat ng I: C u + + (N H 3 )4 + C 4 H 6 C u + (N H 3 .C 4 H 6 + N H 3 Nhng phc ny cng vi butaien-1,3 bn hn so vi phc ca olefin. Khi x l phn on bng dung dch cht hp ph nhit t = 100C 00C, n ch yu l butaien-1,3. Khi gia nhit n 400C, xy ra qu trnh gii hp nhng olefin ni vi phn butaien-1,3. Ti 700C 750C, butaien-1,3 sch c tch ra, cn dung dch hp th sau khi lm sch s quay li thit b hp ph. Ngi ta thc hin qu trnh trong tng ngc ca thit b cng b khuy. Mi thit b c trang b b phn ly v my bm. Dung dch cht hp ph sch c cho vo thit b u tin, cn phn on buten th vo thit b cui, ngi ta thit lp iu kin ti u hp th phn on ha long bng dung dch cht hp th sch, cn ngi ta hp th phn on c c bng dung dch bo ha. Trong s nhng thit b hin i, ngi ta thc hin qu trnh hp th trong mt s thp chit tch, trong phn on lng v dung dch hp th chuyn ng ngc chiu nhau nh s chnh lch t trng (hnh 1.5). Cht hp th lm lnh c cho vo pha trn thit b chit tch u tin (1) v chuyn ng t trn xung qua tt c ba thit b. Ngi ta cho phn on C4 ban u vo on gia b chit tch th ba v n c y ln trn nh nhng phn on nh v n c chuyn t thit b ny qua thit b kia bng bm. Phn on C4 tch khi butaien -1,3 (C4H10 + C4H8) c ly ra t phn trn ca b chit tch (10) - b ny ng vai tr nh b phn ly. Dung dch bo ha t di b chit tch (3) bm vo thp tch hi (4), ti y vi nhit t = 400C phn olefin c chng ct. Bi v chng cha nhiu butaien -1,3 nn chng quay li hp th pha di thp (3). Dung dch t di thp (4) cho qua thp tch hi (5), ti y nh qu trnh gia nhit m butaien-1,3 c gii hp, cn cht hp th ti sinh c lm lnh trong b lm lnh (6) v quay li nhng b chit tch. Hin nay tch butaien-1,3 ngi ta thng dng phng php chng ct chit tch.Theo so snh, furfurol l cht chit tch c u th hn axetonitril v N-metyl-pirolidon. Khi c chng, qu trnh khc bit v qu trnh ha hi tng i ca butaien -1,3 v olefin tng ln nh butaien-1,3 c th lp tc tch khi nhng cu t khc.
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Hnh 1.5. S cng ngh tch butadien -1, 3 t phn on C4 bng phng php hp ph. 1, 3 - Thit b trch ly; 4, 5 - Thit b to hi; 6 Sinh hn; 7 - Thit b un nng; 8 - Thit b ngng t.
izo-buten c tch ra bng H2SO4 40% 60% (H2SO4 khng phn ng vi olefin khc). Khi t n nhit thp to thnh axit tecbutyl-sunfuric v tec-butanol, chng b phn hy n khi to thnh izo-buten, cn to ra nhng sn phm ph l polyme izo-buten thp phn t:
+ H 2O (C H 3 )3 C O H (C H 3)2 C = C H
2
Phn ct C4
-H 2S O
H 2S O
(C H 3)2 C O S O 2O H
S cng ngh tch phn on C4 ca qu trnh nhit phn hydrocacbon lng, bng phng php chng ct chit tch c m t trn hnh 1.6. Phn on C4 cho vo phn gia thp (1), cn phn trn thp cho axetonitril, dung dch di thp cho qua thp tch hi (2), butaien1,3 c chng ct v cht chit ly c ti sinh quay li thp (1). Hn hp hp th butan v buten chuyn n b phn (3) tin hnh hp thu ha hc izo-butan, sau phn cn li n thp chng ct chit tch (4). Pha trn tch c butan ri chng ct thm thu c nbutan v izo-butan ring bit, n-buten trong thp (5) c chng ct khi cht chit ly, cht chic ly quay li thp (4).
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C4 H10
+C4 H8
7 iso-C4H8 CH3 CN
1 C4 H6 2 C4 H10 4 CH3 CN 8 7 n- C4 H8 5
Hnh 1.6. S cng ngh tch phn on C4 bng phng php chng ct chit tch. 1, 4 - Thp chng ct phn on; 2, 5 - Thp to hi; 3 - B phn hp ph ha hc iso-buten; 6 - Sinh hn; 7 - Thit b ngng t; 8 - B cung cp nhit.
