Gio trnh Cng ngh lc du

MC LC
Ni dung Trang

Chng 1. TNG QUAN V NH MY LC DU ............................................. 3 Chng 2. CC QU TRNH X L BAN U .................................................. 8 Chng 3. QU TRNH CHNG CT DU TH............................................... 17 Chng 4. QU TRNH CRACKING NHIT ....................................................... 38 Chng 5. QU TRNH CRACKING XC TC.................................................. 50 Chng 6. QU TRNH HYDROCRACKING XC TC.................................... 71 Chng 7. QU TRNH REFORMING XC TC ............................................... 83 Chng 8. QU TRNH ALKYL HA ................................................................ 119 Chng 9. QU TRNH ISOMER HA .............................................................. 132 Chng 10. CC QU TRNH X L BNG HYDRO .................................... 140 Chng 11. CC QU TRNH LM SCH ....................................................... 152 Chng 12. S PHT TRIN CA CNG NGH LC DU.......................... 186

Chng 1

TNG QUAN V NH MY LC DU

1. Mc ch ca nh my lc du.
Nh my lc du l ni thc hin cc qu trnh ch bin du th thnh cc sn phm du m. C cu v cc sn phm du m phi p ng c nhu cu tiu th ca th trng theo tng khu vc v s phn chia sn xut trn phm vi th gii. Ngoi ra, nh my lc du phi m bo cht lng cho cc sn phm sn xut t nh my theo cc tiu chun cht lng qui nh. Mc ch ca nh my lc du c th pht ha theo s sau:

Ngoi ra, nh my lc du cn cung cp mt lng nguyn liu rt ln cho ngnh cng nghip ha du nh: dung mi, si nhn to, nha, ha cht c bn, phn bn, ... Qui trnh ch bin ca nh my lc du c minh ha trong s sau:

2. Nhim v ca nh my
2.1 Tip nhn v vn chuyn du th C th tip nhn mt lng ln du th v c s lng ln chng loi, nhm trnh s tc ng ca s bin ng rng ln v ngun nguyn liu v c th cu thnh nguyn liu ph hp vi ch cng ngh ca nh my nhm p ng c yu cu v c cu sn phm du m ca th trng. C th tip nhn bng cu cng hoc ng ng. 2.2 Ch bin du th Thc hin cc qu trnh ch bin du th thnh cc sn phm du m hay cht nn. 2.3 Kim tra cht lng Thc hin vic kim tra cht lng cc nguyn liu v sn phm ca nh my nhm theo di cc qu trnh ch bin v m cht lng cho cc sn phm to thnh.

3. Cc qu trnh ch bin trong nh my lc du

Ty vo nguyn liu du th v mc ch ca nh my lc du m qui trnh cng ngh ch bin rt khc nhau. Nhng nhn chung, qu trnh ch bin tng th ca nh my lc du c th m t nh s sau:

S ch bin du th Tuy nhin, cc qu trnh ch bin trong cc nh my lc du lun bao gm cc b phn sau: 3.1 Qu trnh phn tch To ra cc phn on c s nhm p ng mc ch s dng cho cc qu trnh ch bin tip theo (chng ct, trch ly). 3.2 Qu trnh chuyn ho Nhm to ra cc phn t mi c tnh cht ph hp vi sn phm s dng (alkyl ha, isomer ha, reforming, cracking,). 3.3 Qu trnh x l Nhm loi b cc tp cht khng mong mun c mt trong thnh phn cc phn on v sn phm, nhm p ng yu cu lm nguyn liu cho qu trnh ch bin tip theo hay t cht lng sn phm thng phm.

S phn tch du th 3.4 Cc qu trnh bo v mi trng Bao gm cc qu trnh x l mi trng nhm bo m an ton mi trng lm vic v mi trng t nhin xung quanh nh my (bao gm cc qu trnh x l kh, nc thi, cht thi, kh chua ). Thang quy i gia cc dng nng lng 1 tn du th = 1 TOE (tons oil eguivalent) 1 tn than = 0,66 TOE 1000 m3 N.Gas = 0,99 TOE 1000 Kw in = 0,222 TOE

Nh my lc du ti Iraq

Chng 2

CC QU TRNH X L BAN U

1. n nh du nguyn khai
Sau khi c khai thc t cc ging p sut cao, trung bnh v thp du cha n nh, ngha l cha tch cc hp phn nh (etan, propan, butan v mt phn pentan), vn chuyn kh v khng kinh t v trong qu trnh vn chuyn c th tht thot cc hydrocarbon nh l cc nguyn liu c gi tr. Kh thu hi c th c s dng lm nguyn liu b sung cho cc nh my ch bin du, do cn c thu hi trit . Du sau khi khai thc c loi kh nh gim p sut, a vo b cha lng v tch khi nc, sau c a i n nh ha, ngha l tch cc hydrocarbon nh (etan, propan, butan v mt phn pentan). Du n nh c a i x l nhit ha, sau n cm cng ngh loi mui bng in (EDS). Trong du c cha kh ha tan, nc v mui. Hm lng kh trong du khai thc t 12 n 4%. S dao ng ca hm lng kh ph thuc vo dng du, iu kin n nh ha, hnh thc vn chuyn, dng bn cha du trong nh my v iu kin kh quyn Trong qu trnh n nh ha nhn c nguyn liu cho cng nghip ha du; cc phn on du n nh tt khi c chng ct khin cho ch cng ngh trong thp s t dao ng hn, to iu kin ngng t xng trong thit b lm lnh tt hn; loi b kh nng mt mt phn on xng nh do cun theo kh. Loi butan c coi l mc n nh ha ti u ca du. Tuy nhin trong mt s trng hp cn phi loi mt phn phn on pentan (loi 40 80% hm lng ca n trong du).

2. Tch mui - nc
Nu trong du c hm lng nc v mui cao ch cng ngh ca cc qu trnh b ph hy, lm tng p sut trong thit b v gim cng sut. Mui cn c tc hi ln hn. Mui ng trn b mt cc thit b trao i nhit, lm gim h s truyn nhit, dn ti tng chi ph nhin liu, gim cng sut thit b.
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Nc trong du thng to thnh dng nh tng kh ph hy. Nc trong du cha nhiu mui khong khc nhau v mt s kim loi ha tan. Cc cation thng gp trong nc l Na+, Ca2+, Mg2+ v mt lng Fe2+ v K+ t hn. Cc anion thng gp l Cl- v HCO3-, cn SO42- v SO32- vi mt lng t hn. Ngoi ra, trong du cn c mt s oxit khng phn ly nh Al2O3, Fe2O3, SiO2. Hm lng tng ca mui khong ( khong) ca nc c th t di 1% n 20 26%. Mt s mui khong d b thy phn (xem trong phn tip theo), do nc i km theo du m l vn c quan tm. Mui trong du tn ti dng ha tan trong nc hoc tinh th c tnh cht khc nhau. Clorua natri hu nh khng ha tan. Clorua canxi trong iu kin tng ng c th thy phn n 10% v to HCl. Clorua magh thy phn 90% v qu trnh ny din ra c nhit thp. Do nc c th l nguyn nhn n mn thit b. Thy phn clorua maghe: MgCl2 + H2O MgOHCl + HCl Din ra di tc dng ca nc cha trong du v do nc kt tinh clorua magh. n mn di tc dng ca sn phm thy phn din ra trong vng nhit cao (cc ng ca l nung, thit b bay hi, thp ct) v trong cc thit b nhit thp (thit b ngng t v thit b lm lnh). Trong ch bin du do phn hy hp cht lu hunh to H2S l nguyn nhn n mn mnh, c bit khi kt hp vi HCl. H2S khi c nc hoc di nhit cao tc dng vi kim loi ca thit b to sulfur st: Fe + H2S FeS + H2 Mng FeS che ph b mt kim loi, bo v n khng b n mn tip, nhng khi c c HCl mng bo v b ph hy do sulfur st tham gia vo phn ng sau: FeS + 2 HCl FeCl2 + H2S Clorua st chuyn thnh dung dch nc, cn hydro sulfur c gii phng li tc dng vi st. Bi v mui gy n mn ng dn, tch ly li trong sn phm du lm gim cht lng ca chng. Trong qu trnh loi mui bn cnh clorua cng loi 50 70% cc hp cht vanadium v niken, phn ln hp cht angtimon

v cc tp cht khc c kh nng u c xc tc v n mn thit b trong cc qu trnh ch bin tip. Do nc tn ti trong du dng nh tng bn vng nn cc phng php loi nc tp trung vo vic ph nh tng trong du. C 3 phng php ph nh: c hc, ha hc v in. 2.1 Phng php c hc Lng: Lng c ng dng cho nh tng mi, khng bn, c kh nng tch lp du v nc do chng c trng lng ring khc nhau. Nung nng lm tng nhanh qu trnh ph nh do s ha tan ca mng bo v nh tng vo du tng, gim nht mi trng v gim s chnh lch khi lng ring. Trong cc x nghip loi nc bng phng php lng c thc hin trong thit b nung nng-loi nc dng hnh tr ng c ng knh 1,5 2 m v chiu cao 4 5 m (hnh 7). Trong du c hm nng n 60oC bng n t kh lp di y thit b. Trong nh my ch bin du nc c loi tip bng cch gia nhit n 120 160oC v lng p sut 8 15 atm ( nc khng si) trong 2 3 gi.

S thit b nung nng - lng nc I - Nh tng. II - Du th. III - Nc. IV - Kh nhin liu

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Lc: Lc tch nc ra khi du da trn tnh thm t la chn cc cht lng khc nhau ca cc vt liu. Ct thch anh d thm t nc hn, cn pirit (FeS2) thm t du tt hn. lm khan du bng phng php lc s dng bng thy tinh, mn ca. Cc ht nc nh li ti bm vo cc cnh nhn ca mn ca hoc si bng thy tinh, lin kt vi nhau thnh git ln d chy xung di. Lc ng dng trong trng hp khi nh tng b ph nhng nhng git nc cn gi trng thp l lng v khng lng xung y. Hiu qu ca thp lc cao. Th d trong thp lc vi 3 lp bng thy tinh gim hm lng mui t 582 xung n 20 mg/l. Nhc im c bn ca phng php lc l mng lc nhanh b mui v bi ng bt v phi thay th. 2.2 Phng php ha hc Ph hy nh tng trong trng hp ny c thc hin bng cch s dng cc cht hot ng b mt (CHBM) c tc dng nh cht ph nh. Ph nh bng phng php ha hc c ng dng rng ri. Phng php ny c c im l mm do v n gin. Cc cht ph nh tt l cc cht ph nh hiu qu cao, liu lng thp, sn c, khng n mn thit b, khng lm thay i tnh cht ca du, khng c hoc d tch ra khi nc. tng nhanh ph nh cn hm nng du. S cng ngh ph nh nhit ha trnh by trong hnh 8.

S cng ngh ph nh nhit ha trong du 1- B trao i nhit; 2- thit b nung nng bng hi; 3- b lng I- Du nguyn liu; II- cht ph nh; III- nc mi; IV- du loi nc; V- hi nc; VI- nc tch ra.

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2.3 Phng php ph nh tng du bng in trng S dng in trng lm khan nc c ng dng rng ri trong cc x nghip v nh my ch bin du t u nm 1990. Khi a nh tng du vo in trng xoay chiu cc ht nc tch in m bt u di chuyn bn trong git nc, to cho n dng hnh tri l, u nhn ca qu l hng v in cc. Khi thay i cc ca in cc, git nc hng u nhn v hng ngc li. Tn s i hng ca git du bng vi tn s thay i ca in trng. Di tc dng ca lc ko cc ht nc ring l hng v cc dng, chng va chm vi nhau v trong in trng mnh to thnh cc m my in mi, nh cc git nc nh s ln ln, khin cho chng d lng xung trong thng in trng.

S cm lm khan bng in 1- Thit b gia nhit bng hi; 2- thit b trn; 3- thit b lm khan bng in. I- Du nguyn liu; II- hi nc; III- cht ph nh; IV-du khan v loi mui; V- nc tch ra .

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S loi nc- mui bng in vi thit b loi nc nm ngang 1- Thit b loi nc nm ngang; 2- Thit b gia nhit bng hi; 3- B trao i nhit. I- Du nguyn liu; II- cht ph nh; III- nc mi; IV- kim; V- nc lng; VI- du loi nc. S cng ngh loi nc in trng (EDW) dn ra trong hnh, thit b c cng sut 6.000 tn/ngy. Nh tng du sau khi c nung nng s tip xc vi nc mi. Thm cht ph nh vo hn hp ny, sau n c chia vo hai thit b loi nc in. Trong nh tng b ph hy, nc rt ra t pha di vo knh thot nc, cn du ly ra t pha trn v a vo b lng. Du loi mui v nc bm vo b cha, sau vo ng dn. ph nh khng bn qu trnh loi nc tin hnh hai bc: I- ch bin nhitha; II - x l in. ph nh bn vng qu trnh loi nc tin hnh 3 bc: I- nhit ha; II v III- in. Trong qu trnh lm khan hai bc kt hp nhit ha v in mc loi nc t 98% hoc cao hn. Ngy nay thit b loi nc bng in dng nm ngang, lm vic nhit 160oC v 18 atm c ng dng rng ri. Trong hnh 10 gii thiu s loi nc bng in dng nm ngang vi bn thit b, mt thit b loi nc, ba thit b cn li loi mui. S c cng sut 7 triu tn du/nm.
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Loi mui c thc hin bng cch thm nc v cht ph nh. Du t bn cha c bm bng my bm qua h trao i nhit vo cc thit b loi nc lp t ni tip nhau. ng thi np nc nng v cht ph nh vo du. Loi mui din ra trong in trng in th 32 33 kW nhit 120 130oC v p sut 8 10 atm. Du sau khi x l cha 5 10 mg mui/l, cho php cm chng ct du lm vic lin tc trong t nht hai nm. Trc y trong cng nghip ch bin du lc du ch gm cm chng ct kh quyn (AR) vi cng sut khong 3 triu tn du/nm. Vi kt qu hon thin cng ngh ch bin s cp mt mt ngi ta tin hnh t ng ha cc cm AR v AVR, mt khc a vo ng dng cm loi mui bng in (EDS), n nh phn on xng... Cc cm ring l ny c kt hp trong lin hp EDS-AVR. Kt hp cc cm trong khu lin hp tng s thng nht, gim nhn cng, gim thit b cha. Di y xt s cng ngh loi mui, nc bng in EDS. S cng ngh cm loi mui, nc bng in c trnh by trong hnh 11. Du th t ng dn a trc tip vo my bm H-1 v bm qua hai ng song song vo trao i nhit, trong n c nung nng n 140 150oC nh nhit t cc dng sn phm ly ra hoc dng hi lu. Dng du th th nht chy trong khng gian ca ng trao i nhit T-2, trong n c nung nng nh nhit ca dng tun hon th nht ca thp K-2 (thp chng ct kh quyn, hnh 13), sau qua trao i nhit T-17, trong n c nung nng nh dng tun hon th hai ca thp K-2, v i vo b phn thu gom a vo cm loi mui nc bc nht, ri sau vo thit b loi nc bng in A1A5. Dng du th th hai chy trong khng gian ca ng trao i nhit T-1, sau T-16, trong n c nung nng bng nhit ca mazut v i vo b phn thu gom trc khi a vo cm loi mui nc th nht. My bm H-41 bm dung dch kim-soda trung ha clorua v trnh n mn thit b. T my bm H-37 bm 1/3 lng dung dch cht ph nh vo dng cp ca my bm du H-1 (2/3 cht ph nh bm vo thit b loi nc bc hai).

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S cng ngh loi mui, nc bng in. A1-A5- thit b loi nc, mui nm ngang ca bc nht; B1-B5- - thit b loi nc, mui nm ngang ca bc hai; T- b trao i nhit; E- b cha; H- my bm

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 san bng nhit v p sut c hai dng du th trc khi i vo thit b loi nc bng in c kt hp v trn trong b phn thu gom, nc nng t thit b loi nc bng in bc hai cng c bm vo nh my bm H-36 v sau dng nguyn liu c chia thnh nm dng song song i vo 5 thit b loi nc bng in bc nht. phn b u du th trong thit b loi nc, trong mi dng trang b mt thit b chuyn dng v mt lu lng. Du loi mui v nc mt phn t pha trn thit b loi nc bc nht A1 A5 nhp chung v sau chia thnh 5 dng song song i vo 5 thit b loi nc bc hai B1 B5. Trong thit b thu gom trc khi a du vo thit b loi nc bc hai cng trang b my trn, trong trn cht ph nh, du th v nc c bm t my bm H-31 (10% so vi du th). Sau thit b loi nc bc hai du c chia thnh hai dng song song a vo khng gian gia cc ng ca b trao i nhit T-3, T-4, T-18, trong n c nung nng n 220240oC, sau a vo thp K-1 (thp bay hi trc). Dung dch mui t thit b loi nc bc nht c a vo b lng E-18, l b hnh tr nm ngang c dung tch 160 m3 v lm vic 150oC v 10 atm. Trn b lng c thit b by du, t du qua thit b lm lnh T-32 v c a vo b tiu nc E-19. Di b E-18 dung dch mui sau khi lm ngui trong my lm lnh khng kh c a vo b phn lm sch. iu kin ti u loi mui ca cm loi mui - nc ph thuc vo cht lng du. Th d, chn nhit sao cho nht ca du th thp hn 4 cSt; trong iu kin lng nc tin hnh thun li v khng cn tng nhit du th. Cht lng cht ph nh quyt nh lng nh cn s dng. Hiu qu ca cht ph nh c xc nh bi cht lng du sau x l - hm lng mui v nc phi thp nht.

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Chng 3

QU TRNH CHNG CT DU TH
1. C s l thuyt ca qu trnh chng ct
1.1 S si ca dung dch S si ca cht nguyn cht: Mt cht lng s si nhit m ti p sut hi bo ho ca n bng p sut mi trng ln mt thong. V d nh nc s si 1000C ti P = 1 atm (760mmHg). Nhit si ca Butan p sut, atm 1 3.41 4.80 Nhit ,oC 0 36 50

Ta gi cht c p sut hi bo ho ln, c nht si thp l cht d si. Cht kh si c p sut hi bo ho b, c nhit si cao. Thnh phn pha hi sinh ra khi un si mt dung dch: Pha hi sinh ra khi cht lng nguyn cht si l pha hi n cht. Pha hi sinh ra khi mt dung dch si l mt hn hp ca tt c cc hp phn ca dung dch v c thnh phn ph thuc vo thnh phn ca dung dch lng theo nh lut Konovalov.
0 h PA = PA .x lA = P.x A : p sut hi bo ho ring phn ca A.
l h PB = PB0 .x B = P.x B

PB0 Gi = 0 l bay hi tng i ca B so vi A. PA

Nu
> 1 : B d si hn A < 1 : B kh si hn A

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nh lut Konovalov: Khi si mt dung dch lng cho ra mt pha hi giu cht d si hn so vi dung dch lng. 1.2 Nguyn l ca qu trnh chng ct Chng ct l qu trnh tch mt dung dch bng cch un si n, ri ngng t hi bay ra c 2 phn: Phn nh l distillat c nhit si thp, cha nhiu cht d si, cn phn nng cn li l cn chng ct (redue).

Nh vy, php chng ct c th thu c Distillat c thnh phn mong mun bng cch chng ct nhiu ln.

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Nhng chng ct nhiu ln nh vy rt phin phc, tn thi gian m khng kinh t. khc phc nhc im ny ta dng h thng chng ct c ct chng ct. Ct chng ct c s a l thuyt cng ln, th c kh nng cho mt distillat c thnh phn khc cng nhiu so vi dung dch trong bnh un, tc l distillat rt giu cht d bay hi. Dng ct chng ct c nhiu a l thuyt c th thu c distillat l cht d bay hi gn nh tinh khit.

2. C s l thuyt chng ct du m
Nhm phn tch du th thnh cc phn on thch hp da vo nht si ca cc cu t v khng lm phn hu chng. 2.1 Chng ct n gin Chng ct bay hi dn dn: Ch yu dng trong phng th nghim xc nh ng cong chng ct Enghen. Chng ct bay hi mt ln: Cho php nhn c phn chng ct ln hn so vi bay hi mt ln.

Chng ct bay hi nhiu ln: Cho php qu trnh tch cc phn on theo mong mun.

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2.2 Chng ct phc tp Chng ct c hi lu: nng cao kh nng phn chia hn hp lng, ngi ta tin hnh cho hi lu mt phn sn phm nh. Nh s tip xc thm my ln gia pha lng (hi lu) v pha hi trong thp c lm giu thm cu t nh nh m phn chia cao hn. Chng ct c tinh luyn: Da vo qu trnh trao i cht nhiu ln gia pha lng v hi nh vo cc a hay m. Chng ct s c phn chia cao hn nu kt hp vi hi lu

S tip xc gia dng lng v hi trong thp chng ct

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Chng ct chn khng & chng ct vi hi nc: bn nhit cc cu t trong du ph thuc ch yu vo nhit v thi gian lu. i vi cc phn on c nhit si cao, ngi ta cn trnh s phn hu chng (gim nht, bn oxy ho) bng cch hn ch nhit (3200 - 4200C) chng ct. Nu nhit si cao hn nhit phn hu chng ta dng chng ct chn khng hay chng ct hi nc. Hi nc lm gim p sut hi ring phn lm chng si nhit thp hn. 2.3 a chng ct (Tray) Trong cng ngh du kh, chng ct nhng lng khng l (hng triu tn/nm). Ngi ta dng nhng thit b chng ct khng l, hot ng lin tc. Hi nguyn liu s bay ln nh thp v phn lng s chy xung phn di thp. S tip xc gia hai dng ny c thc hin mt cch c bit nh cc a. Ti cc a xy ra qu trnh trao i nhit gia dng hi v dng lng. ng thi ti y cng xy ra qu trnh trao i cht, phn nh trong pha lng bay hi theo pha hi, phn nng trong pha hi ngng t theo dng lng. Nh vy, khi dng hi ln n nh th rt giu cu t nh, cn dng lng i xung y li giu cu t nng hn. C rt nhiu dng a khc nhau c s dng tu vo loi nguyn liu. Nhng mc ch chung nhm m bo s tip xc gia pha lng v pha hi phi ln qu trnh phn tch hiu qu. Hin nay, s dng ch yu cc dng a sau: a nhiu l (Sieve Trays) a chp (BubbleCap Trays) a ng khi (Chimmey Trays) a Van (Valve Trays)

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Mm kiu van
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S phn b dng chy qua van nh hng rt ln n s tip xc pha v cht lng cc phn on. Mt s kiu phn b dng chy trong thp c trnh by nh sau:

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2.4 S Stripping i vi chng ct du th, dng trch ngang lun c ln sn phm nh. loi b cc cu t nh ny, ngi ta thc hin qu trnh ti ho hi ring phn cc phn nh. Qu trnh ny gi l qu trnh stripping. Qu trnh ny c thc hin trong nhng ct nh t 4-10 a, t bn cnh thp chng ct kh quyn v thng dng hi nc trc tip. Ngoi ra c th stripping bng nhit (phn on Kerozen).

2.5 S hi lu (Relux)
Nhm to ra dng lng c nhit thp i t nh thp xung y thp trao i nhit vi dng hi. T lm cho qu trnh trao i cht tch phn on c trit v thu c cht lng distillat mong mun. T l dng hon lu ph thuc vo nhiu yu t, trong yu t kinh t l bi ton quyt nh. Khi t l hon lu tng, s mm gim nhng ng knh thp tng ln. Ch yu c 3 dng sau: Hi lu nng: S dng dng hi lu trng thi lng si. Hi lu lnh: Nhit dng hi lu di im lng-si.
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 Hi lu vng: Ly cc sn phm cc mm di hi lu ln cc mm trn sau khi lm lnh.

3. Chng ct du th p sut kh quyn

Chng ct du v sn phm du vi mc ch tch du th thnh cc phn on, c thc hin bng phng php si dn hoc si nhiu ln. Chng ct bay hi nhiu ln gm hai hay nhiu qu trnh bay hi mt ln. Trong chng ct si dn hi to thnh thot ra khi thit b chng ct ngay lp tc, ngng t trong thit b lm lnh - ngng t v c thu hi di dng distillat. Ngc li, trong si mt ln hi to thnh trong qu trnh nung nng khng thot ra khi thit b ct cho n khi t n nhit no , khi c mt lng pha hi tch ra cht lng. Nhng c hai phng php chng ct ny u khng th phn tch du v sn phm du thnh cc phn on hp v c mt lng thnh phn c nhit si cao ri vo ohn ct (distillat) v mt phn phn on nhit si thp li trong pha lng. Do phi tin hnh ngng t hi lu hoc tinh ct. Vi qu trnh ny, du v sn phm du c nung nng trong bnh cu. Hi to thnh khi chng ct hu nh khng cha thnh phn si cao, c lm lnh trong thit b ngng t hi lu v chuyn sang th lng - phn hi lu. Cht hi lu chy xung di, li gp hi to thnh. Nh trao i nhit thnh phn si thp ca phn hi lu ha hi, cn phn c nhit si cao trong hi s ngng t. Trong qu trnh tip xc ny s phn tch s tt hn. Tinh ct l s tip xc gia dng hi bay ln v dng lng chy xung phn hi lu. tinh ct tt phi to iu kin tip xc gia pha hi v pha lng. S tip xc ny thc hin c nh vo thit b tip xc phn b trong thp (m, mm..). Mc phn tch ca cc thnh phn ph thuc nhiu vo s bc tip xc v lng hi lu chy xung gp hi.

26

S nguyn tc chng ct du p sut kh quyn. 1- L nung dng ng, 2- thp chng ct, 3- thit b lm lnh, 4- b trao i nhit. I- Du th; II- sn phm trn (xng); III- Kerosel; IV- du diesel; V- cn chng ct kh quyn (mazut); VI- hi lu; VII- cht cp nhit ( hi nc). Hnh trn l s nguyn tc cm chng ct du p sut kh quyn. Du th c bm vo b trao i nhit 4, trong n c gia nhit, sau a vo l nung (1) v du c nung nng n nhit cn thit v c dn vo khoang bay hi (vng cp) ca thp chng ct (2). Trong qu trnh nung nng, mt phn du chuyn sang pha hi. Du th hai pha lng - hi c a vo thp ct, trong do gim p mt phn hi nc c to thnh, pha hi tch ra khi pha lng v bay ln trn dc theo thp, cn pha lng chy xung di. Trong thp chng ct c cc mm chng ct, trn c s tip xc gia pha hi bay t di ln v pha lng chy t trn xung. ct phn lng ca nguyn liu di thp ngi ta a nhit vo mm cui cng. Nh phn nh ca sn phm y chuyn sang pha hi v do to hi lu hi. Hi hi

27

lu ny bay ln t mm cui cng v tip xc vi pha lng chy xung v khin cho pha lng giu cc cht c nhit si cao. 3.1 Chng ct du c tc nhn bay hi Mt trong nhng phng php tng hm lng cc cht c nhit si cao trong cn chng ct l a vo phn di ca thp chng ct tc nhn bay hi. Tc nhn bay hi c ng dng l hi nc, kh tr (nit, kh cacbonic, kh du), hi xng, ligroin hoc kerosel. Tc nhn bay hi c s dng rng ri nht l hi nc. Khi c hi nc trong thp chng ct, p sut ring phn ca hydrocarbon gim v dn ti nhit si gim. Nh , hydrocarbon c nhit si thp nht cn li trong pha lng sau khi ct mt ln s chuyn sang pha hi v bay ln. Hi nc chuyn ng dc theo thp chng ct v bay ra cng sn phm nh, lm gim nhit trong thp xung 10 20 oC. Nn s dng hi qu nhit v a n vo thp vi nhit bng nhit ca nguyn liu np vo thp hoc cao hn i cht. Thng hi nc sau khi qua my bm hi v turbin c p sut tng n 2 3 atm, c nung nng trong ng rut g ca l nung dng ng v np vo thp vi nhit 350 450oC. 3.2 S cng ngh cm chng ct kh quyn Trong s chng ct kh quyn, du loi nc v loi mui trong cm EDS c bm vo mm s 16 ca thp bay hi K-1 bng hai dng. T nh thp K-1 sn phm nh trong pha hi c dn vo thit b ngng t bng khng kh T-5, sau vo thit b lm lnh bng nc T-5a v c lm lnh n 45oC, ri i vo b cha E-1. Nc tch t b E-1 c dn vo knh thi. Xng t b E-1 c bm vo thp K-1 bng my bm H-5 lm dng hi lu, xng cn li chy vo b E-12. Ch nhit di thp K-1 c duy tr nh dng nng, l phn du th loi xng ca thp K-1 c bm vo l nung L-1 bng 6 dng nh my bm H-7. Tt c cc dng du t l L-1 nhp li v c bm tr li y thp K-1 bng 2 dng.

28

S cng ngh cm chng ct kh quyn K-1- Thp bay hi trc; K-2- Thp chng ct kh quyn chnh; K-6, K-7, K-9- Thp bay hi; E-1, E-12, E-3- b hi lu; T-5, T-7, T-22, T-23- thit b ngng t bng khng kh; T-2, T-33, T-17, T-19, T-11- thit b trao i nhit du th- sn phm; T-5a, T-7a, T-22a, T-20- Thit b lm lnh; L-1 l nung dng ng; H-3, H-21- My bm..

29

Sn phm y ca thp K-1 l du loi xng c ly ra bng my bm H3 v c nung nng tip trong l L-1 v t y c a vo thp chng ct chnh K-2 di mm th 38. tng thu hi sn phm sng t mazut ngi ta bm hi nc qu nhit vo pha di thp K-2. T nh thp K-2 hi xng v hi nc c dn vo thit b ngng t bng khng kh T-7, trong chng c ngng t v lm lnh n 80oC, sau i vo thit b lm lnh bng nc T-7a. Phn ngng (nhit 45oC) c a vo b cha E-3, trong nc c tch ra khi xng (nc thi ra h thng thi). Xng t b cha E-3 c bm bng my bm H-4 vo trn thp K-2 iu chnh nhit trn thp, phn xng d qua van iu chnh lu lng theo mc cht lng trong b E-3 vo b cha E-12 . ly nhit trong thp K2 s dng 2 dng hi lu: dng th nht vo di ca trch phn on 220 280oC, dng th hai - vo di ca trch phn on 280 350oC. Phn hi lu th nht c ly ra t mm th 12 ca thp K-2 bng bm H-22 v qua thit b iu chnh lu lng ri bm vo trao i nhit T-2, thit b lm lnh T-19 v vi nhit 65 70oC quay tr li mm 11 ca thp K-2, t mm th 10 phn on 180 220oC c bm ln mm trn ca thp K-6. Hi nc qu nhit c a vo y thp bay hi K-6. Trong thp K-6 din ra s bay hi ca phn on xng, hi ny quay tr li mm th 9 ca thp K-2. T y thp K-6 phn on 180 220oC c my bm H-18 bm qua h thng trao i nhit v lm lnh (T-22, T-22a) vo h thng lm sch. Phn on 220 280oC t y thp bay hi K-7 nh my bm H-19 c bm qua thit b lm lnh bng khng kh T-23, bng nc T-20, qua b iu chnh lu lng v i vo ng dn ca nhin liu diesel. T mm th 30 hoc 32 ca thp K-2 phn on nhin liu diesel (280 350oC) c ly ra v a qua thp bay hi K-9. Di thp K-9 hi nc qu nhit cng c a vo. Phn on bay hi ca thp K-9 quay li mm th 24 ca thp K-2. T y thp K-9 phn on 280 350oC c my bm H-20 bm qua h thng trao i nhit T-11 nung nng phn on xng trc thp n nh K8 v c a vo ng dn chung ca nhin liu diesel. Mazut t y thp K2 c my bm H-21 bm sang cm chng ct chn khng.

30

3.3 Ch cng ngh Di y l ch cng ngh c trng ca cm chng ct kh quyn: Thp K-1 Lu lng nguyn liu, m3/h Nhit , oC - Du th vo thp - Dng hi lu - nh thp - y thp p sut thp (trn), atm Chi ph hi, m3/h Thp K-2 Nhit , oC - Nguyn liu vo thp - Dng hi lu: + th I ti ca ra khi thp + th II ti ca ra khi thp + th I ti ca vo thp + th II ti ca vo thp L nung Nhit , oC - ti ca ra khi l - kh khi trn vch ngn - nh thp - y thp p sut thp ( trn), atm 800 800 theo cht lng ca phn on si u - 85oC 240oC 6,0 170 260 70 80 360 200 340 theo cht lng ca phn on si u - 85oC 240oC 6,0 90 Ngng cho php 1.250

31

4. Chng ct du th p sut chn khng

Chng ct du trong cng nghip hot ng lin tc nhit khng qu 370oC - nhit hydrocarbon bt u phn hy - cracking. T du th nhn c cc sn phm sng nh xng, du ha, diesel. Sau khi chng ct kh quyn (AR) cn mazut c a sang cm chng ct chn khng (VR) trong lin hp chng ct kh quyn - chn khng (AVR). Nh chng ct chn khng nhn c thm cc phn on du nhn v cn gudron. Sau khi chng ct du di p sut kh quyn nhit 350 370oC, chng ct tip cn cn li cn chn iu kin loi tr kh nng cracking v to iu kin thu c nhiu phn ct nht. Ph thuc vo nguyn liu t cn chng ct kh quyn (mazut) c th thu c distilat du nhn cho cm sn xut du nhn, hoc gasoil chn khng - l nguyn liu cho cracking xc tc. Phng php ph bin nht tch cc phn on ra khi mazut l chng ct trong chn khng. Chn khng h nhit si ca hydrocarbon v cho php ly c distilat c nhit si 500oC nhit 410 420oC. Tt nhin khi gia nhit cn du n 420oC th s din ra cracking mt s hydrocarbon, nhng nu distilat nhn c sau c ch bin th cp th s hin din ca cc hydrocarbon khng no khng c nh hng ng k. iu ch distilat du nhn th phn hy cn phi t nht bng cch tng hi nc, gim chnh lch p sut trong thp chn khng. Nhit si ca hydrocarbon gim mnh nht khi p sut d thp hn 50 mmHg. Do cn ng dng chn khng su nht m phng php cho php. Ngoi ra, tng hiu sut distilat t mazut a vo thp chn khng hi nc qu nhit hoc chng ct cn chn khng (gudron) vi tc nhn bay hi (phn on ligroin- kerosen). Chn khng to thnh nh thit b ngng t kh p hoc my bm chn khng (bm piston, bm rotary, bm phun hoc bm tia) mc ni tip vi nhau. 4.1 H thit b ngng t kh p - bm phun.

32

S cng ngh to chn khng bng h thit b ngng t kh p- bm phun. 1. Thp chn khng; 2. Thit b ngng t 3. B cha chn khng; 4. Bm phun hi to chn khng; 5. B lng; 6. Hp kh p; 7. My bm. I- Nc lnh; II- hi t bm phun; III- sn phm du. Trong h ny hi thot ra t nh thp chn khng, ngng t ngay lp tc trong thit b ngng t kh p v sau c ht bng my bm chn khng (thng bm phun hi). p sut d trong thit b ngng t kh p ph thuc vo nhit nc thi, nhng khng thp hn p sut hi nc bo ha nhit no . Nc t thit b ngng t kh p b nhim sn phm du v hp cht lu hunh (thng 5,5% so vi mazut). V vy gim dng nc nhim bn trong nh my nc thi c s dng li. Tuy nhin, khi nhit nc vo thit b ngng t kh p s tng i cht v phi trang b thm ph kin cho h cp nc. Trong s to chn khng bng h thit b ngng t kh p - bm phun. Sn phm du ngng t trong thit b ngng t khng ha long bng nc lnh, nh n d dng tch ra khi condensat, c thu gom vo b lng v ging kh p. 4.2 H bm phun - thit b ngng t kh p. Trong s ny hi t trn thp chn khng a trc tip vo bm phun, cn su ca chn khng khng ph thuc vo nhit ca nc thot ra t thit b ngng t kh p. Nh c th to chn khng su hn (p sut d t 5 10 mmHg). su chn khng ph thuc vo i p ti ca ra ca bm phun, v vy to chn khng su cn mc ni tip vi bm phun.

33

S to chn khng su. 1-Thp chn khng; 2- thit b ngng t; 3- bm chn khng; 4- bm phun (ejecter) I- Mazut; II- gasoin nng; III- Gudron; IV- hi lu; V- kh khng ngng t ; VI- hi ; VII- phn ngng t ; VIII- nc

4.3 c im chng ct trong thp chn khng c im chng ct trong thp chn khng tng t nh trong thp chng ct kh quyn. Tuy nhin n cng c mt s c im ring lin quan vi p sut d trong thp thp, iu kin nung nng nhin liu c thnh phn phn on nng. Trong thp chn khng cn to iu kin ct c nhiu nht v phn hy t nht. lm c iu ny cn s dng thit b to chn khng c c p sut chn khng thp nht trong h. gim thi gian lu ca mazut trong l nung v gim tr lc nn s dng l nung hai chiu, a hi nc vo ng xon ca l, gim thiu khong cch gia ca nhp liu vo thp v ca ra khi l nung, tng ng knh ng dn nguyn liu, gim thiu cc ch un gc, dng ch S. Cu to ca thp chn khng khc vi thp chng ct kh quyn nhm gim thi gian lu ca cn trong thp trnh phn hy n di tc dng ca nhit cao. Do lu lng cc dng hi trong thp chn khng ln, nn ng knh ca cc thp ny ln hn nhiu so vi thp ct kh quyn (8 12 m). Do s phn b ca cht lng v bt si khng ng nht nn hiu qu ca mm khng cao. phn b cht lng ng u trn cc mm nn s dng cu trc mm c bit (mm li, van (xupap) v sng). 4.4 S cng ngh cm chng ct chn khng

34

S nguyn tc cm chng ct chn khng K-10- Thp chn khng; T-35- thp ngng t; T-1, T-3, T-4, T-16, T-18, T-25, T-34- thit b trao i nhit ; T-25athit b ngng t bng khng kh; T-24, T-28, T-30, T-31- my lnh; H-1-bm chn khng phun hi; H- my bm; E- b cha; L-3- l nung dng ng, B- b cha.

35

S nguyn tc cm chng ct chn khng trnh by trong hnh 16. Mazut t di thp K-2 c my bm H-21 (khng v trong s ) bm vo ng xon ca l nung L-3 v sau khi nung nng n 400 410oC c dn vo thp chng ct chn khng K-10. gim s phn hy ca mazut khi nung nng nhit cao v to cc trong cc ng l nung v tng phn ct, thm hi nc qu nhit vo tng dng chy qua l nung ti ca vo thp K1. nh thp chng ct chn khng K-10 gi p sut khng qu 50 mmHg. Kh sinh ra khi phn hy mazut cng hi nc c dn sang thit b ngng t T-35, trong hi nc ngng t, cn kh c ht bng my bm chn khng - phun ba cp H-1. Phn ngng t t T-35 c a vo b cha E-22, t vo b cha B, nc t c thi ra cn sn phn du tch t trong b lng c my bm H-40 bm vo ca np ca my bm nguyn liu. T mm 15 ca thp chn khng K-10 dng hi lu trn c my bm H-24 ht ra v bm qua cc thit b trao i nhit T-25, thit b ngng t bng khng kh T-25a, my lnh T-28 v vi nhit 50oC c a tr li mm 18 ca thp K-10. Phn on c nhit si di 350oC d c my bm H-24 bm vo thp K-2 hoc vo ng ng nhin liu diesel. Cng c th a dng hi lu nng vo mm 14 nh my bm H-24. T mm 9 trch phn on 350 500oC ra di dng sn phm trung gian, sau n c my bm H-25 bm qua thit b trao i nhit T-16 (dng nng), sau lng phn on 350 500oC cn thit quay tr li thp nh dng hi lu sau khi qua my lm lnh T-30, phn d qua thit b trao i nhit T-1 v ly ra ngoi. T mm th 9 ca thp K-10 dng hi lu di c my bm H-26 bm vo thit b trao i nhit T-18 v thit b lm lnh T-31, trong n c lm lnh n 170oC v tr v mm s 6, cn phn d quay tr li thp chng ct kh quyn K-2. T bm H-25 v H-26 hai dng nng tr li tng ng ti mm th 8 v th 4. T y thp K-10 gudron (nha ng) c my bm H-27 bm qua thit b trao i nhit T-4, T-3, T-34, my lnh T-24 v vi nhit khng qu 100oC c a vo b cha.

36

4.5 Ch cng ngh S cng ngh cm chng ct chn khng c thit k vi mc ch nhn c phn on 350500oC (nguyn liu cho cracking xc tc) v nha ng (gudron). Thp chn khng c trang b mm van. Tt c cc mm u dng hai dng. Tng s mm l 18.Trn mm np liu v di mm sut dng hi lu gia c lp t li chn. Di y l ch cng ngh ca cm chn khng: Ch ti u Nhit , C - Mazut ti ca ra l L-3 - Vch ngn l L-3 - nh thp K-10 - y thp - Hi qu nhit p sut d trong thp K-10, mm Hg p sut hi vo my phun chn khng, atm
o

Ngng cho php 420 450 100 350 440 50 10,0

400 700 90 345 420 60 11,0

37

Chng 4

QU TRNH CRACKING NHIT

1. Gii thiu
Trong cng nghip ch bin du kh, cc qu trnh ch bin thun ty bi nhit c p dng t lu nhm ch bin cc phn on du khc nhau thnh cc sn phm lng (xng, FO), kh v cc. Cc sn phm kh c cha nhiu olefin rt thch hp cho cng ngh tng hp ho du v ho hc. Da vo nguyn liu, sn phm cn thu v iu kin chnh ca qu trnh (nhit , p sut), ngi ta chia cc qu trnh ch bin nhit thnh cc qu trnh cracking nhit, cc ha, vibreaking, cn qu trnh pyrolise (cn gi l qu trnh cracking hi). Cracking nhit l qu trnh phn hy di tc dng ca nhit, thc hin iu kin nhit khong 470 n 5400C, p sut 20 n 70 at. y l mt qu trnh c th s dng nguyn liu t phn gasoil n cn nng ca du, ph bin hay s dng l cn mazut. Sn phm thu c bao gm kh cha nhiu olefin v xng. Mc ch ca qu trnh l s dng nhit nhm chuyn ho cc phn on nng thnh sn phm lng c gi tr kinh t cao (xng, kh, cc) nhm thu hi xng t phn nng, thu mt s olefin s dng trong cng nghip tng hp ha du. Qu trnh Cracking hi Cracking hi Cracking hi Cracking hi Cracking hi Cracking nhit Cc ho Vibreking Nguyn liu Etan Etan Propan butan Xng nh Gasoil nh Gasoil nh Cn nng Cn nng Etylen propylen Etylen propylen Xng Cc Gim tc nht 720 770 720 -750 469 510 480 530 440 - 480 0,5 2 0,5 2 20 70 1 10 20 - 70 Sn phm chnh Axetylen Etylen Etylen propan Nhit , 0 C 1000 1400 800 850 770 800 p sut, kg/cm3 0,2 0,5 0,2 2 0,2 2

38

2. C s l thuyt ca qu trnh Cracking nhit

2.1 S bin i parafin CnH2n+2 kt C H to H2 Nhit cao, p thp nhiu sn phm kh. Nhit va phi (450 5300C), p sut cao nhiu sn phm lng. C ch: Theo Rice n xy ra theo c ch gc t do: - To gc t do: - Pht trin chui: - Dng phn ng :
t R Rl R * + Rl*

CmH2m + CpH2p+2

Khi n 4 th lin kt C C bn hn C H xy ra hin tng t lin

t gia mch

RH + H * H 2 + R *
R1 H + R * RH + R1*

R * + H * RH
* R1* + R2 R1 R2

2H + H 2

V d:
cao R CH 2 CH 2 CH 2 CH 3 t R CH 2 CH 2 + C H 2 CH 3
0

R CH 2 CH 2 R + CH 2 = CH 2 C H 2 CH 3 H + CH 2 = CH 2 CH 3 CH 2 CH 2 CH 3 + CH 2 = CH 2 CH 3 + R CH 2 CH 2 CH 2 CH 3 CH 4 + R CH 2 CH 2 C H CH 3 R CH 2 CH 2 C H CH 3 R CH 2 + CH 2 = CH CH 3

Nh vy, cracking nhit to ra mt lng ln etylen, sn phm thu c t nhnh, khng nhiu phn ng ng phn ha, kh thu c sn phm vng, v vy m xng thu c t qu trnh cracking nhit c tr s octan thp. 2.2 Bin i ca olefin. Nhit thp, p sut cao olefin d trng hp. Nhit tng phn ng phn hu tng. Ngoi ra, olefin cn tham gia phn ng ngng t, ankyl ho vi naphten to thnh nha v cc.
39

2.3 Bin i ca naphten. u tin xy ra cc phn ng sau: - Kh nhnh ankyl - Kh hydro olefin vng Aromatic - Phn hu naphten a vng n vng. - Kh naphten n vng parafin + olefin / diolefin. To nhiu sn phm lng v no hn so vi nguyn liu v parafin. 2.4 Bin i ca hydrocacbon thm. nhit cao, theo quy lut sau. - Kh nhnh ankyl. - Ngng t vng cc (cacboit) Tc hi ca cc : + Gim tc truyn nhit. + Gim nng sut bm. + Tng chi ph vn hnh.

3. Qu trnh Cracking nhit

C 2 vn cn lu tm: Ngn nga s to thnh cc trong ng phn ng hay thit b trao i nhit v m bo hiu qu s dng cao cc thit b trong dy chuyn. 3.1 Nguyn liu C th s dng phn on mazut ca AD, gasoil nng ca FCC hay cn nng ca qu trnh lm sch (DAO). 3.2 Sn phm Xng cracking nhit: c thnh phn khc vi xng chng ct trc tip Thnh phn ca mt s loi xng (% trng lng) Loi xng Xng chng ct trc tip Xng cracking nhit t mazut Xng cracking nhit t gasoil Xng reforming nhit 25 - 35 40 - 45 19 - 20 Olefin Aren 12 12-17 18 - 20 14 - 16 Naphten Parafin 26 5-8 15 - 20 27 - 32 62 40 45 20 25 33 37

40

T bng trn c th thy rng, trong xng chng ct trc tip, hm lng parafin l ch yu, cn trong xng cracking nhit c nhiu olefin, trong olefin c mt ni i hoc aren c nhnh olefin (styren) chim a phn. Do vy, xng cracking nhit c tr s octan cao hn so vi xng chng ct trc tip. Xng cracking thng cha cc thnh phn (tnh theo % khi lng): t 45 -50% parafin, 5 - 10% naphten, 10 -15% benzen v cc hydrocacbon khng no chim t 25 - 40%. iu ny gii thch ti sao xng cracking c ch s octan cao: MON= 68 - 72 cao hn xng ca qu trnh chng ct ban u (MON = 40 - 45). V xng cracking nhit cha nhiu olefin nn bn km, di tc dng ca nh sng, nhit , cc phn t olefin d b ngng t, polyme ha, trng hp ha to nha dn n chy khng hon ton trong xylanh. Xng cha nhiu olefin d b bin i thnh mu sm. Bi v s c mt ca cc hp cht hydrocacbon khng no lm tng ch s octan nhng cng v vy m cht lng sn phm khng tt do khng n nh d b chuyn ha (oxi ha) bi oxi khng kh (khi tn tr). V vy, sn phm thng c cho thm cht c ch. Ngoi ra, cht c ch cn c cho vo hn hp gia xng cracking nhit v cc ngun xng khc tng kh nng n nh cng nh thi gian tn tr. Cht c ch thng dng: mt vi phn on ca nha (resin) v noxidiphenylamin.Tuy nhin loi xng ny cng c u im l d khi ng my. Hm lng lu hunh trong xng cracking nhit dao ng trong khong 0,5 n 1,2% (cao gp 5 ln cho php i vi xng t). Ni chung xng cracking nhit cha m bo cht lng s dng cho ng c xng; thng phi x l lm sch bng hydro hoc cho qua reforming xc tc nhn c xng c n nh v tr s octan cao. Sn phm kh cha nhiu hydrocacbon olefin v c th cn c H2S, s c dn vo khi phn tch kh tch ring hydrocacbon parafin v olefin dng thch hp cho cc mc ch khc nhau, nh lm nguyn liu cho tng hp hay lm nhin liu. Kh cracking: Cn cha mt lng ln nhng hp cht khng no ch yu, cn ca qu trnh cracking nhit cn c s dng lm nhin liu t l. Thnh phn ca n c th iu khin bi s khc nhau v iu kin cng ngh
41

(ch vn hnh) ca l hi. Cn cracking cn c nhp chung vi cn gurdon v nhng sn phm khc lm nguyn liu cho l hi v nguyn liu ban u cho qu trnh coking. Cn bng vt cht tiu biu ca qu trnh cracking vi hai l t nh sau: Nguyn liu vo, % Phn on > 350oC (du Romakinski) Phn on > 460oC (du Arlanski) Phn on gasoil ca cracking xc tc Sn phm ra, %: Kh hydrocacbon LPG Xng Kerosen gasoil Cn cracking
Tng

Cracking nhit 100

Vibreking 100

100

3,5 3,6 19,7 5,3 67,9

100

10,7 2,3 23,3 28,5 35,5

100

2,3 3,0 6,7

88,0
100

42

S cng ngh Cracking nhit

4. Cc yu t nh hng n qu trnh Cracking nhit

4.1 Nguyn liu Nguyn liu ca cracking nhit ph bin nht l phn on mazut qua chng ct trc tip, phn on gasoil nng ca qu trnh cracking xc tc hay cn nng ca qu trnh lm sch. Cht lng ca nguyn liu l mt thng s quan trng xc nh cht lng ca sn phm. Khi iu kin cracking khng thay i, nu ta dng nguyn liu c thnh phn ct khc nhau s cho kt qu khc nhau. ng thi hm lng cc hydrocacbon trong nguyn liu c nh hng n quyt nh cht lng sn phm. nh hng gii hn nhit si ca phn on n hiu sut xng khi cracking nhit. Nguyn liu Phn on ligroil Phn on karozen Phn on gasoil Phn on xola Gii hn si (oC) 180 - 220 220 - 270 270 - 300 300 - 350 Hiu xut xng (%khi lng) 12,1 14,9 15,8 18,0

43

Nguyn liu cng nng (gii hn si cao) th bn nhit ca nguyn liu cng km, qu trnh phn hy xy ra d hn, dn n tc phn hy nhanh, cho hiu xut xng cng cao. Do vy, nhin liu nng th phn ng xy ra nhit thp hn so vi nhin liu nh. 4.2 Nhit Nu qu trnh tin hnh nhit va phi th qu trnh phn hy xy ra vi s thay i cu trc rt t. V d, nu nguyn liu cha nhiu parafin, s thu c sn phm cha nhiu parafin, nu nguyn liu gasoil c cha mt lng ln hydrocacbon vng th sn phm thu c s c nhiu naphten v aromat. Trong khong nhit chn trc, s thay i cc thng s v nhit v thi gian phn ng c tc dng tng h ln nhau. gi cho su bin i l nh nhau, khi tng nhit cn thit phi gim thi gian phn ng. i lng nhit phn ng l thng s rt quan trng. Khi tng nhit tc phn hy tng ln, v ngc li khi gim nhit th tc phn ng trng hp li tng ln. Gim nhit cracking s lm gim tc ca cc phn ng a t. Nh vy tng hiu sut cc sn phm phn hy (kh, lng) v gim hiu sut cc sn phm a t (cn nha, cc) cn thit phi gi nhit phn ng cao ng vi thi gian phn ng thch hp, l nhim v chnh ca qu trnh cracking nhit. 4.3 p sut p sut xc nh trng thi pha ca h cng nh chiu hng v tc ca phn ng. p sut khi cracking phn an gasoil nh cn phi m bo trng thi lng ca tc nhn phn ng, bi v trng thi lng to iu kin tt cho qu trnh, khng xy ra s qu nhit cc b, s to cc l cc tiu cn hiu sut xng l cc i. Nu cracking cn nng, cn phi gi cho h thng trng thi pha hn hp hi lng. Khi cracking xy ra trong pha lng vi nguyn liu nng nh mazut, gudron th p sut khng nh hng nhiu. Khi p sut v nhit cng cao, v tr t mch nghing v cui mch, iu dn n lm tng hiu sut sn phm kh, sn phm lng gim.

44

Cn nu ch c p sut cao th v tr t mch C - C xy ra gia mch, dn n hiu sut sn phm lng tng. 4.4 Thi gian lu Thi gian lu ca nguyn liu trong vng phn ng cng lu th sn phm to thnh d b ngng t, dn n to nha, to cc, lm gim hiu sut xng v kh. Nh vy, tng hiu sut sn phm kh, xng, v gim hiu sut phn ng trng hp (cn, cc) th vng phn ng, nhit duy tr cao v thi gian lu ca nguyn liu trong vng phn ng phi ngn Cracking nhit n-C16H34 Nhit (0C) chuyn ho (%) Hiu sut phn ng (% khi lng) Sn phm Sn phm phn trng hp hy (xng kh) 55 44,2 T l phn hy/ trng hp 1,26

375

55,2

400

53,5

62,2

37,8

1,65

425

50,8

72,4

27,6

2,26

T bng trn ta thy, khi nhit tng ln, chuyn ho hu nh xp x nhau, song sn phm phn hy tng, cn sn phm trng hp gim. V vy i vi mi dng nguyn liu khc nhau, ta cn nghin cu chn nhit ti u. Thc t li cho thy rng trong cc qu trnh cracking nhit cng nghip, sn phm cc ch yu to thnh v lng ng vng nhit va phi ch khng phi vng nhit ti a.

5. Qu trnh Cc ha

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5.1 Qu trnh Delayed Coking Trong qu trnh Delayed Coking, phn ng Cracking din ra vi thi gian rt ngn trong thit b gia nhit n thit b cc ha. Cc c hnh thnh trong thit cc ha v khi lng cc t n mc yu cu th dng nguyn liu s c chuyn sang l th hai. Trong kh cc s c tho ra khi l cc th nht v c th hai l cc ha s hot ng lin tc thay phin nhau.

46

S cng ngh Delayed Coking L cc ha hot ng p sut t 25 30 psi v nhit t 480 500oC. Lng hi hnh thnh trong thit b cc ha c dn sang thit b phn tch v phn chia thnh cc sn phm nh kh, naphta, kerozen v gasoil. Sn phm ca qu trnh Delayed Coking rt khc nhau ty thuc vo nhp liu ban u. Nhp liu v sn phm ca qu trnh delayed coking c trnh by trong bng sau:

47

5.2 Qu trnh Fluid-Coking v Flexi-Coking Trong qu trnh Fuid Coking, mt phn cc sinh ra c s dng l cht gia nhit cho qu trnh. Phn ng Cracking xy ra bn trong thit b gia nhit v bnh phn ng. Mt phn cc c hnh thnh trong thit b gia nhit, vi nhit cao n c tun hon li bnh phn ng v cung cp nhit cho phn ng cracking. Qu trnh phn ng din ra khong nhit 520oC v sn phm cc c hnh thnh ngay lp tc. Sn phm cc to thnh p ng c cc yu cu ca th trng v cc du m, tuy nhin hm lng lu hunh v kim loi cao.