- Phn on penten: c thnh phn rt phc tp, s liu tng ng bng 1.3. Bng 1.3. Thnh phn cc cu t ca phn on C5 (% khi lng) Crackin Cracking Hp cht Nhit phn Hp cht g xc Nhit phn xc tc tc n-pentan 12 26 Xyclopent 1-2 izo60 24 en 9 pentan 12 12 Pentaien 12 n-penten 16 12 Izo-pren 8-12 izoXyclo penten pentaien Trong s nhng hp cht ny, izo-penten, izo-pren, izo-pentan v xyclopentaien c ngha quan trng nht. tch xyclopentaien, ngi ta dng phng php dime ha n:
2
0
CH2
CH2
Ngi ta gi phn on penten di p sut v nhit t = 100 C 1200C, tin hnh chng ct phn hyrocacbon cn li khi nhng dime c nhit si cao. Sau depolyme ha bng cch gia
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nhit n nhit t = 2000C th thu c xyclopentaien. Hyrocacbon ny v dime ca n l nguyn liu chnh cho hng lot cc qu trnh tng hp. Izo-pren t phn on C5 ca nhit phn hyrocacbon lng c tch khi chng ct chit tch kt hp vi vic chng ct tng phn nhng tp cht v chng ct nguyn liu ca phn on, bi v hp th ha hc bng dung dch ammoniac-ng trong trng hp ny khng hiu qu. 1.3. Hyrocacbon thm V gi tr, hyrocacbon thm l nguyn liu tng hp hu c ha du, ng th 2 sau olefin. Nhit si ca nhng ng phn xylen rt gn nhau, v chng ch c th c tch tng phn bng chng ct tht chnh xc. P-xylen v durola nng chy nhit ln hn ng phn ca chng, nn thng dng phng php kt tinh tch chng. Ngi ta cn dng phng php ny tch naphtalen. S c mt ca h lin hp lm cho hyrocacbon thm c kh nng hp thu cao hn so vi nhng hyrocacbon khc, c bit vi parafin v naphten. Hyrocacbon thm c kh nng ha tan ln trong nhng cht lng phn cc nh dietylenglycol, phenol. Trong nhng hyrocacbon khc, chng tan rt t. Chng d b hp ph bi nhng cht hp ph rn (than hot tnh, silicagen). Nhng tnh cht ny ca hyrocacbon thm c dng trong cng nghip tch chng bng cch chit tch, chng ct chit tch v hp ph Toluen v xylen c nhit bt chy thp nn nguy him chy ca chng rt ln. S c hi ca chng vt tri hn nhng hyrocacbon loi khc v c t trong mu ph hy tun hon mu ty xng. Do nng cho php trong khng kh ti ni sn xut i vi benzen l 20mg/m3 Hyrocacbon thm thu c t qu trnh thm ha cc loi khong sn. C th l phng php nhit phn, reforming xc tc sn phm du m, cc ha than . 1.3.1. Thm ha nhng sn phm du Nhit phn: khi nhit phn sn phm du vi mc ch thu olefin thp phn t, xy ra qu trnh thm ha nhng hyrocacbon mch thng. Kt qu l trong sn phm lng ca nhit phn tch t dn mt lng ln hyrocacbon thm. Reforming xc tc: l mt trong s cc qu trnh quan trng ca cng nghip ch bin du. Qu trnh ny cho php sn xut cc cu t cao octan cho xng, cc hp cht hyrocacbon thm (BTX) cho tng hp ha du. Ngoi ra, qu trnh cn cho php nhn c kh hyro k thut vi gi r nht so vi cc qu trnh iu ch hyro khc. Qu trnh reforming xc tc thng dng nguyn liu l phn on xng c tr s
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octan thp, l phn on xng ca qu trnh chng ct trc tip t du th, hay t phn on xng ca cracking nhit, cc ha hay vibreking. C th ni reforming xc tc nh mt qu trnh thm ha cc sn phm du m. Khc vi qu trnh cracking dng xc tc aluminosilicat, trong reforming ngi ta dng xc tc 2 chc nng. Qu trnh chuyn ha ha hc khi reforming xc tc c xc nh bi 2 chc nng ca xc tc. Trn tm axt xy ra phn ng ng phn ha parafin thnh izo-parafin v naphten vng 5 cnh thnh ng ng cyclohexan; mt khc trn tm kim loi xy ra phn ng ehyro ha to vng no, vng thm. 1.3.2. Qu trnh cc ha than Qu trnh cc ha b ko theo bi qu trnh chuyn ha ha hc su phn hu c ca than. Cng nh trong nhng qu trnh ct mch nhit nhng sn phm du m, trong qu trnh cc ha, nhng sn phm lng v kh c to thnh t than t hn t du m. V vy, hiu sut cc ca n rt ln (75 80%), cn sn phm lng khng ng k (4-5%) 1.3.3. Tch v lm sch hyrocacbon thm Hm lng ca hyrocacbon thm trong sn phm lng thu c t nhng qu trnh thm ha khc nhau dao ng t 30 36% (nhit phn v reforming xc tc) n 95 97% (ankyl ha benzen v nha cc ha than ). Trong chng cn c olefin (t 2 3 n 15%), parafin v naphten. Ngoi ra, trong sn phm cc ha c mt s hp cht ca oxi (phenol, cumol), baz piridin, hp cht vng khng ng nht ca lu hunh (tiofen, tiotolen, tionaphten), chng c nhit si gn vi nhng hyrocacbon thm tng ng. Vi sn phm thu c t phng php ankyl ha benzen v cc ha than . Qu trnh lm sch bao gm nhng giai on c bnsau: Tch phenol bng cch x l phn on sn phm vi dung dch kim, ri t dung dch kim gii phng phenol bng CO2:
A rO H + N a O H 2 A rO N a + H 2 O + CO
2
A rO N a + H 2 O
2 A rO H + N a 2 C O