48

5.3 Qu trnh Vis-Breaking Qu trnh Vis-Breaking l qu trnh cracking cc phn t mch di thnh cc phn t mch ngn hn nhm lm gim nht v im ng c ca sn phm. Trong qu trnh ny, nguyn liu l du nhin liu c nht v im ng t cao v th n khng th vn chuyn v gy kh khn cho qu trnh s dng. Qu trnh Vis-Breaking thng b ry cc phn t gia mch v xy ra khong 450oC trong khong thi gian rt ngn. Cc phn t parafin mch di s b b ry thnh cc phn t c mch ngn hn, phn ng dealkyl s gip b ry cc mch nhnh ca cc phn t hydrocacbon thm.

49

Chng 5

QU TRNH CRACKING XC TC
1. Gii thiu
L qu trnh quan trong trong nh my lc du sn xut xng c ch s octan cao t cc phn on nng hn. p ng yu cu cht lng sn phm ra.

2. C s l thuyt ca qu trnh
2.1 Xc tc cho qu trnh Cracking Xc tc cho qu trnh cracking tng si trong cng nghip thuc lai axit rn, c thnh phn kh phc tp nh sau:

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Thnh phn xc tc cracking tng si trong cng nghip

2.2 iu ch xc tc FCC Quy trnh sn xut xc tc FCC hin i c m t theo s sau (Grace-Davison): Hp phn zeolit Y: L Alumosilicat tinh th ngm nc vi cu trc kiu Faujazit vi l xp 3 chiu ng nht v c kch thc ca s ~ 8A0. V thnh phn ha hc ca zeolt c biu din bng cng thc: M2/nO.Al2O3.x SiO2.y H2O y: x > 2 v n l ha tr ca cation kim lai M Zeolit c to thnh t cc n v cu trc Khi cc n v cu trc c bn ni vi nhau theo cc mt 4 cnh ta c lai zeolit A, nu ni vi nhau theo cc mt 6 cnh ta c lai zeolit X hoc Y c cu trc tng t Zeolit Y c th dng khang t nhin, nhng hin nay ch yu c tng hp t oxyt silic v oxyt nhm, i khi t qu trnh tinh th ha t st nung (Qui trnh Engelhard). Dng Na-Zeolit c iu ch bng phng php kt tinh gel alumosilicat natri. Silicat Natri (Thu c khi x l oxyt silic vi dung dch xt nng) cho tc dng vi aluminat natri (thu c khi ha tan oxyt nhm ngm nc trong dung dch hydroxyt natri)s to thnh hydrogel v nh hnh. Gel ny sau
51

s c tinh th ha trong iu kin kim sat nghim ngt to Zeolit (Alumosilicat tinh th) vi cc ion aluminat v silicat c xp xp theo cu trc nh.

Cu trc c bn ca Aluminosilicat v n v cu trc c bn ca zeolit. Zeolit dng Faujazit c khung tinh th 3 chiu to thnh t cc t din SiO4 hoc AlO4. Lin kt -Si-O-Al- to thnh cc l xp b mt c ng knh c nh t cc hc, knh c kch thc 4-8. Cc cation d dng c trao i v c a ra khi Zeolit. Cu to Faujazit c m t nh hnh:

Cc Zeolit Y c a vo xc tc FCC di cc dng khc nhau: + Trao i mt phn hoc han tan vi dt him, phn cn li c th decation to cc dng REHY hoc REY. + Bin tnh bng phng php x l nhit v (hoc) x l ha hc to cc dng zeolit decation siu bn: H-USY, RE-H-USY hoc dng dealumin: HDY, RE-H-DY.
52

Vai tr ca t him ch yu lm tng bn nhit cho tinh th (vi zeolit dng decation NH4Y, nhit > 5000C tinh th c th b ph hy nhng vi dng REY, nhit > 9000C vn bo ton c tnh cht tinh th. Mt lai zeolit mi hin nay thng c a thm vo xc tc FCC, l ZSM-5 nhm tng ch s octan ca xng v tng olefin. ZSM-5 c t l Si/Al = 50, kch thc l xp tng i nh (5.5), hn ch cc phn t c kch thc ln i qua, do khng lm xy ra cac phn ng cracking i vi chng (Cc parafin mch nhnh, cc Alkyl benzen...) nh th khng lm gim cc hp phn cho ch s octan cao. Hn na n cn tng olefin, khng lm tng hm lng cc. Hin ti, 40% cc cm FCC Ty u a ZSM-5 nh mt ph gia tng ch s octan. Hp phn pha nn (Matrix): Trong qu trnh sn xut cht xc tc, hp phn ny ng vai tr l cht pha lang v cht kt dnh. Cht pha lang phi l cht tr nh cao lanh,ng vai tr ti nhit, hn ch s qu nhit ca cc tinh th zeolit trong qu trnh ti sinh, tng bn c hc ca cht xc tc, lm gim lng Na u c xc tc... cht kt dnh c th l cc gel ca oxyt xilic, cc polymer cha nhm, hp cht cha t st, cng c th l alumosilicat v nh hnh. Cht kt dnh ng vai tr gn kt cc hp phn trong xc tc FCC, to tnh ng b vt l cho xc tc. Cc nh sn xut xc tc chia pha nn thnh 2 phn: Phn hat ng l cc alumosilicat v nh hnh, oxit nhm; phn khng hat ng l cc cht tr nh oxit silic, cao lanh. Pha hat ng c tnh axit thp hn do c hat tnh xc tc v chn la thp hn so vi cc Zeolit. Oxit nhm c hat tnh xc tc thp hn Al-Si v nh hnh, nhng ngi ta thng a vo trong trng hp cracking cc phn an nng. Vic a pha nn vo h iu chnh tnh axit ca xc tc v tng th, so vi cc zeolit hoc Al-Si v nh hnh ring l. c tnh ca xc tc FCC ph thuc ch yu vo 2 thnh phn Zeolit v pha nn hat ng. T l cc hp phn ny c xem xt thn trng trong qu trnh sn xut nhm m bo cc nhu cu ring bit ca nh my lc du v hiu sut v cht lng sn phm. 2.3 C ch hnh thnh trung tm hot ng trn b mt xc tc

53

Xc tc cho qu trnh Cracking l xc tc axt. Cc trung tm hot ng trn b mt cht xc tc l cc tm axit Bronsted v Lewis. Cc trung tm ny hnh thnh do trong mng tinh th ca xc tc ny, bn nguyn t Oxi lin kt vi Nhm nn khng cn bng v hnh thnh mt in tch m. Cc ion nh Na+, Mg2+ hay proton s trung ha in tch ny v hnh thnh tm axt Bronsted

Khi tin hnh x l nhit khong nhit 400 500oC th xut hin cc tm axt Lewis theo s sau:

2.4 Cc giai on phn ng cracking khi c mt cht xc tc S khc nhau c bn gia cracking nhit v cracking xc tc l phn ng cracking khi c mt cht xc tc xy ra theo nhng c ch nht nh v d khng ch. Do sn phm ca cracking xc tc s c tnh chn lc cao hn so vi cracking nhit. Cc giai on phn ng cracking khi c mt cht xc bao gm: Bc 1. Hp ph cc ion Hydride trn cc tm Lewis:

Bc 2. Phn ng gia cc proton t Bronsted vi cc olefin:

54

Bc 3. Phn ng gia cc ion cacboni sinh ra t bc 1 v 2 vi cc hydrocacbon bng cch to ra cc ion hydride

Cc ion hydride ny khng bn s b phn hy thnh cc mch ngn hn, v d nh:

Qu trnh b ry mch cc ion cacbonni tun theo mt s qui lut sau: Cc parafin mch di v cc olefin lun ng phn ho trc khi b cracking. S cracking thng xy ra gia mch v thc t khng bao gi t hn 3 nguyn t C tnh t u mch. Cc nhnh ankyl gn trn vng thm s b ct st vng v cc nhnh ankyl gn vng no s b ct v tr t 3 nguyn t C tr ln tnh t u mch. 2.5 C ch phn ng ho hc xy ra trong qu trnh cracking xc tc C ch phn ng cracking xc tc l c ch ion cacboni. Cc tm hat tnh l ion ccboni c to ra khi cc phn t hydrocacbon ca nguyn liu tc dng vi tm axt ca xc tc. Tm axt xc tc c 2 lai: Lai Bronsted (H+) v Lewis (L). Tm Bronsted l khi tham gia phn ng c kh nng cho proton hot ng (H ) cn tm Lewis th thiu electron nn c xu hng nhn thm in t. Phn ng cracking xc tc sn ra theo cc giai an sau:
+

- Giai an 1: to ion cacboni: V d: trong trng hp i vi cc hydrocacbon mch thng (Alcan):

55

Trng hp phn hy izo-propyl-benzen: Trn tm axt kiu xc tc Lewis:

Trn tm axt kiu xc tc Bronsted:

- Giai an 2: Cc phn ng ca ion cacboni to cc sn phm: Khi cc ion cacboni c tao ra s lp tc tham gia vo cc phn ng bin i khc nh Phn ng ng phn ha:

Phn ng ct mch theo quy tc (ct mch v tr so vi ccbon mang in tch)

Cc ion tip tc tham gia cc phn ng ng phn ha, ct mch tip,alkyl ha hay ngng t. Bin n cc ion cacboni tip din cho n khi c cu trc bn vng nht. bn ca cc ion cacboni c th xp xp theo th t: Ion ccboni bc 3> Ion ccboni bc 2 >Ion ccboni bc 1
56

 bn ca cacboni s quyt nh s quyt nh mc tham gia cc phn ng tip theo ca chng.Cht lng sn phm c quyt nh bi cc phn ng ca cc ion cacboni, c bit l phn ng phn hy, ng phn ha v chuyn v hydro. - Giai an 3: giai an dng phn ng Khi cc ion cacboni kt hp vi nhau, nhng hay nhn nguyn t hydro ca xc tc to thnh phn t trung ha v chng chnh l cu t ca sn phm cracking xc tc.

3. Ha hc qu trnh cracking xc tc
3.1 Cc phn ng mong mun Phn ng ct mch (cracking ): xy ra theo c ch ion cacbonium.

Hot tnh cracking ca cc hydrocacbon gim dn theo th t sau: Olefin > Ankyl Aromatic > Ankyl naphten, isoparafin> n-parafin, naphten>> nhn thm. Tc cracking tng khi s nguyn t cacbon tng, phn nhnh tng. Phn ng isomer ho: Thng xy ra trc phn ng cracking. Nhng sau cracking qu trnh t xy ra do thi gian lu trong bnh FCC ngn v mch ngn ln cn tr qu trnh isomer ho. 3.2 Cc phn ng khng mong mun. Phn ng chuyn v hydro: Phn ng ny xy ra s chuyn v mt phn t hydro t mt hydrocacbon ny sang mt hydrocacbon khc (khng no) dn n hnh thnh cc hp cht no v thm.

57

Lm gim olefin, tng Aromatic tng kh nng to cc. Lm gim ch s octan xng (mt olefin). Lm xng n nh hn. Phn ng ngng t: Polymer ho olefin ng vng dehydro ho to Aromatic.

Ankyl ho Aromatic ng vng nhnh ankyl hydro ho poly Aromatic (cc).

Cng ng vng Diels Alder dehydro ho poly Aromatic. Hai phn ng trn cn hn ch (to cc) nhng khng loi b (gim olefin). Phn ng to hydro: do phn ng dehydro ho, xy ra khi c mt ca Ni lm cht xc tc. Phn ng to C1 C2: sinh ra do phn ng cracking nhit. Cc phn ng ha hc xy ra trn tng dng hydrocacbon ring l c trnh by trong bng sau:

58

Hydrocacbon Parafin

Sn phm qu trnh cracking xc tc -Olefin v parafin -Olefin v hydro -iso-parafin -Cc hp cht olefin c trng lng phn t thp -Parafin v dien -Parafin, naphten v hydrocacbon thm -Polyme, cc -Olefin -Cyclohexan v olefin -Hydrocacbon thm

Olefin

Naphten

Hydrocacbon thm (alkyl thm) Phn ng bc 2: Naphten+ Olefin Hydrocacbon thm +Olefin

-Parafin v alkyl c mch bn ngn -ng phn ha, chuyn v nhm alkyl -Sn phm ngng t v cc. -Hydrocacbon thm -Parafin -Sn phm ngng t v cc

4. Nguyn liu v sn phm

4.1 Nguyn liu Nguyn liu cho qu trnh cracking xc tc thng c khang nhit si t 300-5000C, c th t cc ngun nh sau: Phn an ct chng ct kh quyn ca du th, khang si: 3804100C Phn an ct chng ct chn khng ca du th, khang si: 3805500C Phn ct t qu trnh Coking ca du th DAO (cn chn khng deasphaltene) (5500C) Cn chng ct kh quyn ( > 3800C) ca vi lai du th Nguyn liu l nhng phn ct nh s cho sn phm c hiu sut C3, C4 tng cn H2 v cc gim. Nhng phn an nh (200- 360oC) nhn c t
59

chng ct trc tip l nguyn liu tt nht sn xut xng t v xng my bay. Nguyn liu t cc phn an nng (cc gasoil) chn khng l ph bin nht trong qu trnh cracking xc tc. Nhm ny cho sn phm l xng v cc phn an sn phm trng, qua chng ct chn khng lm gim nhng cu t v hp cht c hi cho qu trnh cracking. Thc t l thnh phn nhng kim lai nng lm nhim c xc tc nh vanadi, niken thng c trong cc hp cht c kim, trong thnh phn ca nha, asphalten l nhng phn t ln, c nhit si cao, khi chng ct chn khng nhng cht ny s li phn cn ca chng ct chn khng, chnh v vy m cc phn ct c lm sch, c lai v c gim cc cht gy nhim c xc tc. Cng chnh cc hp cht nha, asphalten khng nhng cha cc kim lai nng m chng cn l ngun chuyn thnh cc nhiu nht, lm gim hat tnh ca xc tc. Thnh phn ha hc ca nguyn liu nh hng rt ln n hiu sut ca qu trnh. Vi nhm hydrocacbon parafin s cho hiu qu chuyn ha cao nht. Nhm hydrocacbon thm cho hiu sut xng km hn v li tng mc chuyn ha to cc. Nhng cht phi hydrocacbon l c hi cho qu trnh cracking xc tc, chng gy ng c cho xc tc v cn chuyn vo sn phm lm gim cht lng sn phm nh cc hp cht lu hunh. Trong thc t vi s tin b ca cng ngh, qu trnh cracking xc tc c th s dng cn chng ct kh quyn lm nguyn liu trc tip cho qu trnh m khng phi qua chng ct chn khng. Qa trnh ny gi l qu trnh cracking xc tc cn (RFCC). Nhng lai du th parafin, t lu hynh thng c t cc cht gy nhim c xc tc v ch s cc Conradson thp rt thun li cho vic dng thng cn chng ct kh quyn lm nguyn liu cho qu trnh RFCC. tng ngun nguyn liu, ngay c cn chng ct chn khng cng c lm nguyn liu cho qu trnh cracking xc tc sau khi kh nha v asphalten. 4.2 Sn phm Cht lng ca sn phm cracking xc tc thay i trong phm vi rt rng ph thuc vo rt nhiu yu t nh nguyn liu, lai xc tc v cc thng s

60

cng ngh ca qu trnh. Hn hp sn phm ca qu trnh cracking c chuyn tip n thit b chng ct phn ra cc phn an sn phm: - Sn phm kh, - Cc phn an xng, du ha, - Cc phn an gasoil nh v nng. - Phn an cn dng lm nhin liu t l... c im cc sn phm kh v lng thu c t qu trnh cracking xc tc: Kh hydrocacbon Hiu sut kh c th t 10-25% nguyn liu ph thuc vo nguyn liu v iu kin cracking. Trong iu kin nhit cao, tc nguyn liu nh, bi s tun han xc tc ln th hiu sut sn phm kh s ln v ngc li th hiu sut kh nh.Nguyn liu c hm lng lu hynh cao th sn phm kh c nhiu kh H2S v khi nguyn liu c nhiu nit th sn phm kh cracking c nhiu NH3. Sn phm kh, kh kh c dng lm nhin liu kh, Etylen v Propylen l nguyn liu cho sn xut nha Polyetylen(PE) v Polypropylen (PP), Propan-propen lm nguyn liu cho qu trnh polyme ha v sn sut cc cht hat ng b mt v lm nhin liu t (LPG). Propan-propen, butan-buten cn lm nguyn liu cho qu trnh alkyl ha nhn cu t c tr s octan cao pha vo xng, v lm nguyn liu cho cc qu trnh tng hp ha du. Phn an xng Phn an xng thng c nhit 40-200oC, phn an ny l cu t c bn pha trn vi nhng cu t khc t cc qu trnh Reforming, alkylha, v cc phn an naphta t qu trnh chng ct trc tip sn xut cc lai xng t, xng my bay. Phn an xng t qu trnh cracking xc tc khc vi cc phn an c cng khang nhit si t qu trnh chng ct trc tip l c tr s octan cao hn v c bit l c thm thnh phn hydrocacbon olefin. Phn an 200-280oC Dng lm du ha v phn an 200-350oC c dng pha trn v sn xut nhin liu diezen Cc phn an > 350oC
61

c dng lm nhin liu t l F.O hay c dng lm nguyn liu cho qu trnh cc ha.

5. Cc cng ngh cracking xc tc tiu biu

5.1 Cracking vi lp xc tc c nh Dy chuyn cracking xc tc u tin do Houdry, mt k s ngi Php thit k c a vo cng nghip ch bin du t nm 1936. Cng ngh ny hat ng theo kiu gin an vi lp xc tc c nh. Nhc im ca cng ngh ny l hat ng gin an v vy rt phc tp trong vn hnh (qu trnh cracking ng xc tc cho sn phm v ti sinh xc tc trong cng mt thit b). Dy chuyn ny nhanh chng c ci tin v ch nm nm sau, nm 1941 xut hin qu trnh cracking vi lp xc tc chuyn ng. 5.2 Cracking vi lp xc tc tng si Qa trnh cracking c lp xc tc chuyn ng thay th qu trnh Houdry. Qa trnh phn ng xc tc v ti sinh xc tc c thc hin cc thit b ring bit: thit b phn ng (l phn ng) v thit b ti sinh xc tc (l ti sinh). Xc tc lm vic c cha cc chy t l phn ng vo l ti sinh v sau khi ti sinh li ngc v l phn ng (hoc bng t chy hoc bng cng bc) to thnh mt chu trnh lin tc. Nm 1942 quy trnh cracking c lp xc tc chuyn ng (FCC) u tin c a vo hat ng c tn l Up Flow.

62

Nm 1944 ngi ta tng ng knh ca l phn ng v l ti sinh, tch hi sn phm c thc hin ngay trong l phn ng v ti sinh xc tc dng tng si v qu trnh thi cho xc tc chuyn ng t pha di v ly ra ngai y l. Dy truyn hat ng nh vy c tn l Down Flow. Ngi ta lin tc ci tin thit b v c hnh dng ca xc tc. Hnh dng xc tc ph bin l dng vin hnh cu nhm lm gim s mt mt xc tc v gim s mi mn thit b v nng cao hiu qu tch ca xyclon. Model I, t l xc tc/nguyn liu ch t ti a l 3 nhng model II c th tng ti a l 10. Hng M.B.Kellog thit k lai cn bng p sut Model III nm 1946. Hng Standard-Oil (New Jersey) thit k lai FCC mi (Model IV) t ci tin ca Model II v a vo hat ng t 1952. Cng ngh FCC ngy cng c ci tin nhm t hiu sut v cht lng xng cao hn, vi cht lng nguyn liu ngy cng xu hn.

Cng ngh FCC ngy nay

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Cng ngh FCC ca mt s hng cng nghip ni ting gm c: 5.3 Cng ngh ca hng UOP Qua cc bc ci tin lin tc, hin nay cng ngh FCC ca UOP cng p dng cracking nhm chuyn ha cn du nng. Qa trnh ca UOP c cng ty Ashland OilCo pht trin. Chnh hng UOP thit k 2 lai FCC: lai l ti sinh t chy han tan 1 cp v lai ti sinh hai cp. Lai l ti sinh t chy han tan mt cp: l lai thng dng trn tan th gii, nhng UOP ci tin h thng phn phi nguyn liu phn cui ca ng riser, h thng ti sinh xc tc, b phn lm lnh xc tc, xc tc nng cao tnh linh ng ca nguyn liu cng nh sn phm ca qu trnh. Xc tc sau phn ng c t dng tng si, tc cao, nhm chuyn ha han tan CO thnh CO2, khng s dng thm cc ph gia khc v hm lng cacbon cn li trn b mt xc tc sau ti sinh l thp nht so vi cc cng ngh thng thng. Lai L ti sinh hai cp: C bn nh cng ngh FCC thng thng nhng c thit k c bit cho nguyn liu cn nng hn (RFCC, vi 4-10 % cn cacbon conradson trong nguyn liu). L ti sinh xc tc chia lm hai tng, vi b phn lm lnh xc tc c b tr bn trong v c ci tin kim sat lng cc, lng nhit cho phn phn ng. Tng th nht pha trn c nhim v t chy mt phm hm lng cc trn b mt xc tc, tng th hai, lng cc cn li trn b mt xc tc s c t chy han tan. iu ny dn n hm lng cacbon cn li trn b mt xc tc lun < 0.05 % khi lng. 5.4 Cng ngh ca Kellog S vn chuyn xc tc c thc hin theo phng thng ng rt thun li v c th dng van chn iu khin qu trnh tun han ca xc tc. Qa trnh cracking c thc hin han tan trong l phn ng dng ng ng (l ng ng). H thng xyclon c t ngay ca ra ca ng ng. Trong l ti sinh xc tc v khng kh tip xc ngc chiu nhau. Kiu RFCC c trnh by trong hnh 10. c im chnh ca model ny l vi phun nguyn liu c ci tin nhm tng cng s tip xc gia xc tc v
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nguyn liu, b phn lm ngui c thay i bng cch t t pha c thay cho pha lang trong l ti sinh trnh n mn, mi mn trang thit b do xc tc v nhm lm tng tc truyn nhit. Hnh dng b phn lm ngui xc tc do Kellog thit k cng tng t ca UOP ch khc l cch b tr cc ng trao i nhit t ngc chiu 5.5 Cng ngh ca hng Shell Shell c nhiu ng gp trong vic pht trin cracking xc tc phn cn nng (RFCC). Qu trnh Shell LRFCC (Long Residue FCC) cracking xc tc cn nng v rng, c b phn lm ngui xc tc trnh s t chy qu nhit. Thit b trnh by trong hnh sau:

.
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5.6 Cng ngh IFP Total v Stone & Webster Hai hng cng nghip ny hp tc tht k qu trnh RFCC vi ti sinh xc tc 2 cp. Qa trnh nhm cracking xc tc cn nng v c tn l R.2.R Process. Qa trnh cng c trang b b phn lm ngui xc tc, h thng kim tra v iu khin nhit ca khi l phn ng. c im ca cng ngh R.2.R l l ng, ti sinh 2 cp, c s ci tin thit b phun nguyn liu trc tip vo dng xc tc nng.
66

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5.7 Cng ngh Exxon Exxon lin tc nghin cu ci tin cng ngh FCC, t khi a ra model IV v n nay a ra lai model III-R, cracking c c tnh linh hat. C th s dng nguyn liu khc nhau t cc phn ct chn khng n cc lai cn nng.

6. Cc yu t nh hng n cng ngh FCC

c im cng ngh FCC l qu trnh cracking xc tc tng si (gi si), qu trnh thc hin trn dng xc tc chuyn ng lin tc trong l phn ng cng nguyn liu v sang l ti sinh thc hin vic t cc (dng vi oxy khng kh) trn xc tc tham gia phn ng ri li sang l phn ng. Chu trnh trn c lp li mt cch lin tc. Cng ngh FCC hat ng vi nhng thng s quan trng sau: chuyn ha, tc np liu; t l xc tc /nguyn liu; nhit ; p sut. 6.1 chuyn ha chuyn ha C c tnh bng: C = Tng hiu sut (kh +Xng +Cc) C= 100- y(100-z) y: l % th tch ca sn phm c nhit si cui cao hn im si cui ca xng z: l % th tch xng c trong nguyn liu..

S khi qu trnh FCC

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6.2 Tc np liu L t s gia lng nguyn liu c np trong mt n v thi gian trn lng xc tc trong l phn ng.v c k hiu bng M/H/M Khi tng tc np liu s lm gim chuyn ho v ngc li v tc np liu l i lng ngc vi thi gian phn ng. Khi s dng xc tc c hat tnh cao ta c th tng tc np liu khi y s tng nng sut ca thit b. 6.3 T l xc tc/Nguyn liu T l xc tc zeolit/nguyn liu,cn gi l bi s tun han xc tc (X/RH). Vi lai xc tc zeolt th X/RH=10/1 cn xc tc v nh hnh X/RH=20/1. Khi thay i t l X/RH s lm thay i thi gian lu ca xc tc trong l phn ng v l ti sinh v thay i c lng cc bm trn xc tc. ch n nh t l X/RH tng s lm tng chuyn ha v gim hm lng cc bm trn xc tc, khi thi gian tip xc gia xc tc v nguyn liu gim nhng hat tnh trung bnh ca xc tc li tng ln. 6.4 Nhit Nhit trong l phn ng khi vn hnh trong khang 470-540oC. Khi nhit tng ln th tc phn ng phn hy nhanh hn nhng cng thc y cc phn bc 2 nh kh hydro tng ln dn n tng hiu sut hydrocacbon thm v olefin. Khi C1-C3 trong kh tng, C4 gim, t trng v tr s octan ca xng tng ln. Khi nhit cao hiu sut xng gim, hiu sut kh tng v cc khng tng. 6.5 p sut Khi p sut tng th hiu sut xng tng ln, hiu sut C1-C3 gim, hm lng olefin v hydrocacbon thm gim dn ti tr s octan ca xng gim. 6.6 Ti sinh xc tc cracking s dng xc tc c lu, trong cng ngh phi thc hin vic ti sinh xc tc. Nguyn nhn chnh lm mt hat tnh ca xc tc l do cc to thnh bm kn b mt hat tnh ca xc tc.

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 ti sinh xc tc ngi ta tin hnh t cc bng khng kh nng trong l ti sinh. Khi t cc s to thnh CO, CO2, cc phn ng kh cc hp cht lu hynh. C + O2 CO2 C + 1/2O2 CO CO + 1/2O2 CO2 H2 + 1/2O2 H2O S + O2 SO2 SO2 + 1/2O 2 SO3 MeO + SO3 MeSO4 MeSO4 + 4H2 MeO + H2S + 3H2O Nhit lng ta ra c dng cp nhit cho xc tc mang vo l phn ng cracking.

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Chng 6

QU TRNH HYDROCRACKING XC TC

1. Gii thiu
Hydrocracking l qu trnh tng i mi nhng pht trin nhanh chng, l dng khc ca qu trnh cracking xc tc. N c tin hnh vi s tham gia ca xc tc, nhng khc vi cracking xc tc l thc hin trong mi trng hydro, di p sut cao (n 30 MPa) v nhit thp. Ph thuc vo iu kin qu trnh, c bit p sut cao hn, t mt dng nguyn liu c th thu c cc sn phm khc nhau - t kh ha lng n du bi trn v cn du vi hm lng lu hunh thp, t isopentan n phn on nhin liu diesel. Phn on xng thu c c th chia thnh phn nh, c tr s octan cao hn v phn nng, c s dng lm nguyn liu cho reforming xc tc. Hydrocracking khng ch c ng dng trong sn xut cc dng nhin liu khc nhau, nguyn liu cho ha du, m cn sn xut du nhn index cao t nguyn liu c hm lng parafin cao. y l hng pht trin mi v c trin vng trong sn xut du nhn index cao. Hydrocracking cng nh cracking xc tc c kh nng ch bin su du th. ng dng qu trnh ny vo cng nghip c nh hng ln n s hon thin tip cc qu trnh ch bin du. Tnh mm do ca qu trnh - c th lm vic vi nhng nguyn liu khc nhau, vi hiu sut cho sn phm sng v sn phm sm khc nhau, khin cho qu trnh ny tr thnh mt trong nhng qu trnh then cht ca cc nh my ch bin du hin i. ng dng rng ri hydrocracking gip cho cc nh ch bin du gii quyt vn thay i nhu cu sn phm du theo ma (ma xun v h cn nhiu sn phm sng hn, cn ma thu v ng cn nhiu sn phm sm), ngoi ra n cng gip gim nhim mi trng. Nguyn liu c s dng cho hydrocracking l phn on xng ( sn xut kh ha lng); phn on kerosen - diesel v distilat chn khng ( sn xut xng, nhin liu phn lc v nhin liu diesel); sn phm cn ca qu trnh ch bin du sn xut du nhn index cao); du lu hunh cao, mazut
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cha lu hunh v lu hunh cao, semigudron v gudron ( sn xut sn phm distilat hoc nhin liu t l vi hm lng lu hunh thp). Hydrocracking khc vi lm sch bng hydro cc distilat du l din ra vi s ph hy phn t nguyn liu, cho php thu c cc hydrocarbon nh hn t hydrocarbon nng. Th d, t distilat chn khng c th nhn c cc thnh phn xng t, kerosen (du ha) v du diesel. Hydrocracking cng cho php loi lu hunh trong cc sn phm cn ca ch bin du hoc thu c sn phm du sng t cn ny. Qu trnh hydrocracking din ra theo mt bc hoc hai bc. Trong cc s mt bc cc qu trnh lm sch bng hydro, hydro ha v hydrocracking din ra trong cng mt h phn ng. Cc s nh vy c ng dng trong cc trng hp khi cn thu c distilat trung bnh (dng phn on diesel) nhiu nht v kh ha lng hoc xng t nguyn liu nh vi hm lng nit thp. S hai bc c ng dng khi cn tin hnh lm sch bng hydro, hydro ha nguyn liu v hydrocracking tin hnh ring nhm gia tng chuyn ha thnh xng hoc nhin liu diesel t nguyn liu c nhit si cao v cha nhiu nit. Trong trng hp ny trong bc th nht xc tc c s dng l oxit hoc sulfur niken, coban, volfram, cn trong bc th hai - xc tc cha zeolit vi platin hoc kim loi qu khc. Cng c nhng qu trnh tin hnh trong ba bc. Trong cc s hydrocracking cng nghip nguyn liu l distilat hoc cn qu trnh c tin hnh trong mi trng hydro (chi ph khong t 1,2 n 4%k.l) p sut 32 MPa, tc th tch n 1,5 gi-1, bi tun hon n 1.800 m3/m3 nguyn liu, nhit n 430oC trong bc nht v 480oC trong bc hai.

2. Nguyn liu v sn phm

Nguyn liu cho qu trnh hydro cracking rt a dng. Nguyn liu Naphten Kerozen Distillar DAO. Naphten VD, Naphten, kerozen, gasoil, du gc, nguyn liu cho cracking. Sn phm Phn on C3, C4

Gasoil (cracking ) Naphten, kerozen.

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Trong cc ngun nguyn liu trn th phn on gasoil t Visbreaking, Delaycoking v Cycle Oil t Cracking xc tc l thng c s dng nht. c im ca sn phm ca qu trnh Hydrocracking so vi qu trnh Cracking thng thng l t olefin, aromatc v nhiu iso parafin. V d nh xng i t hydrocracking c ch s octan trung bnh kh, n nh cao. Phn on Kerozen c smoke point cao v phn on Gasoil th c ch s cetan kh cao. Ngoi ra, qu trnh Hydrocracking cn to ra phn on C4 vi nhiu iso butan, y l phn on rt hu ch cho qu trnh Alkyl ha trong nhmy lc du. Qu trnh ny cn tn dng c cc phn nng nhiu Aromatic chuyn ho thnh xng, kerozen v gasoil.

3. Cc phn ng ha hc
3.1 Phn ng mong mun Phn ng cracking v hydro ha: y l hai phn ng chnh din ra trong qu trnh Hydrocracking. Hai phn ng mong mun ny c tc dng tng h ln nhau trong cng mt qu trnh. Phn ng cracking s to ra v cung cp olefin cho qu trnh hydro ho v ngc li, phn ng hydro ho s cung cp nhit lng cho qu trnh cracking. Tuy nhin, nhit ta ra t qu trnh hydro ha cao hn so vi nhit ta ra t qu trnh cracking, v th khi xem xt ton b qu trnh th c th xem hydrocracking l phn ng ta nhit. Phn ng cracking ch yu din ra trn cc hp cht naphten c to ra t qu trnh hydro ha cc hp cht aromatic. Phn ng isomer ho: lun din ra ng hnh cng vi phn ng cracking. Trong qu trnh isomer ho xy ra trc, sau cc lin kt C-C s b b gy bi qu trnh cracking. 3.2 Cc phn ng khng mong mun. Bn cnh cc phn ng chnh, vi tc dng ca nhit v cht xc tc, mt s phn ng khc s din ra song song ng thi nh:

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Hydro deankyl ho Aromatic: y l phn ng cracking din ra trn cc mch nhnh ca cc hp cht aromatic. +

Phn ng ny s lm tng dng sn phm kh, do n s lm gim hiu sut ca sn phm chnh. Phn ng HDS, HDN: cc phn ng ny c tc dng loi b cc cht bn nh lu hunh, nit, nhng li lm tiu hao lng hydro trong qu trnh. Tuy nhin, lng hydro trong nh my lc du rt hn ch, v th phn ng ny c xp vo phn ng khng mong mun. Phn ng cc ho: Vi s hin din ca hydro trong phn ng lm gim ng k phn ng cc ha. Tuy nhin vi xc tc axt mnh, cc phn ng cc ha cng c thc y mnh hn.

4. Xc tc cho qu trnh Hydrocracking

Cht xc tc s dng cho qu trnh hydrocracking thng thng l tinh th alumino silicat c mang cc kim loi t him. y l xc tc lng chc, chc nng axt c to ra bi thnh phn alumino silicat, cn chc nng hydro ha c to ra bi cc kim loi. Clor khng yu cu phi a vo thnh phn ca xc tc ny. Cc kim loi t him thng c s dng ch yu Pt, NiMo, NiW. Xc tc cho qu trnh Hydrocracking rt d b u c bi cc tc nhn c hi trong nguyn liu, do phi x l nguyn liu (hydrotreater) trc khi a vo qu trnh ny. Nu trong nguyn liu c mt lng ln hydrosunfua th xc tc s b u c bi lu hunh, anoniac s lm gim chc nng axt ca xc tc, chc nng hydro ha ca kim loi s b bin mt bi cc kim loi bn c trong nguyn liu. Ngoi ra, nguyn liu cn phi c loi tr hi m, v y l tc nhn ph hy cu trc tinh th ca cht xc tc nhit cao. Sau thi gian lm vic xc tc c th mt hot tnh v cc c th hnh thnh ngay khi c mt hydro, do cn phi ti sinh xc tc sau mt chu k lm vic.

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Khi xc tc trng thi c nh (fix bed) th thng xy ra s ngng t cc v qu nhit cc b do vic to dng knh qua lp xc tc. Cn xc tc tng si c nhiu u im hn v mt truyn nhit v truyn khi.

5. Cc yu t nh hng n cng ngh

Kh nng cracking v dng sn phm mong mun ph thuc vo iu kin hot ng xc nh ca qu trnh. Cc yu t nh hng n hot ng ca qu trnh c th k n nh: cht xc tc s dng, tc dng, p sut tng, p sut ring phn ca hydro Mt vi ch hot ng khc khe (sn xut kerozen v naphtha t gasoil nh) i hi phi gim trng lng phn t ca nhp liu v tng lng hydro. Cn i vi ch hot ng nh c ng dng cho cc nguyn liu gasoil nng to ra cc sn phm diesel v fuel oil. 5.1 nh hng ca nhit y l phn ng to nhit, v th qu trnh thch hp nhit thp. Nhng nu nhit qu thp th tc phn ng s gim, do nhit c xem nh tc nhn duy tr hot tnh ca xc tc. Thng thng, i vi ch hot ng nh th nhit ca qu trnh dao ng t 650oF n 750oF, cn ch hot ng khc khe th i hi khong nhit t 750oF n 850oF. 5.2 nh hng ca p sut v lng hydro s dng Lng hydro s dng trong qu trnh va tham gia phn ng v va c tc dng bo v b mt xc tc, hn ch qu trnh to cc. Qu trnh Hydrocracking l qu trnh tng s mole nn n thch hp hot ng p sut thp. Thng thng p sut khong 1.200 psig, lng hydro tiu th khong 1000 2000 scf/bbl. Nhng i vi ch hot ng khc khe th i hi phi ph hy cc hp cht nng v m vng nn n cn p sut khong 2000 psig v lng hydro tiu th khong t 3000 4000 csf/bbl tr ln. Lng hydro s dng cng nhiu th cng c li v mt chuyn ha, n mt khong 25% cho cc phn ng loi lu hunh v bo ha cc hp cht olefin, aromatic. Hm lng hydro ti ca ra ca bnh phn ng yu cu phi

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cao ngn chn qu trnh tch t cc v u c xc tc. Phi tin hnh lm sch v b sung thm hydro cho dng tun hon.

6. S cng ngh Hydrocracking tiu biu

V phn ng chnh l cracking xc tc nn c th xem nh hm lng cc hp cht C1, C2 l rt thp, nu c th ta nhp chung vi dng kh H2S v NH3 Ra bng nc ho tan cc mui c kh nng to thnh.
H 2O + NH 3 + H 2 S NH 4 HS NH 4 + HS

Qu trnh cracking hydro khng c s dng rng ri v l do kinh t nh p sut cao i hi thit b ln, vn hnh cn H2. 6.1 Qu trnh Hydrocracking mt cp Qu trnh Single stage Hydrocracking ch c mt bnh phn ng, n thng s dng cho cc ngun nhp liu t gasoil n distillat. Qu trnh ny i hi phi gii hn hm lng H2S trong nguyn liu sao cho khng nh hng n xc tc.

Single stage Hydrocracking Cht xc tc desunfua thng nm lp trn trong bnh phn ng v xc tc hydrocracking nm lp pha di. Cc phn ng n nh olefin thng l nguyn nhn gy nn qu nhit cc b, v th hydro thng c b sung gia ca lp xc tc nhm mc ch lm mt. Phng n hydrocracking mt bc n gin, kinh t v cho php thu c distilat trung bnh ti a. Tuy nhin s mt bc khng cho php nhn c hiu sut xng cao, do hn ch ng dng trong thc t.
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S hydrocracking mt bc 1- L nung; 2- l phn ng; 3- thp tch p sut cao; 4- thp tch p sut thp; 5- thp debutan; 6- thp chng ct. I Nguyn liu; II- hydro; III- kh; IV- kh hydrocarbon; V- xng nh; VIxng nng; VII- distilat trung bnh; VIII- cn tun hon. Cn bng vt cht ca s hydrocracking mt bc nguyn liu gasoil chn khng: u vo, %k.l. Nguyn liu Hydro Cng Sn phm:, %k.l. NH3 H 2S C1 C2 C3 C4 C5 C6 Phn on C7 177oC Phn on 177 343oC Cng 100 2,69 102,69 0,16 2,57 0,43 0,60 1,43 2,33 2,09 3,72 16,25 73,11 102,69
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Tnh cht ca nguyn liu gasoil chn khng s dng cho hydrocracking nh sau: Khi lng ring 20oC, kg/m3 927 Thnh phn phn on, oC: Nhit si u 310 10% 371 30% 420 50% 449 90% 513 Nhit si cui 546 Hm lng, %k.l. Lu hunh 2,42 Nit 0,13 o Nhit ng c, C 21 cc, %k.l. 0,17 Hm lng hydrocarbon thm, %k.l.50,5 Tnh cht ca sn phm hydrocracking c trnh by trong bng. Tnh cht ca sn phm hydrocracking mt bc Tham s T trng 20oC, kg/m3 Thnh phn phn on, oC: Nhit si u 10% (t.t.) 50% (t.t.) 90% (t.t. Nhit si cui Hm lng, %k.l. Hydrocarbon thm Naphten Parafin Tr s octan (RON) Tr s cetan Nhit ng c, oC Xng nh 661,5 32 41 54 71 82 1 14 85 76 Xng nng 752,3 93 104 129 157 168 6 52 42 55 Nhin liu diesel 825,6 177 202 256 318 343 50 -43

6.2 Qu trnh Hydrocracking hai cp S cng ngh hydrocracking hai cp rt c ng, trong c th ch bin nguyn liu vi hm lng tp cht u c xc tc hydrocracking cao; thay i iu kin qu trnh, cho php thu c nhng sn phm mong mun
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vi hiu sut cao nht nh xng, nhin liu phn lc hoc diesel. Trong trng hp ny trong bc u tin hnh lm sch bng hydro v cracking mt phn, bc hai hydrocracking.

Tnh cht ca sn phm hydrocracking hai bc gasoil chn khng*, tin hnh khng lm sch sn phm ca bc I Tham s Ch nhn c hiu sut cao nht sn phm Xng nh u vo, %k.l. Nguyn liu Hydro Cng Sn phm:, %k.l. NH3 H2S C1- C3 C4 Xng nh Xng nng Nhin liu phn lc Nhin liu Diesel Cng 0,20 2,60 4,20 14,10 24,30 58,54** 103,94 0,20 2,60 2,60 8,58 15,56 23,823* 49,62 102,98 0,20 2,60 2,00 4,67 8,27 26,353* 58,44 102,53 100,00 3,94 103,94 100,00 2,98 102,98 100,00 2,53 102,53 Xng nng Nhin liu diesel

*) Tnh cht ca Gasoil chn khng nh trn **) Nhit si cui ca xng l 177oC 3 *) Nhit si cui ca xng l 142oC

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Tnh cht ca sn phm hydrocracking hai bc ch sn xut nhin liu diesel vi hiu sut cao nht Tham s T trng 20oC, kg/m3 Thnh phn phn on, oC: Nhit si u 10% (t.t.) 50% (t.t.) 90% (t.t. Nhit si cui Hm lng, %k.l. Hydrocarbon thm Naphten Parafin Tr s octan (RON) Tr s cetan Nhit ng c, oC 35 44 59 74 84 1 14 85 80,4 96 109 132 158 175 6 56 38 62,5 177 201 257 318 348 50 -46 Xng nh Xng nng 661,5 754,7 Nhin liu diesel 825,6

Severe Two stage Hydrocracking

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C hai s cng ngh dng ny. Trong s th nht, sau phn ng bc th nht tin hnh lm lnh v tch sn phm phn ng v tch hydrosulfur, amoniac v cc kh hydrocarbon nh ra khi sn phm. Trong s th hai, sn phm ca phn ng bc th nht cng vi hydrosulfur, amoniac c a trc tip vo phn ng bc th hai, v hydrosulfur v amoniac khng phi l cht u c mt s xc tc cho phn ng trong bc th hai.

S cng ngh Hydrocracking hai cp linh hot Qu trnh vi lp xc tc tnh tin hnh iu kin sau: p sut, MPa 5 20 Nhit , oC 250 450 Tc np nguyn liu, gi-1 0,5 2,0 3 3 Bi s tun hon kh cha hydro, m /m 400 1.000 Trong thc t trong cc h thng vi xc tc lp tnh c th thc hin hon nguyn oxy ha xc tc trc tip trong l phn ng. Hon nguyn oxy ha xc tc hydrocracking tin hnh p sut 36 MPa trong dng kh tr tun hon c thm khng kh. Lng khng kh thm vo kh tr c tnh ton sao cho khi t cc trn xc tc nhit khng tng qu 530 550oC. Phng php hon nguyn oxy ha nh vy i hi phi thm vo cc thit b

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chnh ca s my nn khng kh p sut cao, cc bnh cha m p sut cao v ng dn np kh tr v khng kh.

S hydrocracking hai bc khng tin hnh lm sch sn phm ca giai on I. 1- L nung; 2- l phn ng bc th nht; 3- l phn ng bc th hai; 4- thp tch p sut cao; 5- thp tch p sut thp; 6- thp debutan; 7- thp chng ct. I Nguyn liu; II- hydro; III- kh; IV- kh hydrocarbon; V- xng nh; VIxng nng; VII- distilat trung bnh; VIII- cn tun hon. ch bin cn chn khng v nguyn liu c nhit si rng (th d, 170 550oC) thit k cc qu trnh vi xc tc tng si (qu trnh H-oil, HC..). Mc ch chnh ca qu trnh ny l thu c phn on distilat trung bnh.

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Chng 7

QU TRNH REFORMING XC TC
1. Gii thiu
T sau nm 1900, t ra i thc y vic sn xut xng t nh my lc du. Lc xng ch yu ch ly t chng ct trc tip. n khong 1912 th chng ct trc tip khng cn tho mn vi nhu cu v xng ngy mt tng cao. Mt khc xng loi ny cha mt lng ng k kh t C1-C4 lm cho bay hi ca xng tng v kh nng chng kch n khng cao ( th hin qua ch s octan ch xp x 60). T cc nh lc du nghin cu v pht trin mt lot cc qu trnh ch bin du nhm sn xut ra xng c cht lng cao hn. V c bn xng thng phm ngy nay c pha trn t cc sn phm ca cc qu trnh sau : xng chng ct trc tip t du th, xng t cracking nhit v cracking xc tc, xng reforming xc tc, xng t ng phn ha, alkyl ha, c th c thm cc hp phn t hyrdocracking, t polymer ho . Ngy nay vic s dng cc ng c c h s nn cao i hi cht lng nhin liu, c bit l ch s octan cao. p ng yu cu , ngi ta pha trn vo xng cc ph gia hoc tng cng cc hp phn hydrocacbon cho ch s octan cao. Hin ti vi cc tiu chun nghim ngt v mi trng mt loi ph gia truyn thng l tetraetyl ch, tuy lm tng ch s octan ln 15-20 s nhng li gy c hi i vi sc khe con ngi, nn gn nh c loi b hon ton. i vi cc ph gia thay th hu hiu nh MTBE, TAME cng c mt s kin nghi ng v kh nng chm phn hy ca chng trong mi trng. Hin ti Vit nam xut hin mt s ph gia mi cha Mn, Fe c th thay th tm thi cc ph gia truyn thng. Nhng cc ph gia trn c s kim loi ny cng cn gy nhiu tranh lun, cn c tip tc lm sng t v kh nng nhim mi trng. Ngi ta c xu hng la chn phng n th hai, tng cng cc hp phn pha ch t cc qu trnh ch bin su nh cracking, reforming, ng

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phn haCc hp phn ny cho ch s octan cao hn nhiu so vi xng t chng ct trc tip, m li t gy nhim mi trng. Xng pha trn nhm mc ch t nhng ch tiu quan trng sau : p sut hi bo ha (RVP- Reid Vapor Pressure) : o p sut hi ca cc hydrocacbon, cn thit cho s khi ng ca ng c. Ch s octan : o mc chng kch n ca xng, ch tiu quan trng v ng c kch n thp s hot ng hiu qu hn v tit kim c nng lng. c hi : o cc hp phn c hi trong xng. Cc nh my lc du thng ch n hm lng benzen, olefin, lu hunh. Ch s octan l i lng c quan tm hn c v thng c la chn nh gi v iu chnh cht lng xng. Ty thuc vo ch s octan m ngi ta c th chia thnh xng thng (regular) hoc xng cht lng cao (premium). nhiu nc, cc phng tin vn ti la chn mc cht lng xng theo ch s octan theo s hng dn ca cc nh ch to ng c. C 2 mc cht lng 87 v 89, thng s dng mc 87 hn. Cn hiu y l gi tri trung bnh gia ch s octan o theo phng php nghin cu v ch s octan o theo phng php m t: (RON+MON)/2. cc cy xng VN ngi ta nim yt gi xng theo ch s RON. C th thy i vi phn on xng nh (ts-80oC) tng i kh c th ci thin ch s octan bng cc chuyn ha ho hc, ngoi tr mt qu trnh duy nht c th p dng, l ng phn ha, trong cc n-parafin c chuyn thnh cc isoparafin, lm tng ng k ch s octan. Vi cc phn on xng nng (ts > 80oC ) giu parafin v naphten c th lm tng ch s octan nu chuyn ha chng thnh cc hydrocacbon thm (aromatics). y chnh l nguyn tc ca qu trnh reforming xc tc. Reforming xc tc l qu trnh lc du nhm chuyn ha phn on naphta nng c chng ct trc tip t du th hoc t mt s qu trnh ch bin th cp khc nh FCC, hidrocracking, visbreaking, c ch s octan thp (RON =30-50) thnh hp phn c s ca xng thng phm c ch s octan cao (RON =95-104). V mt bn cht ha hc y l qu trnh chuyn ha cc n-parafin v naphten c mt trong phn on thnh cc hydrocacbon thm. Chnh cc
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hydrocacbon thm vi ch s octan rt cao lm cho xng reforming c ch s octan cao ng hng u trong s cc xng thnh phn Thnh phn xng thng dng hin nay trn th gii thng cha : - Xng cracking xc tc : 35% t.t - Xng reforming xc tc : 30% t.t - Xng alkyl ha : 20% t.t - Xng isomer ha : 15% t.t T cc s liu trn cho thy, xng reforming ng th hai trong xng thng phm, ch sau xng cracking. Thm ch mt s khu vc nh M, Ty u, xng reformirng c phn vt tri.
United States

3% 10% 3% 5% 12%

Butane Isomerate FCC gasoline Polymerisation gasoline reformate

36% 1%

30%

Ether Alkylate HYC gasoline

Phn b thnh phn xng thng mi M Mt s tnh cht ca reformat : - Thnh phn ct: thng thng t 35 190oC - T trng : 0,76 0,78 - Ch s octan RON : 94 103 (tu thuc iu kin cng ngh) Do v tr quan trng ca xng reforming trong thnh phn xng thng phm, c bit l xng cht lng cao m hin nay trong mi nh my lc du trn th gii thng c ti thiu l mt phn xng reforming xc tc. Cng
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sut ch bin nm trong khong 40 tn/gi n 150 tn/gi. Tng cng sut ca cc phn xng reforming xc tc trong tt c cc nh my lc du Php ln ti 18 triu tn trong mt nm. Ngoi ra, reforming cn cung cp nguyn liu BTX cho ho du v cung cp H2 cho qu trnh x l v chuyn ho bng H2 trong nh my lc du.

2. Nguyn liu v sn phm

2.1 Nguyn liu ca qu trnh Xut x: Xng t chng ct trc tip, Xng t qu trnh Visbreaking, Hydrocracking, Phn on gia ca sn phm FCC Thnh phn: Hn hp hydrocarbon t C7 n C11 (trong trng hp nh my khng c phn xng isomerisation c th s dng phn on C5 n C11) Tnh cht: - Khong chng ct: 60-180C T trng: 0.7-0.8 g/cm3 Trng lng phn t trung bnh: 100-110 RON: 40-60 : 40-60 wt% : 0 wt% : 20-30 wt% : 10-15 wt%

Thnh phn nhm: Paraffin Olefin Naphtene Aromatic

Hm lng tp cht: Xc tc rt nhy vi cc cht c c trong nguyn liu, do cn thit phi lm sch nguyn liu (dng cc cng ngh lm sch HDS, HDN, HDM). Gii hn tp cht cho php trong nguyn liu (sau khi lm sch): S < 1ppm N (hu c) 1 ppm H2O (v cc hp cht cha oxy) 4 ppm Kim loi (AS, Cu, Pb...) 15 ppb Olefin v cc diolefin = 0 Halogen (F) 1 ppm

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Metals (Pb, As, Sb, Cu...) < 1ppb V nguyn tc ngi ta c th s dng phn on naphta t 60180oC tin hnh qu trnh reforming. Nhng ngy nay ngi ta thng s dng cc phn on c gii hn si u 80oC lm nguyn liu. Gii hn si u uc thit lp nh vy nhm loi bt cc hp phn C6 d chuyn ha thnh benzen l mt hp cht c hi, cn tin ti loi b theo tiu chun mi v mi trng. Gii hn si cui ca nguyn liu thng c chn trong khong 165180oC. Gii hn si cui ca nguyn liu khng nn cao qu 180oC v xng reforming cha nhiu hydrocacbon thm, c nhit si ln hn nguyn liu khong 20oC. M gii hn si cui ca xng thnh phm (cha t 40-50% reformat) theo tiu chun th gii ch cho php n 200205oC. Ngoi ra nu im si cui ca nguyn liu qu cao s dn ti qu trnh cc ha cc hydrocacbon nng, lm gim hot tnh xc tc. nh hng chiu di mch cacbon (lin quan n im si cui ca nguyn liu) n chuyn ha naphten t thy r v phn ng xy ra nhanh. i vi parafin, chiu di mch cng tng (trng lng phn t cng cao) th qu trnh dehydro vng ho cng thun li. Tuy nhin mch cacbon cng cng d gy hn do cracking. Phn ng dehydro ha naphten thnh hp cht thm xy ra d dng, vi vn tc ln hn nhiu so vi phn ng dehydro vng ha parafin thnh hp cht thm. Nh vy, nguyn liu cng giu parafin cng kh chuyn ha thnh reformat so vi nguyn liu giu naphten. C th m t nh tnh s chuyn ha trn hai phn on nh hnh sau:

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kh

kh

N
t P

N t P

A N
t N

N
A Naphta giu parafin

A
A

t N t A A Naphta giu naphten

A

t A

reformat

reformat

V vy, t uc cht lng sn phm mong mun (v d, vi RON nh trc) nguyn liu giu parafin i hi nhit phn ng cao hn ( tng khc nghit ha ca qu trnh). Trong cng nghip ngi ta thng nh gi kh nng chuyn ha ca nguyn liu thnh sn phm thm da vo gi tr N+2A (N, A - % trng lng ca naphten v aromat tng ng c trong nguyn liu). Gi tr ny cng cao th kh nng thm ha cng ln, khc nghit ca qu trnh vn hnh cng gim. Ch s N+2A bin thin trong khong 30- 80. Hng UOP (M) c a ra h s KUOP c lin quan n ch s N+2A theo cng thc sau: KUOP = 12,6 (N+2A)/100. Vi mc ch sn xut BTX cho ha du th vic la chn ngun nguyn liu v gii hn im ct phn on ng vai tr quan trng. thu tng BTX ngi ta thng chn phn on 60- 145oC. Nu ch thu benzen chn phn on 65-85oC. Thu toluen chn phn on 85-120oC. Thu xylen chn phn on 120-145oC. Thnh phn v tnh cht ca mt s nguyn liu reforming Naphta trung bnh t hydrocracking ASDTM D86, oC IBP 10% Naphta Trung ng Naphta giu parafin ( rp) 92 106 Naphta giu naphten (Nigeria) 88 107

98 115

81 105

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30% 50% 70% 90% FBP Thnh phn,% V Parafin Naphten Aromatic N+2A RON d415

127 140 157 180 201 33 55 12 79 62 0,775

113 119 129 143 166 45 45 10 65 55 0,754

115 123 132 147 155 66,8 21,8 11,4 44,6 50 0,716

115 123 132 145 161 29,3 61,9 8,8 79,6 66 0,779

Trong cng nghip nguyn liu cn c x l nhm mc ch loi tr cc cht u c xc tc reforming (hp cht S, N, nc, cc kim loi), iu chnh im ct nguyn liu ph hp. C th tm tt cc bc x l s b nguyn liu nh sau: Cho nguyn liu v hidro i qua l phn ng c cha xc tc NiMo (hoc CoMo) nhm loi tr cc kim loi, cc hp cht cha lu hunh v hp cht cha nit (gi chung l cc qu trnh x l dng hidro). - Trong trng hp nguyn liu l cc phn on xng cracking cn thm giai on x l lm no ha olefin nhm loi tr kh nng to nha. Tip theo cho nguyn liu qua ct tch loi H2S v nc. Trong nhiu trng hp, cn tch phn on xng nh ( a vo phn xng isomer C5/C6) ra khi phn on xng nng (dng cho reforming xc tc).

2.2 Sn phm ca qu trnh reforming xc tc C th m t mi tng quan gia nguyn liu v sn phm ca qu trnh reforming xc tc theo gin sau :

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 R e fo rm a t R O N > 95 N a p h th a 40<R O N <60

C A T A L Y T IC R E F O R M IN G

A r o m a t ic s BTX H y d ro g e n

Nh vy, t naphta nng ban u vi ch s octan thp sau khi tin hnh reforming xc tc, ngi ta thu c cc sn phm vi hiu sut sau: - Reformat (xng C5+ ) : 80 - 92% Trong C4 : 3 - 11% : 2 - 9% C3 Kh nhin liu C1-C2 : 2 - 4% Hidro : 1,5 - 3,5 % cc sn phm quan trng hn c l reformat (xng C5+), cc

hydrocacbon thm - m ch yu l benzen, toluen, xylen (BTX) v kh hydro k thut. a. Sn phm xng reforming xc tc Mt s tnh cht ca xng (reformat) : - Thnh phn ct: thng thng t 35190oC - T trng: 0,76 0,78 Ch s octan RON: 94 103 Thnh phn hydrocacbon: ch yu l aromatic v paraffin, naphten

ch chim < 10%, olefin khng ng k. Do c cht lng cao (ch s octan cao nht trong s cc xng thnh phn, thu c t qu trnh lc du), hm lng olefin li rt thp nn xng reforming c th s dng lm xng my bay. S thay i thnh phn v tnh cht ca xng reformat trong cc gii hn nu trn ph thuc vo nguyn liu ban u, iu kin cng ngh, cht xc tc. V d tng quan gia nguyn liu l naptha Trung ng v sn phm reforming trnh by trn bng sau. So snh Nguyn liu Sn phm reforming t du th Trung ng

90

ASTM D86 d
4 15

Thnh phn , %V FBP 166 185 P N A N+2A RON 65 115 55 95

IBP Nguyn liu Sn phm C5+ 0,754 0,701 81 60

10 % 105 93

50 % 119 118

90 % 143 152

45 45 10 40 5 55

Thnh phn parafin trong nguyn liu kh nh hng n cht lng xng C5+. Nu ch s dng ton b reformat lm xng thng phm s khng kinh t, do hm lng hydrocacbon thm qu cao, to nhiu cn trong ng c v gy nhim mi trng. Xng ny li c p sut hi bo ha thp, lm cho ng c kh khi ng. Chnh v vy ngi ta a vo xng thng phm cc hp phn khc nh xng ng phn ha, xng alkylat, butan, MTBE... b. Kh hydro k thut y l sn phm kh quan trng ca qu trnh reforming xc tc. Hm lng hydro trong kh chim 70 90%. Thnh phn nguyn liu, cht xc tc v iu kin cng ngh cng nh hng n hm lng hydro trong kh. Kh ny mt phn c s dng li cho qu trnh reforming, cn phn ln c s dng cho cc qu trnh lm sch bng hydro (HDS, HDN, HDM...) hoc cc qu trnh chuyn ha c hydro (hydrocraking, hydroisomer ha). y l ngun thu hydro kh r, hiu sut cao ( thu c khong 90 120 Nm3/m3 nguyn liu) v c th lm sch tu mc ch s dng. Vic ci tin cng ngh, xc tc cho qu trnh reforming nhm lm tng hiu sut xng th cng ko theo s gia tng hm lng H2 trong sn phm v thc y thm s pht trin cc qu trnh s dng hydro. c. Kh ho lng LPG Kh ha lng thu c sau khi cho sn phm i qua thp n nh xng, bao gm ch yu propan v butan. Hiu sut kh ph thuc vo tnh cht ca cht xc tc m trc tin l axit. y l sn phm khng mong mun trong iu kin reforming, v s lm gim hiu sut ca sn phm chnh l reformat. d. Sn phm hydrocacbon thm

91

Qu trnh reforming cn cung cp ngun nguyn liu BTX (benzentoluen-xylen) cho ha du. Cc sn phm thm trong qu trnh ny chim ti 65-75% trong tng sn phm lng hoc c th cao hn na vi cc cng ngh v xc tc hin i. Trong c bit quan trng l paraxylen- nguyn liu cho sn xut cht do, si tng hp, cao su nhn to, nguyn liu cho cng nghip dc phm, m phm, thuc nhum

3. Cc phn ng ha hc
Nguyn liu ban u cho reforming ch yu l phn on naphta nng, c nhit si nm trong khong 80-180oC, cha nhiu parafin v naphten, di tc ng ca nhit cao (khong 480-540oC ), xc tc a chc nng v mt p sut va phi (530 atm ), c th xy ra cc hng chuyn ha c bn sau: n-Parafin Aromat Parafin nh (C7 C10) iso- Parafin Naphten (C6 C10) 3.1 Nhm cc phn ng chnh Cracking hydrocacbon parafin Parafin l thnh phn quan trong cacc phn an gasoil. Nng lng hat ha ca phn ng cracking parafin gim dn theo chiu di ca mch parafin tng. V vy khi cracking mch hydrocacbon parafin cng di th cng d b gy. S phn nhnh v s lng nhnh ca parafin l rt quan trng trong qu trnh cracking, chng lin quan n s to thnh ion cacboni v do quyt nh n tc to thnh sn phm. V d trng hp chuyn ha parafin n-C6 (n-hecxan) khi cracking trn xc tc aluminosilicat: C-C-C-C-C-C Chuyn ha 14 % Aromat Parafin nh

Chi tit hn, chng ta chia cc phn ng xy ra lm 2 nhm nh sau:

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C- C-C-C-C C C-C- C-C-C C C- C- C C C C C C-C C C C

----------

25 %

----------

25 %

------------

32 %

---------------10 %

Phn ng chnh to sn phm ph thuc vo s tng quan gia phn ng cracking theo quy tc v phn ng chuyn hydro ca ion cacboni.
+

R1H ------

RH +
+

R1 olefin

R2

Cracking hydrocacbon Naphten Trong qu trnh cracking xc t Naphten chuyn ha thnh olefin C3 c C4 .Cc naphten c mch bn di hn thng b ct nhnh to thnh cyclohexan v olefin. Vng naphten tip tc c th b kh hydro to thnh hydrocacbon thm.
R

+L +H

R-C+-R

Ion cacboni b ng phn v cracking to thnh izo-parafin.(L l tm axit Lewis v H l tm axit Bronsted).

93

Cracking cyclohexan
A(H+) -H2

H+ C = C -C - C -C- C dut vong

- H+ CH3 +H2 -H+

CH3

Nh vy qua cracking c th thu c sn phm l vng nh hn hoc vng i v cho nhiu sn phm lng hn.Do vy ngi ta cho rng naphten l thnh phn u im nht i vi nguyn liu cracking xc tc. Cracking hydrocacbon thm (Aromatic) Do cc hp cht alkyl thm c vng thm rt bn nn khi cracking s sy ra qu trnh ct nhnh alkyl trc . Toluen c bn rt ln v khng th tch nhm metyl hay etyl trong iu kin cracking .Mch alkyl cng di th cng d b b gy v nu mch alkyl li c nhnh th tc ct nhnh cng ln. V d khi cracking xc tc propylbenzen, phn ng sy ra nh sau: C6H5 CH2 - CH2 CH3 C6H6 + CH3-CH=CH2

Phn ng ng phn ha i vi hydroccbon thm Para-Xylen Meta Xylen Orto-Xylen

Phn ng khp vng to ra hydrocacbon thm a vng v cui cng hydrocacbon thm a vng tham gia phn ng ngng t to cc. Tm tt qu trnh cracking xc tc i vi hydrocacbon ring l nh sau:

94

Hydrocacbon Parafin

Sn phn qu trnh cracking xc tc -Olefin v parafin -Olefin v hydro -izo-parafin -Cc hp cht olefin c trng lng phn t thp -Parafin v ien -Parafin, naphten v hydrocacbon thm -Polyme, cc -Olefin -Cyclohexan v olefin -Hydrocacbon thm -Parafin v alkyl c mch bn ngn -ng phn ha, chuyn v nhm alkyl -Sn phm ngng t v cc. -Hydrocacbon thm -Parafin -Sn phm ngng t v cc

Olefin

Naphten

Hydrocacbon thm (alkyl thm) Phn ng bc 2: Naphten+ Olefin Hydrocacbon thm + Olefin 3.2 Nhm cc phn ng ph

Vi nguyn liu l parafin ngai phn ng chnh l ct mch cn km theo phn ng dehydho ha V d: C4H10 toC, xc tc CH4 + C3H6

C4H10 toC, xc tc C4H10 toC, xc tc

C2H6 + C2H4 C4H8 + H2

Vi nguyn liu l olefin th ngai phn ng cracking cn c phn ng trng hp: 2CH3-CH2-CH=CH2 Phn ng ng phn ha:
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CH3-(CH2)5-CH=CH2

CH2=CH-CH2-CH3

CH3-C=CH2 CH3

CH3-CH=CH-CH3 Phn ng kt hp Hydro to parafin: R-CH=CH2 + H2 R-CH2-CH3

Phn ng khp vng sau c th b kh H2 thnh cc aromatic:

CH2=CH-CH2-CH2-CH2-CH3

-3H2

CH 2 -CH 2 -CH 2 -CH 3

toC, xuc tac + 5H2

CH 2 - CH 2 -CH 2 -CH 3

Ngai ra cn sy ra phn ng ngng t v to cc:

-H2

-2H2

Trong qu trnh cracking xc tc, phn ng to cc cn tm gii php hn ch v chng lm gim hat tnh ca cht xc tc. Phn ng to kh (C1, C2) cng cn gii hn, v mc tiu chnh ca cracking xc tc l sn xut xng t c ch s ctan cao. Cc phn ng trn dn ti lm gim hiu sut sn phm reformat v hidrogen, lm tng im si cui ca reformat (do to cc hydrocacbon thm a vng, cc olefin mch di v bn thn cc) v lm gim hot tnh xc tc.
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Phn ng hydrocracking to nhit (H = -10 kcal/mol) v iu kin reforming thun li cho hydrocracking, mc d qu trnh xy ra chm. nhit cao phn ng xy ra p o so vi ng phn ha v dehydro ho parafin. Sn phm cracking ch yu l cc hydrocacbon nh C1C5, mch thng v mch nhnh. V phng din no qu trnh ny thun li c th to thnh cc sn phm isoparafin c ch s octan cao hn so vi cc sn phm ca qu trnh ng phn ha trong iu kin reforming. V d, n-octan c ch s octan cc thp (<0), trong iu kin reforming ch cho ra hn hp cn bng ng phn C8 vi ch s octan = 35, trong lc hydrocracking C8 thnh isopentan v propan, cho ch s octan xp x 90 i vi hp phn C5 . 3.3 C ch phn ng reforming v s tng ch s octan nh hng nhit ng hc n c ch phn ng: Nhit phn ng ca mt s phn ng chnh trong qu trnh reforming c nu trong bng sau: Nhit phn ng ca mt s qu trnh STT 1 2 3 4 5 Phn ng Dehydro ha parafin Dehydro ha naphten Dehydro vng ha parafin ng phn ha parafin Hydrocracking H (Kcal/mol) 31,5 52,8 63,6 -1 -5 -10

Dehydro ha naphten v dehydro vng ha parafin l cc phn ng thu nhit mnh (endothermic), dehyro ha parafin thu nhit va phi, cn ng phn ha parafin to nhit nh (exothermic). Ba phn ng u xy ra thun nghch, c s gia tng s phn t trong sn phm phn ng (do hnh thnh H2), nn thun li nhit cao, p sut thp.

97

Ph thuc nhit cn bng t chuyn ha 90% vo p sut Phn ng Nhit cn bng chuyn ha 90%, oC 1 atm 1. Dehydro ha : Cyclohexan Benzene + 3H2 MethylCyclohexan Toluene + 3H2 2. Dehydro vng ha : n-Hexan Benzene + 4H2 n-Heptan Toluene + 4H2 3. Dehydro ng phn ho : MethylCyclopentane Benzene+ 3H2 294 315 354 305 315 10 atm 355 391 487 428 391 15 atm 443 492 562 496 492 50 atm 487 540 623 550 540

T bng trn, iu kin l thuyt thun li v p sut v nhit c th t chuyn ha 90% cho cc phn ng thm ha l 1atm v khng qu 350oC. Tuy nhin trong thc t ngi ta khng tin hnh qu trnh reforming iu kin trn, l do ti sao chng ta s xem xt tip theo trong phn ng hc. nh hng ca nhit v p sut n cn bng nhit ng gia parafin v aromatic t C6 n C9 c biu din trn hnh sau:

98

Xi 1.0 P H 2 = 10 B ars
AR iP iP

P H 2 = 30 B ars

AR

0.5

C6

nP

nP AR AR iP

1.0
iP NA nP

0.5

M axi

C7

nP AR iP AR

1.0

0.5

iP nP nP AR iP nP 400 450 5 0 0T C 3 5 0 400 45 0 5 0 0T C AR

C8

1.0

0.5

C9

iP nP 3 50

Cn bng nhit ng hc cc phn ng ca qu trnh reforming T hnh chng ta thy, nu tng p sut H2 ln qu cao (30atm) s lm gim hm lng cc hydrocacbon thm to thnh, c bit i vi cc hydocacbon c s C thp hn. Chng ta cng thy, i vi hydrocacbon no c trng lng phn t cng cao th hiu ng thun li ca nhit v p sut cng r rt. Ngha l trong cng mt iu kin, cc hydrocacbon mch di hn (c s nguyn t cacbon cao hn) s d chuyn ha thnh sn phm thm hn. Nghin cu nh hng nhit v p sut n tc cc phn ng khng mong mun l cc ha v cracking, ngi ta nhn thy: Tc hnh thnh

99

cc gim khi tng p sut H2 v gim nhit phn ng, tc cracking gim khi gim p sut H2 v gim nhit phn ng. Mt khc, nh phn nhit ng hc nu, vic tng p sut hoc lm gim nhit u nh hng khng thun li n qu trnh chnh to cc sn phm thm. V vy, trong thc t ngi ta cn c s la chn cc thng s vn hnh ti u tha mn c hai yu t nhit ng hc v ng hc, ngha l bo m cho hiu sut cc phn ng thm ha cao ng thi hn ch cc sn phm cracking v cc ha (v d t 3-4% cc trn trng lng xc tc trong khong 6-12 thng). Trong cng ngh bn ti sinh ngi ta chn p sut vn hnh khong 10-20 atm, trong cng ngh CCR chn p sut t 3,5-4 atm v nhit phn ng l 500oC. Nh trn nu, trong iu kin reforming, thun li cho cc phn ng chnh l dehydro ha naphten, dehydro ng vng ha parafin, dehydro ng phn ha naphten v ng phn ha parafin. Ba phn ng u to nn cc sn phm l hydrocacbon thm v phn ng cui cho sn phm l cc parafin mch nhnh. Chnh cc sn phm ny ng gp vai tr chnh lm cho ch s octan ca xng thu c sau qu trnh reforming (cn gi l reformat) tng ln rt nhiu so vi nguyn liu naphta ban u. RON nguyn liu = 40-60 RON sn phm = 95-105 Ty thuc vo hiu sut reformat thu c m ch s octan c th cao hn hay thp hn. V d, reforming vi cng ngh bn ti sinh cho hiu sut xng ~ 80% th RON t ~90 cng ngh ti sinh lin tc cho hiu sut reformat ~ 90% cho RON ~100.

4. Xc tc s dng cho qu trnh Reforming

Xc tc reforming l xc tc lng chc nng do trong thnh phn ca n cha hai pha c th thc hin hai chc nng chnh sau: - Chc nng hydro-dehydro ha c thc hin bi cc kim loi dng phn tn. Chc nng axit nhm sp xp li cc mch cacbon (ng phn ha, ng vng ..) c thc hin bi oxyt nhm c b mt ring ln v c clo ha iu chnh lc axit thch hp.

100

Chc nng kim loi ng vai tr chnh, gip hnh thnh cc hp cht hydrocacbon khng no v dehydro ho cc naphten. Cn thit lp c s cn bng gia hai chc nng c th c hot tnh xc tc cao v la chn tt. Nu xc tc qu axt s d xy ra cracking lm gim nhanh hot tnh xc tc. Trong cng nghip ngi ta lun kim tra hm lng Cl- a vo m bo cn bng trn lun n nh. S di y m t tng qut cc phn ng chnh xy ra trong qu trnh reforming vi s tham gia ca hai loi tm xc tc:

Isoparafin

Alkylcyclopentan

Pt,axit Sn phm Cracking Pt,axit Pt, axit

Pt

Pt, axit

n-Parafin

Alkylcyclohexan

Aromatic

Hydrocracking

Isomer ha Parafin

Dehydro ng vng Isomer ha Naphten

Dehydroha Naphten

Hydrocacbon nng

cc

Nghin cu cc phn ng dehydro ha v dehydro ng vng ha cc hydrocacbon ring r nh cyclohexan, n-heptan ... ngi ta thy vic a cc kim loi ph gia nh Re, Sn, Ir, Ge (cn gi l cc cht xc tin) lm tng tc phn ng dehydro ha v dehydro vng ha (nht l vng p sut thp) ca h xc tc lng kim so vi xc tc ch cha Pt. vng p sut thp, cc kim loi ph gia cng ng vai tr quan trng trong vic gim tc cracking v hydro phn (hydrogenolysis) t lm gim kh nng to cc v tng hiu sut sn phm chnh.

101

+ 3 H2
activity (mole/h/g) x 102 40 5 % coke

30

PtIr

PtRe 20 Pt 10 PtSn 0 0 5 10 15 20 pH 2 (bar)

nh hung ca kim loi th 2 n qu trnh dehydro ha Cyclohexan Trong s cc h xc tc lng kim, chng ta thy hai h xc tc Pt-Sn v Pt-Re t ra u vit hn c, chng cho php lm vic p sut thp (<10 atm) m vn bo m hot tnh dehydro ha v dehydro ng vng ha cao. Ring h xc tc Pt-Sn hi c bit, ch th hin hot tnh cao vng p sut thp. Ln hn 5 atm, h xc tc ny khng pht huy c tc dng tch cc so vi Pt v cc h lng kim khc trong phn ng dehydro v dehydrovng ha.

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(n + i) C 6
h y d ro g e n o ly s is a c tiv ity (C a rb o n c o n v e rte d w t % ) 40

H2

C 53 5 0 C W H S V = 2 .5 h - 1

30

P tR e (R e /P t= 2 )

20

P tR e (R e /P t= 1 )

10

P t (0 .4 0 % )

P tS n 0 0 5 10 15

P tR e -S (R e /P t= 1 ) 20 25 p H 2 (b a r )

nh hng ca cc kim loi ph gia n qu trnh hydrogenolysis Nu nh thp nin 70 ch khong 30% reformat thu c t h xc tc lng kim th n nhng nm 80 th phn ln ti 80%. Chng ta xem xt k hn v vai tr ca 2 kim loi ph gia c a vo xc tc reforming cng nghip hin nay l Re (Renium) v Sn (Thic). Ngi ta nhn thy Re c cc chc nng sau: thay i c ch to cc v c tc dng bo v kim loi chnh Pt v lm tng bn v tui th xc tc, t lm tng chu k hot ng ca xc tc. Cn Sn th li c cc vai tr nh lin kt vi Pt lm thay i c ch phn ng theo hng c li. Cho hiu sut v la chn theo reformat cao iu kin p sut thp (< 5 atm). Tuy nhin loi xc tc ny km bn hn so vi xc tc cha Re. Vi cc c im trn, ngi ta thng s dng Re trong cng ngh bn ti sinh v Sn trong cng ngh ti sinh lin tc (CCR). C th lit k mt s mc xc tc lng kim mi ca cc hng xc tc tn tui trn th gii :

103

UOP (M) IFP (Php) Criterion (M) Exxon Amoco Engelhard (M) IMP (Mexico) Lin x (c)

Bn ti sinh: R-56, R-62, R-72 Ti sinh lin tc (CCR): R-132, R-134 Bn ti sinh: RG-102, RG-104, RG- 482 CCR: CR- 201 Bn ti sinh: PR- 8, PR- 28 CCR: PS- 20, PS- 40 KX-120, KX-130, KX-190, KX-200 PHF-5, PRHP-30, PRHP-35, PRHP-50, PRHP-58 RD- 150, E- 501, E- 601 RNA- 1, RNA- 2, RNA- 4, RNA- 4M A- 56, A- 64, KP-108, KP-110

4.1 S mt hot tnh xc tc nh hng u c xc tc Cc cht xc tc reforming rt nhy vi cc tp cht c trong nguyn liu v kh tun hon (H2, N2). nh hng u c c th l thun nghch v khng thun nghch. nh hng thun nghch l sau khi cht c thi tc dng, bng bin php x l c bit (qu trnh ti sinh xc tc), b mt v tnh cht xc tc c phc hi tr li. nh hng khng thun nghch l b mt v tnh cht xc tc khng th khi phc li c. Cc cht u c thun nghch Nc v cc hp cht cha oxy: Tc dng vi clo c trong xc tc lm gim tnh axit ca xc tc, t dn ti lm gim hot tnh xc tc. Cc hp cht cha oxy th li d dng to thnh nc trong iu kin reforming. Cn bng H2O/Cl cn c quan tm gi axit n nh cho xc tc. vic a thm Cl vo h trong qu trnh vn hnh l cn thit. Ngoi ra nc cn gy n mn thit b. C th s b loi b nc bng cch cho qua cc ct hp ph cha ry phn t (zeolit 5A). Lng nc cho php trong nguyn liu ti a l 4 ppm. Hp cht cha lu hunh: Trong iu kin reforming s d dng chuyn ha thnh H2S, u c chc nng kim loi do hnh thnh sulfua platin:
Pt + H2S Pt S + H2

104

T , chc nng quan trng nht ca xc tc l dehydro, dehydro ng vng ha b u c. Trong s cc hp cht cha lu hunh th mecaptan (R-S-H) v H2S c nh hng u c ln hn c, lm gim hiu sut v cht lng reformat, lm tng t trng kh cha hydro, tng mc lng ng cc. H2S c tnh axit nn cn gy n mn thit b (Hm lng cho php < 0,5 ppm). Cc hp cht cha nit: Cc hp cht nit hu c d dng chuyn ha thnh amoniac trong iu kin reforming. Cht ny s tc dng vi Cl trong xc tc to NH4Cl, lm gim chc nng axit ca cht xc tc, ko theo s gim hot tnh xc tc, lm tng s hnh thnh hydro. NH4Cl li d bay hi trong vng phn ng lm tng nhit thit b. Mt khc, NH4Cl d kt tinh nhng phn lnh hn ca h thng, gy h hng thit b:
Al O Al Cl OH , H
+

+ NH
3

Al O Al Cl OH

NH

H 2O

Al O Al OH + N H 4C l

C r is ta llis a tio n in c o ld p a r ts o f th e e q u ip e m e n t

Cc cht u c khng thun nghch a. Cc kim loi kim v kim th lm trung ha tnh axit ca cht mang (Al2O3), to thnh hp cht aluminat kh bn. b. Cc kim loi As, Cu, Pb, Zn, Hg, Si, Fe kt hp vi Pt to mi lin kt bn, u c vnh vin tm kim loi khng phc hi li c.T d lm mt chc nng chnh l hydo-dehydro ho ca xc tc. Cc kim loi ny cn tch t trong c 4 l phn ng, lm gim nhit vng phn ng, dn ti mt hot tnh xc tc tng th (hm lng cho php i vi mi kim loi l 5 ppb). bo v hu hiu cc cht xc tc reforming bin php bt buc v hiu qu trong cng ngh l phi c phn xng x l s b nguyn liu bng
105

hydro (hydrotreating) nhm loi b cc cht c thun nghch v khng thun nghch trn, nht l trong trng hp c s dng nguyn liu t cc ngun ch bin th cp khc (hydrocracking, FCC, visbreaking...) c hm lng ng k cc cht u c trn so vi nguyn liu naphta t ngun du th. 4.2 Cc phng php hot ha (ti sinh) xc tc: Trong qu trnh lm vic xc tc c th b mt mt phn hot tnh xc tc do nh hng ca s lng ng cc trn b mt xc tc, do nh hng ca cc cht u c... Mt iu cn lu l, chng ta cng c gng la chn iu kin vn hnh cho hiu sut xng cao nht hoc ch s octan tt nht (v d, tng nhit hoc gim p sut) th s lng ng cc cng tr nn trm trng hn (xem phn c trng ng hc ca qu trnh reforming). Vi mt lng cc qu ln, s che ph v lm gim ng k s lng cc tm hot ng. Lc , tu thuc vo cu to cht xc tc, s mt i mt phn hoc ton b cc chc nng xc tc. Cn thit phi c qu trnh ti sinh xc tc tr v trng thi hot ng ban u. Qu trnh ny c th c tin hnh bng mt s phng php sau: - Phng php oxy ha (phng php t): Cc lng ng trn b mt cht xc tc c loi b bng cch t chy trong dng khng kh pha long vi Nit nhit 350 500oC. cn ch trnh hin tng qu nhit cc b lm gim b mt, gim bn c hc ca cht mang hoc lm tng qu trnh thiu kt lm gim phn tn kim loi. Chu k ti sinh xc tc ph thuc vo iu kin vn hnh h thng, nhng thng khong 6 thng mt ln. Sau mi ln ti sinh, hot tnh xc tc tr v trng thi ban u, nhng sau nhiu chu k ti sinh xc tc s gi ha v gim kh nng xc tc. Vic ti sinh xc tc s tr nn thng xuyn hn., cho n khi cn phi thay th xc tc mi. Thi gian tn ti ca xc tc reforming thng khong vi nm. Qu trnh t cc c biu din bng phong trnh sau : + Q CnHm + O2 CO2 + H2O y l qu trnh ta nhit, nhng khi nh hng n cht lng xc tc cn gim thiu lng nhit ta ra ( T 0oC ). iu ny cn thit v nhit cao lm gim din tch b mt v c th lm thay i pha ca oxyt

106

nhm Al2O3, nhit cao cng lm xy ra qu trnh thiu kt lm gim phn tn ca Pt. Trong cng ngh CCR (ti sinh xc tc lin tc) qu trnh oxy ha c thc hin trong vng t (Burn Zone). - Phng php kh: Thc t cho thy, cc hp cht lu hunh khng c loi b hon ton bng qu trnh oxy ha, cn tn ti ch yu cc hp cht dng sunfat. Phng php kh c tin hnh nhm loi b trit cc dng hp cht ny v.cc kim loi tp c hi trong xc tc, quan trng hn c l kh Pt oxyt v dng Pt n cht. Trong cng ngh CCR, qu trnh kh xy ra ti vng kh (Reduction Zone). - Phng php clo ha: Trong qu trnh lm vic axit ca xc tc gim, mt phn do cc lng ng che ph b mt oxit nhm, mt phn do lng clo trong xc tc gim do nh hng ca H2O trong nguyn liu v trong kh tun hon. Clo cng c th mt do cun theo sn phm phn ng. Do cn phi b sung axit cho h xc tc bng cch bm thm mt lng nh Cl hu c. Lng Cl trn xc tc c gi mc 1% khi lng. Qui trnh ti sinh xc tc Qui trnh ti sinh hon chnh cht xc tc gm cc bc sau: Trng ra h thng: Dng dng nit thi sch cc hydrocacbon cn st li sau phn ng . t cc: t bng dng khng kh pha long vi N2 (c kim sot hm lng oxy trong kh) v nng dn nhit t theo chng trnh: - Nhit : t 370oC n 480oC - Oxy : t 0,5 n 2,0 % th tch Oxy-clo ha: Bm cc tc nhn cha Cl vo h nhm gi n nh lng Cl cn thit cho xc tc (1% trng lng ). - Nhit : 510oC - Oxy: 5% th tch Qu trnh nung: Mc ch lm kh xc tc v phn tn li platin - Nhit : 510oC - Lng oxy : 8% th tch - Thi gian: 4 gi
107

Qu trnh kh: Mc ch nhm chuyn Pt t dng b oxit ha v dng kh (dng hot ng). Loi oxy bng cch trng vi nit. Sau a hydro vo h. - Nhit : 480oC - Hm lng H2 ti thiu 50% th tch - Thi gian: 4 gi

5. Cc yu t nh hng n qu trnh Reforming

Cc yu t nh hng chnh n qu trnh reforming bao gm: Nhit thit b phn ng p sut thit b phn ng Tc np liu T l mol H2/ nguyn liu Cht lng nguyn liu

5.1 nh hng nhit Trong cng nghip ng nht vic nh gi hot tnh xc tc vi nhit c cung cp u vo thit b phn ng (i vi nguyn liu c th, RON cho trc). Nhit c th thay i nhm iu chnh cht lng sn phm, v d: Thay i ch s octan ca reformat. Ph thuc cht lng ca nguyn liu np. B tr s gi ha xc tc (gim hot tnh xc tc ) qua nhiu chu k hot ng.

B tr mt hot tnh xc tc tm thi do cc tp cht gy ra. Nhit tng lm tng kh nng chuyn ha thnh sn phm thm dn ti tng ch s octan nhng li lm gim hiu sut xng. Ngc li nhit gim c li cho hiu sut xng, gim kh, gim hiu sut to cc. Nhit thng c chn trong cng ngh khong t 490-540oC. 5.2 Tc np liu c xc nh bng lu lng dng nguyn liu (th tch hoc trng lng) i qua trong 1gi trn 1 n v xc tc (trng lng hoc th tch lp xc tc).
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Khi tng lu lng nguyn liu hay gim lng xc tc u lm tng tc np liu, ni cch khc l lm gim thi gian tip xc ca cc cht tham gia phn ng vi lp xc tc. Hu qu dn ti lm tng hiu sut reformat (do gim kh), nhng ng thi lm gim cht lung reformat v gim ch s octan. iu ny cng d hiu v cc qu trnh c tc chm nh dehydro ng vng to thm, hydrocracking, dealkyl ha s kh xy ra hn nu thi gian tip xc t. Hiu ng ny c th c b tr nu tng nhit l phn ng. Trong thc t, hn ch bt hyrdrocracking v cc sn phn cc ha ngi ta thng p dng nguyn tc sau : gim tc th tch: gim nhit u vo cc l phn ng sau gim lu lng liu np . tng tc th tch: tng lu lng liu np sau tng nhit

l phn ng. C th gim tc th tch tng ch s octan. Tuy nhin trong vn hnh ngi ta khng c php gim tc trn nh hn mt na so vi thit k hoc < 0,75 h-1. V nh vy s khng kinh t, lm tng tc kh hot tnh xc tc. Tc c la chn ph thuc vo cc iu kin cng ngh c th: p sut vn hnh, t l mol H2/nguyn liu, thnh phn nguyn liu a vo v cht lng reformat mong mun. V d cng ngh CCR mi thng chn V = 1,5 -2,5 h-1. 5.3 p sut vn hnh Cc phn ng chnh c li cho reforming u xy ra thun li p sut thp. p sut cng thp hiu sut reformat v hidro cng cao. Tuy nhin nh hng cc s cng trm trng hn. Do cn la chn p sut thch hp va hn ch qu trnh to cc va t nh hng n hiu sut to xng. p sut vn hnh i vi mt phn xng cng ngh c th l gi tr c nh m ngi ta la chn trc nhm tho mn cht lng sn phm nht nh. Ngy nay nh ci tin cng ngh (s dng cng ngh ti sinh lin tc) v ci tin xc tc (tm c cc h xc tc c th lm vic p sut thp, cho hiu sut xng v RON cao) m ngi ta c th vn hnh qu trnh p sut

109

thp nht m vn p ng yu cu v cht lng sn phm, vn u t v hiu qu kinh t. Cng ngh CCR tin tin nht (platforming, octanizing) s dng xc tc Pt-Sn/Al2O3 cho php vn hnh p sut t 3-5 atm (trc y cn vi chc atm). 5.4 T l H2/ nguyn liu Xc nh bng t l gia lu lng (mol/h) hydro tun hon v lu lng nguyn liu np (mol/h). Thm mt lng ln kh tun hon cha H2 (80-90% tl) nhm lm gim s lng ng ca cc trn b mt xc tc ( do tng qu trnh hydro ha cc hp cht khng no trung gian l tin cht to cc). T l H2/NL thay i trong khong rng (1-10). Gii hn di ph thuc lng H2 yu cu nh nht nhm duy tr p sut ring phn ca H2 trong h thng. Gii hn trn xc nh bi cng sut my nn, kch thc l phn ng v tnh kinh t qu trnh. Thay i t l ny t lm thay i cht lng sn phm. Mt khc vi cc cng ngh CCR hin nay p sut thc hin ch >3 atm, gim t l H2/NL trong trng hp ny tng ng vi vic lm gim p sut ring phn ca H2 nn c tc ng thun li n hiu sut sn phm. nh hng cc thng s vn hnh n hiu sut v cht lng sn phm S gia tng cc thng s p sut (atm) Nhit (oC) Tc khi (h-1) H2/nguyn liu 0,85N +A Nguyn im si u liu im si cui RON reformat Hiu sut reformat Hm lng cc

110

6. Mt s cngngh Reforming tiu biu

Hin nay trn th gii tn ti 2 loi cng ngh reforming ch yu l cng ngh bn ti sinh v cng ngh ti sinh lin tc (CCR). 6.1 Cng ngh bn ti sinh Mt s c im c bn l: Xc tc c nh. H thng dng nguyn liu c chuyn ng t thit b phn ng ny sang thit b phn ng khc. Ngng hot ng ton b h thng ti sinh cht xc tc ti ch, ngay trong thit b phn ng, khi lng cc trn lp xc tc chim 15-20% trng lng. Thng th chu k lm vic ca xc tc trong khong 6 thng n 1 nm. Thi gian ti sinh xc tc mt khong 2 tun l. Trong mt s cng ngh bn ti sinh ngi ta s dng cc thit b phn ng (reactor) c cc van ng m c lp, hoc lp thm mt thit b phn ng d tr, cho php ti sinh xc tc tng thit b ring bit m khng cn dng ton b h thng. Tuy nhin vn hnh cng ngh cng tr nn phc tp hn. Cng ngh bn ti sinh tng i lu i (cng ngh truyn thng), cc ci tin ch yu ch tp trung vo xc tc. T nhng nm 1949-1950 cht xc tc trn c s Pt (xc tc n kim loi) c a vo s dng cho xc tc tng c nh. Loi xc tc ny tuy cho hot tnh xc tc cao, nhng c nhc im l rt d b cc ha nn phi vn hnh trong iu kin p sut hidro kh cao (xp x 40 atm). Khong nhng nm 60, mt s kim loi ph gia c a thm vo h xc tc Pt (xc tc lng kim), khc phc tnh trng gim nhanh hot tnh xc tc. Cht xc tc tr nn bn hn vi qu trnh cc ha, gip qu trnh cng ngh c vn hnh p sut thp hn (khong t 15 n 30 atm). S n gin ca cng ngh bn ti sinh c trnh by trn hnh 19. M t hot ng ca s : Nguyn liu (phn on naphta nng ) c lm sch t qu trnh hydro ha, c trn vi kh hydro t my nn, sau khi qua cc thit b trao i nhit c dn ln lt vo cc l phn ng (c th t 3-4 l) c cha lp
111

xc tc c nh . Cc sn phm c to thnh sau khi ra khi h thng phn ng , qua thit b trao i nhit, thit b t nng v thit b lm lnh. Qua thit b ngng t, sn phm lng gi li, kh khng ngng c s a vo thit b tch kh . Phn ln kh c nn li nh my nn kh v tun hon tr li l phn ng. Phn kh cn li c dn sang b phn tch kh. Hydro c tch ra t y c th c s dng cho cc qu trnh lm sch dng hydro. Phn lng tch ra c a vo thp n nh, thc cht l mt thp chng ct vi mc ch tch phn nh (LPG) nhm tng n nh ca xng v gim p sut hi bo ha. LPG tch ra c a vo thit b ngng t.

112

Xng sn phm ra y thp, mt phn c un nng v hi lu tr li thp n nh, phn ln c lm lnh v a vo b cha. Cng ngh bn ti sinh hin nay vn cn rt thnh hnh Php v mt s nc khc. V d, Vin du m Php ((IFP) lp t c 600 phn xng bn ti sinh trn th gii so vi 120 phn xng CCR. 6.2 Cng ngh ti sinh lin tc (CCR) c im : Lp xc tc c chuyn dng nh nhng, lin tc trong h thng thit b phn ng vi vn tc va phi (trong khong 3- 10 ngy). Ton b h thng c vn hnh lin tc. Lp xc tc sau khi ra khi h thng phn ng c a ra ngoi ti sinh trong mt h thng ti sinh ring. Sau c quay tr li h thng phn ng. Cu to mt l phn ng dng ng thng vi lp xc tc chuyn ng dng trong cng ngh CCR c m t trn hnh sau:

Cu to theo mt ct dc l phn ng reforming xc tc Kch thc l phn ng thay i trong khong: ng knh 1,5 3,5m, Chiu cao 4 12m, Th tch lp xc tc 6 80 m3.

61

113

Chi tit hn chng ta thy cm h thng thit b phn ng bao gm 3 - 4 l phn ng c kch thc, iu kin vn hnh, lng xc tc np vo khng ging nhau, t phn b thnh phn sn phm ra t mi l cng khng ging nhau. H thng cu to t nhiu l phn ng gip cho dng hn hp nguyn liu v kh giu hidro (kh tun hon) t c nhit phn ng v b tr nhit nng t cc phn ng ha hc xy ra trong qu trnh reforming. Nhit gim nhanh trong l th nht do s xut hin ca cc phn ng thu nhit quan trng (ch yu l phn ng dehydro ha naphten), lng xc tc tiu th cho giai on ny chim 10-15% trng lng. l phn ng th 2 nhit gim t hn, lng xc tc tiu th chim 20-30%. Ti l phn ng cui cng , nhit gn nh n nh do c s b tr nhit gia cc phn ng thu nhit nh vi cc phn ng ta nhit kiu nh hydrocracking
O ve n 1 O ve n 2 O ve n 3

R e a c to r 1 R e a c to r 2

T 0

R e a c to r 3

T 0 -2 5 T 0 -5 0
1 0 -1 5 % v o l% 2 5 -3 0 % 5 5 -6 5 %

w t% c a ta ly s t

P 0 = 6 0

P a r a ffin s A r o m a tic s

N 0 = 3 0 A 0 = 1 0
N a p h te n e s

S thay i thng s vn hnh v phn b sn phm theo v tr l phn ng

114

a. S cng ngh PLATFORMING ca UOP: Thit b phn ng c xp chng ln nhau . Xc tc i t trn xung qua h thng thit b phn ng, sau tp trung li v c nng ln thit b ti sinh nh kh nng. Sau khi ti sinh, cht xc tc c a tr li thit b phn ng th nht. Nh c ly ra tng phn v ti sinh lin tc m hot tnh xc tc n nh cao hn so vi trong trng hp lp xc tc c nh (cng ngh bn ti sinh). Cng ngh ny hin nay c s dng ph bin hn c (chim 70% th phn cng ngh CCR trn th gii). Tuy nhin cng c nhc im l vn hnh kh khn do chiu cao h thng thit b phn ng.

Qu trnh Platforming xc tc chuyn ng ca UOP b. S cng ngh OCTANIZING ca IFP (Php): H thng thit b phn ng c sp xp theo hng ngang. Tuy khc phc c nhc im v chiu cao nhng li tn din tch xy dng v ng ng dn ln dn n tng gi thnh xy dng v chi ph vn hnh cao. Ngoi ra c th k n cng ngh ti sinh lin tc POWERFORMING (Anh) v cng ngh hn hp DUALFORMING (Php), trong kt hp 2 h thng bn ti sinh v ti sinh lin tc vi 2 loi xc tc khc nhau.

115

Phn xng reforming xc tc ca nh my lc du s 1 Dung qut Vit nam c lp t theo cng ngh Platforming ca UOP (M). Phn xng ny c nhim v cung cp hp phn pha xng (reformat) cht lng cao v p ng mt phn nguyn liu (BTX) cho ha du.

116

6.3 c im ca thit b xc tc chuyn ng v ti sinh lin tc So vi qu trnh bn ti sinh hoc ti sinh tun hon (trong ln lt tng thit b phn ng c th dng ti sinh xc tc m khng nh hng n vn hnh chung ca h thng), th qu trnh ti sinh lin tc cho hiu sut reformat (xng C5+ ) lun n nh theo thi gian.
sem iregenerative cyclic regenerative
naphtha naphtha fixed bed swing reactor

reform ate

reform ate

reform ate yield

reform ate yield

6-12 m onths

2-4 weeks

tim e

tim e

Continuous regenerative

naphtha m oving bed

regenerator

reform ate

reform ate yield

tim e

S tng quan gia c th cng ngh v hiu sut sn phm reformat. S khc bit v cc c trng k thut (p sut vn hnh, t l H2/nguyn liu, loi xc tc, chu k ti sinh xc tc) v hiu sut, cht lng sn phm gia 2 cng ngh bn ti sinh v ti sinh lin tc c trnh by trn bng sau. Cng ngh ti sinh lin tc t ra u vit hn v hiu sut v cht lng sn phm v vn hnh p sut thp hn.
117

Xu hng cng ngh hin nay trn th gii thin v s dng cng ngh reforming ti sinh xc tc lin tc vi p sut thp nht. Tuy nhin cng ngh ny cng c hn ch l chu k hot ng ngn hn do phi ti sinh xc tc lin tc, i hi chi ph nng lng v chi ph u t cao hn . So snh cc c trng cng ngh v cht lng sn phm gia 2 cng ngh bn ti sinh v ti sinh lin tc Thng s p sut (bar) H2/HC (mol) Xc tc Chu k hot ng C5+ (wt %) H2 (wt %) RON MON Bn ti sinh 12 - 25 5-7 Pt-Re 6 - 15 thng 75 - 84 1.5 - 2 % 95-98 85-88 Ti sinh lin tc 3 -10 1.5 - 4 Pt-Sn 3 - 10 ngy 85 - 92 2 - 3.6 % 100-102 90-92

H 2 /H C (m o l/m o l) 9 8 7

S e m i-R e g

Pt
6
S e m i-R e g

5
CCR

4 3 2 1 0

Pt - Sn
3

Pt - Re

10

15

20

25

30

35 P (b a r)

Tng quan gia cc c trng cng ngh v cht xc tc gia 2 cng ngh bn ti sinh v ti sinh lin tc.

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Chng 8

QU TRNH ALKYL HA
1. Mc ch ca qu trnh
Vo nhng nm 1920 1930 tng ch s octan cho phn on xng ngi ta thng s dng cc phng php nh ph gia Tetra Ethyl Ch, phn on reformat, Nhng vo nhng nm sau 1930 qu trnh alkyl ha c pht trin bi Vladimir Ipatieff da trn xc tc nhm-clor c kh nng nng cao ch s octan cho nhin liu hng khng. Bn cnh , T nh my ch bin kh c th nhn c cc hydrocarbon nh nh phn on metan - etan, propan, butan v pentan. ch bin cc hydrocarbon nh c hng lot qu trnh: polymer ha, alkyl ha, ng phn haNh cc phn ng ng ny c th nhn c nhiu sn phm c gi tr. Bng Alkyl ha v polymer ha nhn c xng octan cao (xng alkyl) v nhiu bn sn phm khc. Ngoi ra, vic pht trin ca cng ngh Cracking xc tc lm gia tng hm lng cc sn phm nh nh C3, C4 v C5 (iso v olefin) cng gp phn cung cp ngun nguyn liu v thc y s pht trin ca qu trnh Alkyl ha. y l qu trnh dng sn xut phn on xng (C5 C12) t cc nguyn liu nh. Thnh phn ch yu ca sn phm l cc isoparafin c phn nhnh cao nh vo phn ng alkyl ha cc olefin (butylen) bng cc nhm alkyl (isobutan). Phn on sn phm ny gi l ankylat c ch s octan kh cao (RON 93 95).

2. Nguyn liu v sn phm

Nguyn liu cho qu trnh alkyl ha bng xc tc axit sulfuric l phn on butan-butylen. Trong thnh phn ca phn on ny c 80 85% l hydrocarbon C4, phn cn li l hn hp C3 v C5. Phn on butan-butylen thu c t cc cm phn on kh ca cc nh ch bin du, trong c cc qu trnh xc tc nhit v cracking xc tc. Tt nht i vi phn ng l c 1% butylen c 1,2% isobutan.
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Propan, butan v cc hp cht khc cha trong nguyn liu tuy khng tham gia vo phn ng nhng c nh hng n qu trnh; chng chim ch trong vng phn ng v gim hm lng isobutan. to iu kin tt hn cho alkyl ha nn loi n-parafin cng trit cng tt. Trong cm alkyl ha cng c thp chng ct (thp butan), trong n-butan tch mt phn ra khi isobutan v tun hon li trong h. Thp propan cng c s dng loi propan. Nguyn liu cho alkyl ha khng c cha etylen v butadien, v khi tip xc vi axit sulfuric chng to thnh sulphat etyl, butyl v polymer t olefin, ha tan trong axit v ha long axit. Trong nguyn liu cng khng nn cha hp cht lu hunh, nit v nc. Nu trong nguyn liu c hp cht lu hunh, nit chng phi c kim ha v trc khi tip xc vi axit sulfuric cn loi nc ra khi nguyn liu. Hm lng v thnh phn olefin cng c vai tr quan trng. Trong alkyl ha isobutan bng butylen s hin din ca olefin nh trong nguyn liu lm tng chi ph axit v gim tr s octan. Cc olefin cao c xu th to polymer, cng lm gim tr s octan ca alkylat. Nguyn liu cn cha lng isoparafin ln hn olefin, do isoparafin mt mt khi tun hon. nhn c alkylat cht lng cao hm lng isobutan trong dng hydrocarbon ra khi l phn ng khng thp hn 55 60%. S ph thuc ca cht lng v hiu sut alkylat vo nguyn liu olefin C3-C5 lit k trong bng. Ta thy, alkylat cht lng cao nhn c trong alkyl ha isobutan bng butylen. S liu v sn xut alkylat cho xng t Tham s Nguyn liu propylen butylen amilen 175187 170172 160* 111117 9294 9296 96140 8789 8890

Hiu sut alkylat so vi olefin, % t.t. Chi ph isobutan, %t.t. so vi olefin nguyn liu 127135 Tr s octan ca alkylat: 8790 - theo phng php ng c 8991 - theo phng php nghin cu (*) hiu sut alkylat loi pentan

Trong nhng nm sau ny ngun olefin tng nh ngun propylen v amilen tng. iu kin alkyl ha isobutan din ra thun li khi nng
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propylen khng qu 55% t.t.; nh tng axit-hydrocarbon phn b cao nh khuy trn; tng hm lng axit trong nh tng (n 60 65% t.t.). Cc iu kin khc tng t nh trong alkyl ha bng butylen. Sau y l s liu v qu trnh alkyl ha nguyn liu vi nng propylen khc nhau: T l propylen: butylen Tc th tch (theo olefin), gi-1 T l isobutan: olefin trong nguyn liu Nhit trong l phn ng, oC Nng axit trong nh tng, % Chi ph axit, kg/tn alkylat Nng axit c s dng Tnh cht ca alkylat: - gii hn si, oC - p sut hi bo ha,mm Hg - tr s octan, RON 97:3 79:21 0,175 0,160 10 8 66 190 90 11,7 7 65 115 90 55:45 45:55 0,300 0,210 9, 5 6 60 120 91,5 11 9 50 110 90

57191 56184 44202 32188 233 300 543 88,6 91,5 93,5 95

Ngay c khi s dng nguyn liu vi 97% propylen cng c th nhn c alkylat c cht lng t tiu chun. Nhng khi phi thay i ch , c bit l nhit v nng axit sulfuric trong nh tng v tng ng k chi ph axit. Cht lng alkylat ph thuc ch yu vo thnh phn nguyn liu olefin. Tr s octan ca sn phm khi s dng propylen, butylen v amilen tng ng l (RON): 89 91; 92 96 v 86 90. Trong alkyl ha isobutan bng butylen trong nguyn liu lun c mt lng olefin khc, khng th loi b hon ton, do cn chia sn phm phn ng thnh alkylat my bay tr s octan cao nht v alkylat t tr s octan thp nht. Alkyl ha bng axit sulfuric cht lng alkylat gim khi gim axit ca xc tc. Gim axit do hai nguyn nhn: b nc cha trong nguyn liu ha long; phn ng ca axit sulfuric vi sn phm ca polymer ha v cc sn phm ph khc.

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Trong thc t, tr s octan ca alkylat cng cao khi nng isobutan trong pha hydrocarbon trong l phn ng cng cao v cng thp khi tc np olefin cng cao. Khuy trn cng ng vai tr to ln. Ngoi sn phm lng (alkylat) trong qu trnh alkylat cn nhn c kh kh (propan, trong mt s trng hp c th c s dng nh sn phm c lp), phn on butan-butadien sau phn ng v axit sulfuric. Cc hydrocarbon c s dng trong cc qu trnh khc, cn axit sulfuric c hon nguyn hoc s dng lm sch sn phm.

3. Cc phn ng ha hc ca qu trnh Alkyl ha

3.1 C ch phn ng Alkyl ha Phn ng alkyl ha isoparafin bng olefin c m t bng phng trnh phn ng:
CnH2n+2 + CmH2m Cn+mH(n+m)+2

Theo c ch ca Smerling, phn ng din ra theo 5 bc sau: Olefin kt hp vi proton:

CH3-CH = CH CH3 + H CH3-CH-CH2 -CH3
+ +

Ion mi xut hin phn ng vi isoparafin nhn c ion mi v parafin:

CH3 CH3 CH CH3 + CH2 CH3 CH3
+

CH3 CH3 C+ + CH3-CH-CH2 -CH3

+

CH CH3

Lin kt ion mi vi phn t olefin th hai, to thnh ion c phn t lng cao hn
CH3 CH3 C+ CH3 CH CH3 + CH CH3 CH3 CH3 CH3
+

CH3 C CH - CH - CH3

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 Chuyn nhm trong ion mi nh chuyn dch ion dc theo mch cacbon:
CH3 CH3 CH+ C(CH3)2 CH3 CH3 CH3 CH3 C C+ CH2 CH3 + CH3 C+ CH3 C CH2 CH3

CH3 CH3 C+ CH CH CH3

CH3 CH3

CH3 CH3 CH3 CH3 C C+ CH2 CH3

CH3 CH3

Tng tc ca ion mi hnh thnh vi isoparafin ti lin kt tam cp cacbon-hydro v to thnh sn phm cui v ion carboni mi, c kh nng pht trin mch tip:
CH3
+

CH3

C CH CH3 + CH3

CH CH3 CH3

CH3 CH3 CH3

CH3 C+ + CH3 CH CH CH - CH3 CH3 CH3 CH3 CH3

Ion carboni tam cp phn ng trc tin vi isobutan, sau n ion bc hai. 3.2 Cc phn ng mong mun Phn ng chnh xy ra trong qu trnh l phn ng Friedel Crafts. Cc cht xc tc axt Lewis (HF hay H2SO4) gip to ra cc ion cacboni ti cacbon bc ba ca cc hp cht iso-parafin v chng nhanh chng kt hp vi cc ni i trn cc hp cht olefin m chng tng tc (propylene, butylen v pentylen).
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Phn ng din ra trong pha lng vi pha axit/phn ng trng thi nh tng v nhit va phi. Cc olefin nh propylene, butylen v pentylen u c th s dng, nhng butylen l tt nht v n to ra sn phm alkylat c ch s octan cao v lng cht phn ng tiu th thp. Phn ng Alkyl ha c c ch rt phc tp v c th to ra rt nhiu sn phm khc nhau. C ch phn ng gia iso-butylen v butan c th din t nh sau:

3.3 Cc phn ng khng mong mun Phn ng oligome ho cc olefin (C12):

C4 C4 C4 + iC4 + C4 iC8+ iCi+ iCi+ 12 16
+ C4 + iC iC 8 8 +iC 4

y l phn ng to thnh t 2, 3, 4 monomer c tc dng lm cho sn phm nng hn v lm gim hiu sut alkylat. trnh phn ng oligomer ho ta tng hm lng iC4 trong ngun nguyn liu ban u, t l gia iC4 so vi cc thnh phn khc khong:
+ iC 4 = 5 18 C4

- Phn ng cracking: xc tc cho qu trnh alkyl ho l xc tc axit nn n xy ra phn ng cracking, phn ng ny lm cho hp cht nh hn (s hin din ca C5 trong thnh phn ca snphml l hiu qu ca cracking) - Phn ng oxi ha: do xc tc cho qu trnh l xc tc axit rt mnh nn n xy ra qu trnh oxi ho to ra cc hp cht nng, cn, nha

124

4. Xc tc s dng cho qu trnh Alkyl ha

Alkyl ha c th thc hin vi s tham gia ca xc tc (axit sulfuric, axit hydrophosphoric, clorua nhm , ftorua bor) v khng c xc tc cho phn ng nhit cao. Alkyl ha nhit c th din ra vi hydrocarbon mch thng v nhnh, cn alkyl ha xc tc ch din ra vi parafin c cha nguyn t cacbon tam cp. Hin nay trong cng nghip ng dng alkyl ha hydrocarbon thm bng olefin vi s tham gia ca cc xc tc axit sulfuric, axit phosphoric, clorua nhm v hn hp ca ftorua bo vi axit hydrophosphoric v cc xc tc khc. Do cng ngh n gin, sn lng alkylbenzen cao v nhu cu sn phm tng nhanh nn cc qu trnh pht trin nhanh trong cng nghip. iu ch alkylbenzen bn cnh xc tc cng nghip clorua nhm khan c th s dng axit sulfuric, axit phosphoric, ftorua bo alumo-silicat t nhin v tng hp. Ph thuc vo xc tc qu trnh alkyl ha din ra trong h ng th hoc d th. La chn xc tc cng ng thi xc nh thng s ca qui trnh cng ngh - nhit , p sut, yu cu mc lm sch nguyn liu. Alkyl ha c th din ra trong pha hi hoc pha lng.
4.1 Xc tc trn c s clorua nhm

Do c nhiu phn ng ph (polymer ha v alkyl ha phn hy) v nhng nhc im (ht m, n mn thit b....) ca clorua nhm, ng thi sn phm ca phn ng tng tc vi axit clohidric, ftorsulfon, monoftor-phosphor v ftorbor, nn alkyl ha bng xc tc AlCl3 khng c ng dng rng ri trong cng nghip.
Xc tc axit sulfuric, hydrofloric v phosphoric

Di y l tnh cht ca xc tc axit sulfuric, hydrofloric cng nghip:

H2SO4 (98%) HF

Phn t lng 98,8 Nhit si, oC 290 Nhit ng bng +3 Trng lng ring (hm lng 98%), g/cm3 1,84 nht, cPs 33 (15oC)
125

20,1 19,4 -83 0,99 0,26 (0oC)

Sc cng b mt, Dina/cm axit ha tan ( 27oC), % k.l: isobutan trong axit (nng 100%) isobutan trong axit (nng 99,5%) axit trong isobutan axit trong propan

50 (20oC) 9,4 2,7 0,1 (13oC) 0,44 0,90

8,1 (27oC) 8,9 -

trnh nh hng ca oxy ha axit sulfuric cn tin hnh phn ng nhit thp (thng 5 10oC). L phn ng s dng axit hydrofloric c nhit 20 40oC. Sn phm khi s dng axit sulfuric c tr s octan cao hn trong trng hp axit hydrofloric. Hot ca axit sulfuric trong mi trng hu c cao hn trong nc 450 ln. Do isobutan c phn ly rt thp, nn hot ca axit sulfuric khi tip xc vi n rt cao v tc tng tc ca axit v hydrocarbon c xc nh bng ha tan ca hydrocarbon trong lp axit b mt. nng axit thp kh nng ha tan ca isobutan gim v tc phn ng alkyl ha gim. Do axit ca axit sulfuric trong dung dch hydrocarbon cao hn nhiu so vi trong nc, do gim hot xc tc trong alkyl ha trc tin ph thuc vo mc pha long axit bi nc v t ph thuc vo dung dch ca hydrocarbon phn t lng cao trong xc tc. Do gi hot tnh cao cn phi lm khan nguyn liu trc khi a vo vng phn ng.Trong h thng np axit c nng 98%. Trong qu trnh lm vic nng ca axit gim xung n 85%, c ly ra ngoi. S dng axit m c hn khng nn v s din ra oxy ha hydrocarbon v cc qu trnh phc tp khc, dn ti to nha t sn phm, tch anhydric lu hunh ra khi hn hp phn ng v hiu sut alkylat gim. Cng cn trnh s dng axit long v chng c kh nng kch hot phn ng polymer ha olefin v to thnh alkylsulphat. Thm mt s ph gia vo axit sulfuric trong iu kin cng nghip lm cc tham s ca qu trnh alkyl ha tt hn - hiu sut alkylat tng, chi ph isobutan v axit gim. Ngoi axit sulfuric cn s dng axit hydrofloric lm xc tc cho qu trnh alkyl ha. i vi xc tc axit hydrofloric khan c c trng l khng ch butylen v amilen m c propylen u alkyl ha isobutan. Khi c HF, khc vi phn ng vi xc tc axit sulfuric, phn ng alkyl ha din ra khng km theo phn ng ph ngay nhit cao. Mc d vy, nhng vi kh nng bay
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hi cao v tnh c cao nn HF gp kh khn trong vic ng dng rng ri vo thc t. Trong nhiu patent ngi ta s dng xc tc florua bo hidrat ha vi HF cho phn ng alkyl ha isoparafin bng olefin. Phc BF3.H2O.HF khi c hot ha lin tc bng florua bo c hot n nh; 1 th tch xc tc cho 88 th tch alkylat; khi c hot ha bng florua bo khan 195 th tch. Hn hp florua bo vi axit phosphoric cng c s dng lm xc tc alkyl ha. Xc tc hiu qu nht c coi l hp cht phc BF+ H3PO4 v BF3.H2O.HF. Cc xc tc ny loi b c cc yu im ca xc tc axit sulfuric v hydrofloric, chng khng i hi thit b phc tp v bin php phng nh khi s dng axit hydrofloric v c bit quan trng l cho php thu c alkylat hiu sut cao v hu nh khng c sn phm ph. Hai xc tc ny c th c s dng nhiu ln m khng mt hot tnh, dn ti gim chi ph xc tc n ti thiu. Xc tc cha zeolit. Hot ca xc tc zeolit do cc tm axit Bronsted qui nh. Trn cc tm axit ny to thnh ion carboni trung gian, c kh nng tham gia vo phn ng alkyl ha hydrocarbon thm. Trong thi gian sau xut hin qu trnh alkyl ha mi tng tr s octan. S dng nguyn liu l buten-2 hiu sut alkylat debutan l 180 220% so vi olefin, cn tr s octan RON t 95,5 98,5.
4.2 So snh gia xc tc HF v H2SO4

C hot tnh tng t nhau cho phn ng Alkyl ha. Cng ngh alkyl ha vi xc tc H2SO4 i hi hot ng nhit thp (0 100C), cn cng ngh s dng HF hot ng nhit cao hn (10 400C). Lng xc tc tiu hao vo khong 40100kg H2SO4/1m3 alkylat v 1kg HF/1m3 alkylat. V tc ng n mi trng th nng H2SO4 s dng l kh cao (90%) nn phng php tinh ch rt kh, v th hin nay phng php x l ch yu lng xc tc qua s dng l em t thu hi v ti sinh. Cn HF l hp cht d bay hi iu kin thng thng v c

127

tnh c hi cao (210ppm gy m mt, ln hn 20ppm gy nguy him n tnh mng). Trong hai axit trn th H2SO4 th thng c s dng hn HF bi tc ng n mi trng c xem nh yu t hng u cho vic chn la xc tc.

5. nh hng ca cc yu t n qu trnh Alkyl ha

Thc o chnh dng nh gi v so snh s thnh cng ca cc qu trnh Alkyl ha khc nhau l: Ch s octan ca sn phm alkylat. Th tch tiu th ca olefin v isobutan trn mt th tch sn phm. Mc xy ra ca cc phn ng ph. Lng axt tiu th. Ty thuc vo iu kin phn ng m hiu qu ca cc qu trnh khc nhau l khc nhau. Nhng nhn chung hiu qu ca qu trnh alkyl ha ph thuc ch yu vo cc iu kin phn ng sau: Ngun olefin s dng (propylene, butylen hoc penten). Nng ca isobutan. Phng php phun v phi trn olefin. Nhit phn ng. Loi v mnh ca cht xc tc.
5.1 Loi olefin

Khi so snh sn phm ca cc qu trnh alkyl ho trn cc ngun olefin khc nhau ta nhn thy ngun nguyn liu butylen l tt nht cho qu trnh ny, v sn phm ca n c ch s octan cao (RON = 93-95), lng butylen tiu th thp v hn ch c cc phn ng ph. Propylene th cho sn phm c ch s octan khng cao (RON = 89-92) v tiu th nhiu propylene v axt. Cn sn phm t olefin penten l mt hn hp v kh nng xy ra cc phn ng ph l rt cao.
5.2 Nng ca isobutan

T l ca th tch ca isobutan/olefin trong nhp liu thng thng dao ng trong khong t 6 10, khi nng isobutan vt qu mc yu cu th
128

n s hn ch kh nng tan ca isobutan trong pha axit v lm tng phn ng polyme ha cc olefin.
5.3 S khuy trn v phun isobutan/olefin

S khuy trn v phun nguyn liu rt quan trng i vi cc h thng s dng axt sunfuric, bi v nht ca n chu nh hng rt nhiu bi iu kin nhit ca phn ng. Cc h thng thit b mi vi thit k phun a im c th gip tng t l ca isobutan/olefin, v h thng phun ny gip tng kh nng ha tan ca isobutan. i vi cc h thng phun mt im th rt d xy ra hin tng qu ti olefin trong h nh tng, iu ny lm gim cht lng sn phm v tng s tiu hao axt do cc phn ng ester ha.
5.4 Nhit phn ng

Nhit l thng s rt d bin i trong c hai bnh phn ng, s gia tng nhit phn ng t l nghch vi ch s octan ca sn phm. i v h thng s dng HF thng hot ng nhit 95oF, cn h thng s dng axit sunfuric th hot ng nhit 45oF.

6. Mt s cng ngh Alkyl ho tiu biu

6.1 Cng ngh Alkyl ha vi xc tc H2SO4

Nhit c xem l thng s quan trng nht ca qu trnh, trong qu trnh phn ng n dao ng trong khong t 0 100C. Nu nhit nh hn 00C th nht ca axt tng, kh nng phn tn ca n s gim. Cn khi nhit ln hn 100C chuyn ha ca phn ng alkyl ha s gim. Thng s p sut cng kh quan trng, n gip duy tr m bo nguyn liu trng thi lng trong bnh phn ng. Nng axit ban u l 98%, khi gim xung 90% th phi thay axit mi. S cng ngh Alkyl ha bng axt sulfuric c m t nh s sau:

129

S thit b phn ng

130

S cng ngh alkyl ha vi cht xc tc l H2SO4

6.2 Cng ngh Alkyl ha vi xc tc HF

Qu trnh Alkyl ha bng xc tc HF v bng axit sunfuric cho kt qu tng t nhau, tuy nhin cng ngh Alkyl ha s dng HF hot ng nhit khong t 10 400C, p sut c duy tr nguyn liu vn trng thi lng trong bnh phn ng. S khuy trn cng ngh s dng HF i hi khng cao bng khi dng H2SO4. Nng acid s dng ti u l t 83 91%.

131

Chng 9

QU TRNH ISOMER HA
1. Mc ch ca qu trnh
Mc ch ca qu trnh isomer ha trong ch bin du l tng tnh chng kch n ca xng my bay v xng t. Trong cng nghip ch bin du trc tin chng c ng dng sn xut isobutan t n-butan. Isobutan sau c alkyl ha bng butylen nhn c isooctan. Qu trnh isomer ha cng nghip pht trin vi mc ch l tng ngun isobutan - l nguyn liu sn xut alkylat, l thnh phn tr s octan cao cho xng my bay. Nguyn liu ca qu trnh l n-butan tch ra t kh ca nh my ch bin du. Qu trnh ng phn ha n-butan c bit c quan tm trong cc nh my khng c cracking xc tc (kh cracking xc tc cha nhiu isobutan). Xc tc cho qu trnh ny l nhm oxit clo ha, hot ha bng HCl v s dng trong ch nhit n ha (90 120oC) v p sut cao. ng phn ha cc hydrocarbon xng nh nh n-pentan v hexan t ph bin hn, c ng dng sn xut cc thnh phn xng octan cao. Nhng nm sau chin tranh th gii th hai nhu cu v xng my bay gim nn qu trnh isomer ha trong thi gian ny cng t c quan tm hn. Tuy nhin sau nhu cu v ng phn ha li tng do i hi v cht lng xng t tng. Qu trnh reforming xc tc l thnh phn khng th thiu trong cc nh my ch bin du. Nguyn liu ca qu trnh ny l xng c gii hn si 62 85oC hoc 80 180oC, cn phn nh hn ca xng chng ct trc tip li trong nh my. Nh qu trnh ny nhn c cc thnh phn octan cao vi hm lng hydrocarbon thm cao. Trong xng t cht lng cao (RON 93 v RON 98) cn cha t 25 n 45% isoparafin, nhn c trong qu trnh alkyl ha v isomer ha. Thm chng vo cc thnh phn thm ca xng cracking xc tc v reforming cho php tng tnh ng dng ca xng. Nh isomer ha c th tng tr s octan ca phn on xng nh (si u n 85oC) ln 15 20 n v. Do cng vi s tng trng sn xut xng octan cao th isomer ha cng tng.

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Gi tr to ln ca qu trnh isomer ha l nguyn liu c s dng l cc thnh phn octan thp - nh phn on t si u n 62oC v rafinat ca reforming xc tc. Trong cc nguyn liu ny cha ch yu l phn on pentan v hexan. Cc nguyn liu ny c ng phn ha trong mi trng c hydro to thnh isoparafin vi tr s octan cao. Tnh chng kch n cao v bay hi cao ca sn phm ng phn ha cc hydrocarbon C5 C6 khin cho chng tr thnh cc cu t c gi tr cho xng cht lng cao. Th d, nhexan (c nhit si 69oC) v tr s octan l 26, cn cc ng phn ca n c tr s octan cao: 2 - metylpentan 73,5 3 - metylpentan 74,3 2,2 - dimetylbutan 93,4 2,3 - dimetylbutan 94,3 Tr s octan c bit cao khi pha trn isomerat vi hydrocarbon thm. Nu tr s octan ca sn phm ng phn ha cc hydrocarbon C5 C6 l 98 th ca hn hp vi aromat s l 103 104. Do v phng din ny isomerat khng thua km sn phm ca qu trnh alkyl ha isobutan bng butylen. ng phn ha khng ch c quan tm trong cng nghip ch bin du m c trong cng nghip ha du do isopentan dehydro ha s to thnh isopren l nguyn liu sn xut cao su tng hp. Nh vy, isomer ha va c ng dng sn xut xng octan cao v c cao su tng hp.

S mt phn ca qu trnh lc du y l qu trnh c pht trin rt mnh trong nhng nm gn y khi nhu cu v sn phm xng c ch s octan cao cng nhiu v gii php tng
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ch s octan bng cch pha ph gia Tetra Etyl Ch b hn ch s dng do tc ng n mi trng.

2. Nguyn liu v Sn phm

2.1 Nguyn liu

Nhp liu chnh cho qu trnh isomer l phn on naptha nh vi thnh phn chnh l pentan, hexan v mt lng nh heptan. Nguyn liu phi c x l nhm loi lu hunh v nit trc khi a vo bnh phn ng bo v hot tnh ca cht xc tc, c th x l bng cc qu trnh nh Merox, x l Clay hay hydrotreating. Thng thng i vi nhp liu l naptha nh th thng chn qu trnh x l bng hydro (hydrotreating).
2.2 Sn phm

Sn phm ca qu trnh isomer bao gm: Mt lng nh sn phm kh sinh ra do qu trnh Cracking. Mt phn nguyn liu cha chuyn ha. Isoparafin v cycloparafin Nu tng tnh nghim khc ca cng ngh th cng nng cao c ch s octan ca sn phm nhng cng lm tng hiu sut phn on kh to thnh. Hiu sut chuyn ha ca cng ngh ph thuc vo tnh cht ca nhp liu v ch s octan ca sn phm. Nu tnh cht ca nguyn liu khng tt th chuyn ha ch khong 85% hoc hiu sut sn phm lng s thp, cn nu tnh cht ca nguyn liu tt th chuyn ha c th t n 97%.

3. Cc phn ng ha hc ca qu trnh Isomer ha

3.1 C ch isomer ha

Phn ng ng phn ha n-parafin din ra trong vng nhit thp v nhit thp to thnh isomer phn nhnh nhiu hn. Do parafin cu trc phn nhnh c tr s octan cao hn, do nu phn ng din ra nhit thp nhn c xng cht lng tt hn. Nghin cu c ch phn ng ng phn ha cho thy, phn ng ny din ra theo c ch ni tip, ngha l cc ng phn cha hai, ba nhm metyl to

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thnh qua cc giai on to isomer vi mt nhm metyl. Nh vy, tng su chuyn ha hm lng isomer phn nhnh cao tng v nh tr s octan tng. Phn ng ng phn ha hydrocarbon vi xc tc axit din ra theo c ch ion cacboni. Xt phn ng isomer ha n-butan. Vt olefin trong hn hp khi mo phn ng. Kt hp olefin vi xc tc sinh ra proton xc tc v ion cacboni: CH3-CH2-CH=CH2 + HA CH3-CH2-C+H-CH3 + AIon cacboni tng tc vi phn t n-butan sinh ra ion cacboni mi t nbutan: CH3-CH2-C+H-CH3 + CH3-CH2-CH2 CH3
+

CH3-CH2-CH2CH3 + CH3-C H-CH2-CH3 Ion cacboni ny chuyn ha tip thnh ion cacboni bc ba: CH3-C+H-CH2-CH3 C+H2 CH-CH3 CH3 CH3-C -CH3 CH3

Ion cacboni bc ba cng c th to thnh qua giai on to hydrocarbon vng trung gian: CH3-CH2-C+H -CH3 H2C-CH-CH3 + H+ CH2 Hydrocarbon vng t theo lin kt gia cc nhm metylen: H2C-CH-CH3 H C+H2 -CH-CH3 CH2 CH3 Ion cacboni bc ba hnh thnh theo cch ny tip tc tham gia vo phn ng dy chuyn vi cc phn t n-butan mi v trong qu trnh ny iso-butan to thnh:
+
+

CH2 -C-CH3 + CH3-CH2-CH2 CH3 CH3 CH2 -CH-CH3 + CH3-CH2-CH CH3 CH3
+

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Tc ng phn ha cc parafin mch thng tng khi phn t lng tng. Th d, tin hnh ng phn ha trn xc tc sulfur volfram tc ng phn ha tng i ca cc n-parafin nh sau: n-pentan- 1,0; n-hexan 1,2; n-octan 4,2. Do i vi phn ng ng phn ha phn on xng nh nn tin hnh iu kin khc nghit hn. ng phn ha parafin trn xc tc rn din ra theo hai hng: hydro ha dehydro ha v isomer ha. Khi phn t hydrocarbon tip xc vi xc tc mt trong cc nguyn t hydro ca phn t ny hp ph trn tm kim loi, cn nguyn t cacbon lin kt vi n hp ph trn tm axit. Phn t b hp ph ng phn ha v di tc dng ca hydro phn t n ri khi b mt xc tc. Phn ng ha hc chnh ca qu trnh l phn ng chuyn ha cc paraffin mch thng thnh cc isoparafin. Cc hp cht olefin c th hin qu trnh isomer v chuyn i v tr ca lin kt i. Cn cc hp cht cycloparafin (naphten) c th thc hin qu trnh isomer ha v thc hin b gy vng thnh olefin.

4. Xc tc cho qu trnh isomer ha

S pht trin ca qu trnh isomer lun i km v chu s chi phica s pht trin ccht xc tc, xc tc cho qu trnh isomer ha pht trin theo bn giai on sau y.
4.1 Th h xc tc th nht

l xc tc Fridel Crafts n l hn hp ca AlCl3 HCl. Xc tc ny c hot tnh cao v th c th tin hnh iu kin nhit thp (80 1000C). Tuy nhin, n li kh s dng v d b u c v gy n mn rt mnh.
4.2 Th h xc tc th hai

L xc tc Pt/Al2O3, xc tc ny d s dng, t nhy vi tp cht c trong nguyn liu, khng gy n mn. Tuy nhin, do c hot tnh km nn m bo hiu qu chuyn ha n phi lm vic nhit cao (350 5500C).
4.3 Th h xc tc th ba

ci tin nhc im ca th h xc tc th hai, ngi ta c th nng cao hot tnh ca xc tc ny bng cch thc hin qu trnh clor ha xc tc
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Pt / Al2O3 thnh Pt/Al2O3 clor ha. Kt qu l tng axt, v th gim nhit lm vic xung cn khong 150 1800C. Tuy nhin, xc tc ny cng gp mt s vn kh khn l d b u c bi nc.
4.4 Th h xc tc th t

y l th h xc tc hiu qu nht v c s dng ph bin nht hin nay. N pht trin da trn s ra i ca cc cu trc zeolite. Tuy nhin, tng hot tnh cho qu trnh isomer ha ngi ta thng cho mang cc kim loi t him nh Pt ln cu trc ca zeolit v thng c k hiu tt l Pt/zeolite. Xc tc ny rt d s dng, khng chu nh hng bi nc. axt tng i, iu kin lm vic khong 2500C. Hin nay cc nh my lc du ch yu s dng xc tc th h 3, 4.

5. Cc yu t nh hng n qu trnh Isomer ha

5.1 Nhit

Nhit c xem nh thng s chnh iu khin qu trnh Isomer ha, nhit cao th tng tnh nghim khc ca qu trnh (bao gm c qu trnh hydrocracking). Ngoi ra qu trnh isomer ha cn chu nh hng ca cc yu t khc nh sau:
5.2 p sut tng

p sut cao c th lm ng tui th ca cht xc tc nhng cng lm tng cc phn ng ph khc nh hydrocracking.
5.3 p sut ring phn ca hydro

p sut ring phn ca hydro cng cao th lm tng hiu sut phn ng hydrocracking nhng cng c kh nng bo v v ko di tui th ca cht xc tc. Hiu sut ca qu trnh isomer chu s tc ng tng hp ca tt c cc yu t k trn, tuy nhin yu t iu khin ch yu l da vo s cn bng ca cc phn ng ha hc trong qu trnh isomer ha. V th nng cao hiu sut ca qu trnh c th thc hin phn tch cc hp cht isoparafin ra khi nguyn liu trc khi a vo qu trnh isomer.
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6. Mt s cng ngh Isomer ha tiu biu

y l qu trnh c sn phm vi cht lng cao v to ra phn on phc v cho qu trnh pha ch xng thng phm. C th so snh xng t qu trnh isomer vi cc qu trnh sn xut xng khc nh sau:

Hin nay c rt nhiu cng ngh isomer ha khc nhau, nhng nhn chung chng u thuc hai dng nh sau.
6.1 Cng ngh isomer ha One Through

y l qu trnh isomer ha c in, nhp liu trc khi a vo qu trnh thng c tch butan v x l loi lu hunh v nit. Hydro sch l rt cn thit tng tnh n nh ca cc olefin. Qu trnh isomer ha ny c th lm tng ch s octan (RON) ln khong 70 n 83.

s cng ngh isomer ha mt dng (One Through)

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6.2 Cng ngh isomer ha ci tin

Cc qu trnh ci tin ch yu da trn s kt hp gia cc thit b phn tch v qu trnh isomer, thit b phn tch gip tch isopentan ra khi nguyn liu v c th nng cao ch s octan ca sn phm ln khong 84. Vic kt hp thm thit b tch pentan trn dng sn phm v tun hon n-pentan gip lm tng RON ln khong 86. Mt s cng ngh hin nay s dng thit b phn tch s dng ry phn t c th nng cao hiu qu qu trnh phn tch v RON ca sn phm c th t n 89.

s cng ngh isomer ha c tun hon n-pentan Qu trnh Isomer ha khng i hi iu kin nghim ngt nh qu trnh Reforming xc tc. Lng hydro b sung khong 70 scr/bbl, lng hydro tun hon 4 trn t l mole hydro nhp liu, n lm vic p sut khong 400 psig v nhit khong 400oF. Cn qu trnh isomer ha n-butan nhm mc ch chuyn ha n-butan thnh isobutan cung cp nguyn liu cho qu trnh Alkyl ha v dng lm ngun nguyn liu sn xut methyl tertiary butyl ether (MTBE).

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Chng 10

CC QU TRNH X L BNG HYDRO Hydrotreating

1. Mc ch ca qu trnh
Hu ht cc nhp liu trc ch bin v sn phm to thnh u cha mt lng nh cc hp cht aromatic v cc cht bn khc, qu trnh Hydrotreating c dng x l nguyn liu hoc hon thin cht lng cc sn phm sau ch bin. N da trn cc qu trnh loi tr tp cht nh tc ng ca tc nhn hydro v b ry cc lin kt ca cc hp cht aromatic to thnh cc sn phm c phn t lng thp hn v nhiu sn phm nh hn. Cc qu trnh hydrotreating c th k n nh: Qu trnh loi Lu hunh (Hydrodesunfua). Qu trnh loi Nit (Hydrodenitro). Qu trnh lai Oxi (Hydrodeoxygen). Qu trnh n nh cc hydrocacbon. Cc qu trnh x l ny rt thun hi cho vic x l cc ngun nguyn liu cho cc qu trnh reforming, cracking xc tc v hydrocracking. Qu trnh Hydrotreating ra i da trn s xut hin ca sn phm hydro t qu trnh reforming vo nhng nm 1940. Ban u ngun hydro ny c dng x l phn on distillat vi mc ch chnh l loi lu hunh v n nh cc hp cht vng nhm nng cao ch s cetan ca Diesel v tng im smoke point ca Kerosen.

2. Ngun cung cp Hydro trong nh my lc du

Ngun hydro trong nh my lc du c ngha rt quan trng trong vic bo v cc xc tc kim loi (xc tc reforming), ngoi ra n cn c tc dng x l nguyn liu v hon thin cht lng cc sn phm.
2.1 Ngun hydro t Reforming

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Ngun hydro s dng cho cc qu trnh hydrotreating ch yu c cung cp t qu trnh Reforming, vi qu trnh reforming lien tc c th cung cp 90%V lng hydro cho nh my, cn i vi qu trnh bn lin tc th c th cung cp khong 80% vi p sut khong 50 psig. Ngun hydro ny c s dng cho cc qu trnh nh: Loi lu hunh trong thit b amin. X l loi lu hunh cho cc sn phm nh distillat, kerosene, jet fuel, diesel, cc qu trnh ny tiu th khong 100-200 csr/bf (mt na c cung cp t reforming). S dng li cho cc qu trnh hydrotreater v hydrocracking.
2.2 Ngun hydro t khi offgas ca FCCU

Ngun kh offgas t qu trnh FCCU cha khong 5% l hydro, cn li l cc kh khc nh metan, etan v propan. Mt s phng php c s dng thu hi ngun hydro t ngun offgas ny nh: Ngng t nhit thp S dng cht hp ph Dng mng lc phn tch
2.3 Ngun hydro t qu trnh Steam reforming Metan

y l phng php chung nht dng sn xut hydro, cc ngun nguyn liu dng sn xut hydro l metan, etan v cc thnh phn nng hn. Qu trnh reforming s chuyn ha cc kh nguyn liu trn thnh hydro, CO2 v nc theo chui ba phn ng sau: u tin Metan thc hin phn ng di tc dng ca cht xc tc v chuyn ha thnh Hydro, CO v ta nhit. CH4 + H2O CO + H2O 3H2 + CO + Q H2 + CO2 - Q Tip , CO s tc dng vi hi nc: Sau cng CO2 s c tch ra khi hn hp kh bng cc qu trnh hp ph. Tuy nhin trong qu trnh ny cng xy ra phn ng ngc li, l mt lng nh CO v CO2 s phn ng vi H2 ti to li CH4 v nc.

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3H2 + CO CH4 + H2O - Q Sn phm hydro thu c t qu trnh ny c tinh khit khong 90 n 95%.
2.4 Ngun hydro t kh tng hp

Qu trnh kh ha l qu trnh oxi ha ring phn cc phn on nng nh asphalt, resid, v cc phn on lng nng khc. Sn phm kh tng hp thu c t qu trnh ny cha ch yu l CO v H2 nm trng thi cn bng vi nhau, ngoi ra n cn cha khong 5% CO2 v mt lng nh cc kh khc nh metan, nit, nc v lu hunh. Sau hydro s c thu hi t kh tng hp bng cc phng php nh s dng cht hp ph, dng mng lc phn tch, u im ca qu trnh ny l c th tn dng cc phn on nng c gi tr kinh t thp v gy nhim chuyn thnh cc kh c gi tr cao. Tuy nhin hydro thu hi t qu trnh ny t hn qu trnh reforming.

3. Ha hc ca qu trnh Hydrotreating
C ch ch yu ca cc qu trnh hydrotreating l s dng lng hydro b ry lin kt v tch cc cht ra khi sn phm. Phn ng ch yu l phn ng hydro ha, n l phn ng ta nhit nn cn phi lu tm n vn an ton v hot ng n nh ca thit b phn ng.
3.1 Qu trnh tch Lu hunh (Hydrodesunfua)

Vi s pht trin mnh m ca ngnh nng lng, trong cc nh my nhit in s dng cc nhin liu cn lu hunh v lu hunh cao, dn n nhim mi trng. Cn du c c trng l c trng lng ring v hm lng lu hunh cao, hp cht vng phn t lng cao v c cha vanady v cc kim loi khc. Cc tnh cht ny c bit c trng cho cc sn phm thu c trong ch bin du nhn c trong ch bin du lu hunh. Trong cng nghip ch bin du ng dng rng ri cc qu trnh lm sch bng hydro cho cc phn on xng, kerosen v diesel. N cng c ng dng ph bin lm sch

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parafin v du bi trn thay cho lm sch bng t st. Ngoi ra trn th gii hin ny cng ng dng qu trnh hydrodesulfur lm sch mazut. Trong lm sch hydrocarbon phn t lng cao d b cht xc tc hp ph, cn kim loi c bit vanady v niken lng ng trong l xp ca xc tc. Mc d vy hydrodesulfur vn c ng dng cho x l cn du. Bn cnh hydrodesulfur trc tip trong cng nghip cn c cc phng php khc ch bin cn du. Cc phng php ny c tm tt trong bng. Cc phng php x l sn phm cn du
Nguyn liu 1) t lu hunh (<1,5% lu hunh) 2) Lu hunh trung bnh (1,5-3% lu hunh) 3) Lu hunh trung bnh, kim loi cao 4) Lu hunh cao (> 3% lu hunh) 5) Lu hunh cao, kim loi cao Hm lng lu hunh trong nhin liu t l, % 1 0,5 0,3 A + HAG V+VC+HVG V+HVG+HC V+C+HVG+HD V+HVG V+HVG+HC V+VC+HVG -

V+C+HVG+HD V+C+HVG+HD V+C+HVG+HC V+HAG+VC+ HC+HVG V+C+HVG+HD

(Trong : A- Chng ct kh quyn; V- chng ct chn khng; HAG- lm sch bng hydro Gasoil kh quyn ; HVG- lm sch bng hydro Gasoil chn khng; HD- lm sch bng hydro distilat qu trnh cc ha; HC- lm sch bng hydro cn du; VC- Visbcrakinh; C- qu trnh cc ha.) Hydrodesulfur trc tip cn du c th tin hnh trong lp xc tc tng si hoc lp tnh c x l trc nguyn liu hoc khng. Vic la chn h thng ch bin ph thuc vo kh nng duy tr hot v la chn ca xc tc trong thi gian di. Trong cn du asphanten c hm lng kim loi cao, do lm tng mnh s u c xc tc s dng trong qu trnh HDS cn du. tng chuyn ha HDS cn tng nhit v gim tc np nguyn liu, iu ny ng thi cng lm tng tc lng ng kim loi, dn n tng du c xc tc. Trong trng hp ny c s ph thuc tuyn tnh gia su loi lu hunh v kim loi.

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Nguyn t hot ng cho xc tc HDS trc tip cn du l Ni, Co, Mo v W; cht mang l oxit nhm v silic, alumo-silicat t nhin v tng hp. Cht mang ng vai tr quan trng trong c ch to cc v lng kim loi trn b mt xc tc. Khi tng b mt hot ng, th tch v bn knh l xp tng, tuy nhin xc tc l xp ln c bn vng km. Qu trnh lm sch bng hydro tin hnh trong mi trng c hydro v s dng xc tc alumo-coban v alumo-niken-molibden nhit 325 455oC,p sut 3 7 MPa, tc np nguyn liu 1 10 gi-1 v bi s tun hon kh cha hydro (hm lng hydro 60 94%) 160 900 m3/m3 nguyn liu trong pha hi (xng t cc qu trnh khc nhau) cng nh trong pha lng (kerosen, nhin liu diesel, du bi trn v parafin). Trong mt s cng trnh nghin cu s dng thnh cng xc tc AHM x l nhin liu t l cha hm lng lu hunh di 1% (khi lng) nhn c trong qu trnh deasphanten mazut, trong loi 90 95% niken, vanady, asphaten v tip theo l lm sch bng hydro deasphantizat 15 30 MPa, 360 440oC, chi ph hydro l 0,45% (k.l.). Mc ch chnh ca lm sch bng hydro l tng cht lng cc phn on du nh loi hp cht khng mong mun (lu hunh, nit, oxy, nha, hydrocarbon khng no). Nng cn li ca lu hunh trong sn phm sau khi lm sch bng hydro khng cao, c th: - Xng cha 1,2.10-4 2.10-6 % lu hunh c s dng tip trong reforming; - Nhin liu phn lc: 0,002 0,005 %; - Nhin liu diesel: 0,02 0,2%. Sn phm ca lm sch bng hydro bn cnh thng phm chnh cn nhn c kh, phn ct (t phn on kerosen v nng hn) v hydrosulfur. Kh cha hydro, metan v etan c s dng trc tip lm nguyn liu trong cc nh my; phn ct - phn on xng tr s octan thp lm thnh phn cho xng t hoc ph gia cho nguyn liu ca reforming; hydrosulfur lm nguyn liu sn xut lu hunh v axit sulfuric. Trong qu trnh Hydrodesunfua, lu hunh c trong nguyn liu c chuyn ha thnh H2S nh vo phn ng b ry lin kt gia S v mch

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cacbon, sau hydro s thc hin phn ng hydro ha n nh mch cacbon. Nh vy qu trnh Hydrodesufua s to ra cc sn phm nh hn. RSH + H2 RH + H2S 17 Kcal/mol R S R + 2H2 RH + RH + H2S - 28 Kcal/mol S + 4H2 C4H10 + H2S 67 Kcal/mol

Lu hunh tn ti trong cc nguyn liu ch yu cc dng nh mercaptan (thio) hay sunfua. i vi cc ngun nguyn liu nng th lu hunh c th nm dng disufua v thiophen.
3.2 Qu trnh tch Nit (Hydrodenitro)

Nit c trong du th vi hm lng nh hn lu hunh 5 20 ln, s c mt ca nit c kh nng lm mt hot tnh ca xc tc mt cch nhanh chng (Nit s trung ha cc tm axt ca xc tc). Ngoi ra phi loi tr nit trong sn phm tng tnh nh v cc hp cht ca nit c kh nng to mu v nha trong qua trnh tn tr v s dng. y l qu trnh c ngha rt quan trng i vi cc nguyn liu nng. Khi nguyn liu nng thm nng hp cht nit tng. Cc amid vng c trong du l hp cht nit trung ha. S hin din ca cc hp cht ny u c nhiu xc tc. Do mc ch ca qu trnh hydro ha l loi cc hp cht nit ra khi phn on xng-ligroil (l nguyn liu cho reforming xc tc), distilat trung bnh v cc nguyn liu nng cho cracking xc tc. Nh hydro ha cc hp cht nit to thnh hydrocarbon parafin hoc thm vi cc radical alkyl ngn (C1 C3) v amoniac. Tng phn t lng ca phn on mc loi hon ton hp cht nit gim. Thnh phn xc tc v cht mang nh hng n kh nng loi nit. Trong hydrocracking c xc tc disulfur volfram trn cht mang alumosilicat s hin din ca hp cht nit trong nguyn liu lm gim phn ng ng phn ha dn n to thnh amoniac v amin. Trong cc qu trnh lm sch bng hydro cng nghip nhin liu t l, du diesel v du bi trn c th loi b hon ton hp cht nit tnh kim, l nguyn nhn lm gim bn vng ca sn phm du v to cn khng ha tan trong thi gian tn tr.

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Nit c loi tr ra khi nguyn liu bng cch chuyn n thnh dng NH3 di tc dng ca hydro. RN + 2 H2 RH + NH3 Nit nm trong hn hp vi cc hydrocacbon cc dng nh Pyridin hay Pyrrol. c th thc hin qu trnh tch nit t cc hp cht ny th phi thc hin qu trnh hydro ha chuyn cc hp cht ny thnh naphten trc, sau qu trnh denitro mi c th thc hin c trn cc vng naphta. Nh vy qu trnh hydrodenitro kh khn hn so vi qu trnh hydrodesufua v tiu tn lng hydro gp bn ln qu trnh hydrodesufua. Cc hp cht nit hydro ha v nguyn tc nh hp cht lu hunh, nhng sn phm to thnh l amoniac. Th d, ha hc phn ng hydro ha theo s sau:
C3H7
+2H2

C3H7

+H2
NH NH3

+H2

+ NH3

Phn ng trc tin bt u bng no ha nhn d vng, sau m vng hydro ha cc v tr khc nhau v to thnh amin bc nht v bc hai. Giai on sau l hydro ha tip to hydrocarbon thm vi mch nhnh ngn, parafin v amoniac t do. Hp cht cha nit hydro ha kh khn hn hp cht lu hunh v hp cht cha oxy, cng nh dien v cc olefin. Xc tc s dng trong hydro ha hp cht nit tng t nh trong phn ng hydrodesulfur.
3.3 Qu trnh tch Oxy (Hydrodeoxygen)

Qu trnh hydrodeoxygen l qu trnh tch loioxy ra khi nguyn liu di dng H2O. Oxy hin din trong nguyn liu di dng cc hp cht nh phenol v peoxit. Cng ging nh qu trnh tch loi nit, thc hin qu trnh tch loi oxy th phi thc hin qu trnh hydro ha cc aromatic trc, v th qu trnh ny tiu tn nhiu hydro. Lng hydro cn cho qu trnh hydrodeoxygen gp khong hai ln so vi qu trnh hydrodesunfua.

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Ngoi ra mt lng nh hydro cn c dng tch loi cc hp cht clor hu c v chuyn ha thnh HCl, cng nh kh cc kim loi bm trn b mt ca xc tc trnh lm gim hot tnh ca cht xc tc.
3.4 Qu trnh n nh cc Hydrocacbon (Saturation of Hydrocacbons)

Bn cnh vic s dng hydro vI mc ch tch loi cc cht bn, hydro cn c s dng nh tc nhn hydro ha cc olefin nhm nng cao tnh n nh ca sn phm. Lng hydro tiu th t l vi s lien kt pi trong cc hp cht. Cc olefin thng c nhiu trong cc sn phm ca cc qu trnh c xy ra phn ng cracking qu trnh visbreaking, cracking xc tc. Tuy nhin vi cc cht xc tc c tnh chn lc cao th d n thc hin phn ng hydrotreating loi lu hunh nhng n li khng thc hin c phn ng n nh cc olefin, v th n vn duy tr c ch s octan kh cao cho sn phm xng. Nhng cc aromatic th c th chuyn ha thnh naphten v s chuyn ha ny xy ra thng xuyn trong cc qu trnh Hydrotreating distillat nng, gasoil v Hydrocracking.
3.5 Xu hng pht trin ca qu trnh Hyrotreating

Trong cc nh my lc du hin nay lng hydro thng thiu ht do cc qu trnh x l bng hydro tr nn ph bin v s thiu ht ny cng tng. Khi m nguyn liu ngy cng xu i th tnh nghim ngt ca cc qu trnh x l bng hydro cng tng v lng hydro tiu tn cng s cng tng. Chnh v th xu hng pht trin ca cc qu trnh s dng hydro chu s chi phi ca cc tc nhn nh: Du th ngy cng nng v cha nhiu lu hunh hn Nhu cu v cc sn phm F.O nng gim. Qu trnh Hydrodesunfua tng mnh do yu cu v hm lng lu hunh trong F.O ngy cng thp. Lng hydro tiu tn nhiu hn cho vic bo v cht xc tc. Do nhu cu v cc sn phm coke phi c cht lng cao.

4. Xc tc cho qu trnh Hydrotreating

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Cht xc tc s dng cho qu trnh hydrotreating ch yu l xc tc kim loi, c hai dng thng c nh sau: Xc tc Co-Mo l loi xc tc rt tt cho qu trnh Hydrodesunfua v n nh nh cc olefin, n c u im l hot ng ch rt mm v t tiu tn hydro. Loi xc tc th hai l Ni-Mo, c hot tnh rt cao i vi cc phn ng Hydrodenitro v n nh cc hp ht aromatic.

5. Cc yu t nh hng n qu trnh Hydrotreating

5.1 Nhit v p sut

Nhit v p sut ti u vo ca bnh phn ng nh hng trc tip n hiu qu ca cc qu trnh hydrotreating. Nu nhit ca phn ng tng th cng lm tng phn ng hydro ha nhng ng thi lm gim s tm hot ng ca cht xc tc, do vic iu khin nhit phn ng da vo s b p lI s gim hot tnh ca cht xc tc. Cn khi tng p sut ring phn ca hydro th ng ngha vi vic tng tnh nghim ngt ca qu trnh hydro ha.
5.2 Lng hydro tun hon

Lung hydro nhp liu phi nhiu hn lng hydro nhu cu cho phn ng, v th phi tun hon hydro sau cho m bo c p sut hydro ti u ra ca bnh phn ng kh nng ngn chn qu trnh cc ha v u c xc tc. Lng hydro tun han ny c ngha quan trng i vi cc nguyn liu distillat nng cha nhiu resin v asphalten.
5.3 Lm sch hydro

Cng nh hng ng k n qu trnh, v n gip duy tr nng cao ca hydro bng cch tch loi cc kh nh.

6. Mt s qu trnh Hydrotreating tiu biu

Mt s qu trnh hydrotreating tiu biu trong nh my lc du bao gm: Naphtha hydrotreating. Distillate (light and heavy) hydrotreating.

Gas oil hydrotreating.

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Chng ta c th so snh mc nghim ngt ca cc qu trnh hydrotreating da vo biu sau:

6.1 Naphta Hydrotreating

Trc tin nhp liu v hydro c a qua l nung v ti y hn hp ny s c nng ln n nhit khong 700oF, sau c dn n bnh cha xc tc thc hin qu trnh phn ng. Hn hp sn phm u ra ca bnh phn ng c lm ngui nhanh n 100oF thc hin qu trnh tch cc phn nh. Phn sn phm lng cn li s c dn n thit b stripping loi ht cc phn nh cn li, H2S v nc chua ra khi sn phm.

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iu kin thc hin phn ng hydrotreating naphta l khong 700oF v 200psig, iu kin ny c th thay i ty thuc vo hot tnh ca cht xc tc v tnh nghim ngt ca qu trnh x l. Lng hydro tun hon khong 2000scf/bbl. Qu trnh stripping c tc dng tch v tun hon hydro, ngoi ra n cn gip loi tr H2S. Lng hydro tiu th cho qu trnh ny khong t 50250 scf/bbl, v qu trnh ny phi cn n t 70-100 scf/bbl tch ht 1% lu hunh ra khi sn phm.
6.2 Distillate Hydrotreating

Hu ht cc phn on distillate u cha lu hunh, v th cn phi loi chng ra m bo yu cu v cht lng sn phm. Ngoi ra qu trnh ny cn gip n nh cc hp cht olefin nng cao ch s cetan ca diesel.

Cc qu trnh hydrotreating cc phn on distillate nh (Kerosen, jet fuel) tiu tn nhiu hydro hn so vi qu trmh hydrotreating naphta. iu kin thc hin cc phn ng ny khong 600-800oF, 300 psig hoc cao hn. Lng hydro tun hon khong 2000 scf/bbl v tiu th khong 100400 scf/bbl. iu kin phn ng ph thuc ch yu vo tnh cht ca nhp liu v tnh nghim ngt ca cng ngh.
6.3 Gas Oil Hydrotreating

Nhp liu cho qu trnh cracking xc tc (gas oil kh quyn, gas oil nh chn khng, gas oil thu t qu trnh deasphalt) th yu cu phi x l rt
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nghim ngt nhm mc ch loi lu hunh, m vng thm, tch cc kim loi. Xc tc Ni-Mo c xem nh xc tc ch yu v hiu qu nht c s dng cho qu trnh hydrotreating.

Bnh phn ng thng c hai lp, do trong qu trnh phn ng cc phn ng hydro ha ta nhit rt ln v cn phi c b sung hydro v lm ngui trung gian. Bnh tch p sut cao c nhim v tch v tun hon hydro, cn bnh tch p sut thp c nhim v phn tch phn nh. Nhit lc ban u khong 650oF, nhit ny p sut hydro ring phn s gip n nh v thc hin qu trnh tch lu hunh ra khi cc hp cht di dng H2S.

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Chng 11

CC QU TRNH LM SCH
1. Gii thiu
Qu trnh lm sch v phn tch phn on du c s dng dung mi la chn c ng dng rng ri. Phng php ny c ng dng trong sn xut nhin liu, du bi trn v hydrocarbon rn, ng thi cng c dng phn tch cc sn phm ch bin du vi mc ch nhn c nguyn liu cho cho tng hp ha du, thnh phn nguyn liu v cc sn phm khc (tch hydrocarbon thm ra khi xng platforming, kh ngng t, xng ct trc tip...). Trong lm sch bng dung mi la chn t nguyn liu tch cc cht sau: asphten, nha (smol), hydrocarbon thm a vng v hydrocarbon naphten-thm vi mch nhnh ngn, hydrocarbon khng no, hp cht lu hunh v nit, parafin rn. Hiu qu ca qu trnh lm sch v phn tch bng dung mi la chn ph thuc trc tin vo kh nng ha tan v iu kin ca qu trnh (dng dung mi, bi hi lu ca n so vi nguyn liu, nhit lm sch). Hin nay c s dng cc qu trnh lm sch v phn tch sau: loi asphaten, loi asphaten chia phn on, lm sch la chn v tch hydrocarbon thm, loi parafin v tch sp nhn c du nhn loi parafin v hydrocarbon rn. ng dng cc qu trnh ny trong sn xut du nhn cho php sau khi lm sch du nhn loi parafin thu c du nhn gc, sau khi trn chng vi du nhn gc khc v ph gia thu c du nhn thng phm. Cc qu trnh lm sch bao gm: X l bng amin Lm sch bng axit Lm sch bng NaOH Tch cc hp cht cha lu hunh Tch hydrocarbon thm a vng ngng t sn xut du gc Tch sp Tch asphaten

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2. X l bng amin
Kh du m v kh thin nhin bn cnh thnh phn chnh l hydrocarbon cn cha cc kh chua-kh carbonic, dihydrosunfur v cc hp cht lu hunh hu c: COS, CS2, mercaptan (RSH), tiophen v cc hn hp khc, lm phc tp qu trnh vn chuyn v s dng kh trong iu kin xc nh. S hin din ca CO2, H2S, RSH to iu kin xut hin n mn kim loi, chng lm gim hiu qu ca cc qu trnh xc tc v gy u c xc tc. CO2, H2S, RSH l cc cht c. Tng hm lng CO2 cn lm gim nhit lng chy ca nhin liu kh, gim hiu qu s dng h thng dn kh chnh do tng t trng v ch. lm sch H2S, CO2 v cc hp cht ph cha lu hunh, oxy trong kh thin nhin v kh ng hnh ng dng phng php hp th. Ph thuc vo kh nng tng tc ca cc hp cht ny vi dung mi - cht hp th c chia thnh cc nhm sau:
2.1 Qu trnh hp ph ha hc lm sch kh bng cc dung mi l dung dch nc alkanamin: monoetanolamin (MEA), dietanolamin (DEA), diglikolamin (DGE) ...

t c s trn phn ng ha hc ca cc hp cht khng mong mun vi alkanamin. Qu trnh amin cho php lm sch n mc tinh hydrosunfua v kh carbonic cc p sut v hm lng ca chng trong nguyn liu khc nhau; ha tan trong cc cht hp th khng cao. Cng ngh v thit b ca cc qu trnh n gin v ng tin cy. Nhc im chnh ca qu trnh: khng lm sch hon ton H2S, CO2, RSH, COS v CS2 trong kh; mc tch mercaptan v cc hp cht lu hunh thp; mercaptan, COS v CS2 tng tc vi mt s dung mi to thnh cc hp cht ha hc khng th hon nguyn trong iu kin phn ng; qu trnh thc hin c cn c bi s hi lu cht hp th cao v chi ph nhit nng ln; cht hp th v sn phm tng tc vi cc hn hp cha trong nguyn liu, trong khng t trng hp to thnh cc cht c hot tnh n mn cao. Khi tng hm lng hot cht v mc bo ha ca hydrosunfua v cc hp cht khng mong mun khc trong dung mi hot n mn ca cht hp ph alkanamin tng. V vy, kh nng hp thu ca chng
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thng khng do iu kin cn bng nhit ng hn ch m do gii hn mc bo ha kh chua cho php ca cht hp th.
2.2 Qu trnh lm sch kh bng phng php hp th vt l cc hn hp tp cht bng cc dung mi hu c: propylencarbonat, dimetyl ter polyetilenglicol (DMEPEG), N-N-metylpirolidon ...

Chng t c s trn hp th vt l, ch khng phi phn ng ha hc. Cc dung mi hu c v c bn c th c s dng lm sch hon ton H2S, CO2, RSH, COS v CS2 trong kh p sut ring phn cao trong iu kin hp th; cc cht hp th ny khng to bt v khng n mn thit b, nhiu cht hp th c nhit ng bng thp. Vi p sut hn hp tp cht cao thc hin qu trnh lm sch bng dung mi hu c i hi u t v chi ph sn xut thp hn so vi qu trnh hp ph ha hc amin, v kh nng hp thu ca dung mi hu c t l thun vi p sut ring phn ca kh chua v cc hn hp tp cht khc. Hon nguyn cc cht hp th vt l trong nhiu trng hp khng cn phi gia nhit m nh h p sut trong h. Khuyt im c bn ca cc qu trnh ny l: dung mi hp ph tt hydrocarbon; lm sch tinh kh trong nhiu trng hp ch c th thc hin sau khi thc hin cc qu trnh lm sch trc bng dung mi alkanamin .
2.3 Qu trnh lm sch kh bng dung mi l hn hp dung dch nc ca alkanamin vi dung mi ha c - sunfolan, metanol...

Chng t c s trn vic hp th vt l cc hp cht khng mong mun bng cc dung mi hu c v tng tc ha hc vi alkanamin. Cc qu trnh ny c nhiu u im c ca hp th ha hc v vt l. Chng c th c ng dng lm sch tinh H2S, CO2, RSH, COS v CS2. Khuyt im c bn ca cc qu trnh ny l: dung mi hp th tt hydrocarbon (c bit l hydrocarbon thm), iu ny lm hn ch lnh vc ng dng ca qu trnh nhm hai v ba. Tt c cc qu trnh u da trn hp th ha hc hoc vt l ca cc hp cht cha lu hunh-oxy v gii hp chng sau ra khi cht hp th v chuyn kh chua cha hydrosunfua sang thit b sn xut lu hunh dng Clause.

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2.4 Lm sch kh bng dung mi alkanamin

Vi p sut ring phn ca kh chua thp kh nng hp thu ca cht hp th alkanamin i vi hydrosunfua v carbonic tng ln. Trong lnh vc ny cc cht hp th ha hc cnh tranh c vi dung mi vt l. Dc y trnh by tnh cht ha l ca cc dung mi alkanamin:
MEA DEA DIPA DGA

Phn t lng T trng, kg/m3

61 1.018

105,1 1.090 187 150 1,33

133,2 989 248,7 167 133 1,33 42 0,198 ( 45oC) 87 722,5

105,1 1.055 221 1,33 9,5 0,026 ( 24oC) Hon ton 917,4

Nhit si(oC ), p sut (Pa): 110 171 660 100 1320 69 p sut hi bo ha 20oC, Pa 48 Nhit ng bng, oC nht tuyt i, Pa.giy ha tan trong nc 20oC,% k.l. Nhit ha hi 105 Pa, J/kg

10,5 28 0,241 0,38 ( 20oC) ( 30oC) Hon ton 96,4 1486,4 1205,9

Qu trnh tng tc CO2 v H2S vi monoetanolamin c vit bng phng trnh tng qut : 2RNH2 + H2S (RNH3)2S (RNH3)2S + H2S 2 RNH3HS CO2 + 2 RNH2 + H2O (RNH3)2CO3 CO2 + (RNH3)2CO3 + H2O 2RNH3HCO3 Trong R l nhm -OHCH2CH2. nhit thp phn ng din ra theo hng t tri sang phi, nhit cao-t phi sang tri: trong trng hp u H2S v CO2 "tng tc" vi cht hp th, trong trng hp th hai - din ra qu trnh hon nguyn cht hp th v thu hi kh axit hp ph (H2S v CO2).

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Hiu ng ta nhit ca phn ng nh sau: khi tng tc H2S v CO2 vi dung dch MEA l 1.905 v 1.917,6 J/kg, khi tng tc H2S v CO2 vi dung dch DEA l 1.189 v 1.515,7 J/kg.

3. Lm sch bng axit

Lm sch phn on du bng axit sulfuric loi hydrocarbon khng no, hp cht lu hunh, nit v nha, l nhng cht khin cho bn ca nhin liu gim trong qu trnh bo qun, khng bn mu v lm xu mt s tnh cht ng dng khc. Trong cc qu trnh lm sch thng thng axit sulfuric khng tc dng ln parafin v naphten. Tuy nhin, trong sn phm ph ca qu trnh hu nh lun lun pht hin thy cc hydrocarbon ny, do khi c axit sulfur v eter axit ca axit sulfuric cc hydrocarbon ny to thnh nh tng t cc sn phm lm sch. Cc hydrocarbon thm b sulfur ha khng nh nhau. Mc sulfur ha ca chng ph thuc vo s phn b ca cc nhm alkyl. Mc kh sulfur ha ca hydrocarbon thm tng khi tng chiu di v s mch nhnh. Cc hydrocarbon naphten-thm a vng b sulfur ha khi c chi ph axit cao. Cc hydrocarbon khng no phn ng vi axit sulfuric to thnh cc eter axit v sn phm polymer ha. Eter axit to thnh di tc dng ca axit sulfuric ln hydrocarbon khng no v nhit thp: R C = CH2 + H2SO4 R R R C OSO3H CH3

Eter axit ca axit sulfiric ha tan trong nc, khi trung ha to thnh mui tng ng. Di tc dng ca nc v c bit l dung dch nc kim chng d dng hydrat ha, to thnh ru tng ng: R C R OSO3H CH3 + H2O H2SO4 + R R C OH CH3

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Phn ng ny din ra nhit thng. Eter axit ca axit sulfuric phn ng vi hydrocarbon thm nhit thp, to thnh hydrocarbon th alkyl. Khi tng tc vi hydrocarbon khng no cc eter ny to thnh polymer tng ng - l cc cht nha snh. Eter tp trung trong cn axit cha cc sn phm khng tan trong distilat sch ca phn ng axit sulfuric vi hydrocarbon v dn xut cha lu hunh v axit. Eter trung bnh ca axit sulfuric c to thnh khi tng tc gia axit sulfuric vi hydrocarbon khng no nhit cao (trn 40oC): R C = CH2 R + R C = CH2 R R OH OH SO2 R C CH3 R SO2 R C CH3

Eter trung bnh cng c th c to thnh khi nung nng eter axit ca axit sulfuric: R C R R C R OSO3H R OSO3H CH3 t H2SO4 + R C CH3 O R CH3 R C O SO2 CH3

Eter trung bnh ca axit sulfuric l cht lng c khng mu, khng ha tan trong nc, nhng ha tan tt trong dung mi hu c. Lng ng k ca eter ny d dng ha tan trong sn phm sch.

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Trong cc hp cht cha lu hunh hydrosulfur, mercaptan v tiophen phn ng vi axit sulfuric. Hydrosulfur khi tng tc vi axit sulfuric to thnh lu hunh, anhydric lu hunh v nc: H2S + H2SO4 2 H2O + SO2 + S Lu hunh ha tan trong distilat sch v trong chng ct th cp sn phm lm sch n phn ng vi hydrocarbon v li to thnh hydrosulfur. Do trc khi lm sch bng axit sulfuric distilat cn phi c loi sch hydrosulfur bng cch ra bng dung dch kim. Vic loi hon ton hydrosulfur c nhn bit qua vic to lu hunh nguyn t khi oxy ha bng oxy khng kh. Phn ng ca mercaptan vi axit sulfuric din ra theo phn ng sau: 2RSH + H2SO4 RS SR + SO2 + 2H2O Disulfur to thnh d dng ha tan trong sn phm ca qu trnh lm sch. Khi tc dng axit sulfuric c vi tiophen v ng ng ca n to thnh tiophensulfoaxit. Disulfur, sulfur, tiophan v sulfon khng phn ng vi axit sulfuric, nhng ha tan tt trong n, c bit l nhit thp. Mt phn axit naphten cng ha tan trong axit sulfuric v mt phn sulfur ha. Phn t lng ca axit naphten cng cao n cng d b sulfur ha. Ha tan trong axit sulfuric hoc to thnh sn phm sulfur ha axit naphten lm gim nng ca axit v dn ti gim tc dng ca n. Do trc khi lm sch bng axit sulfuric cn loi axit naphten. Cc cht nha phn ng vi axit sulfuric theo ba hng: mt phn nha ha tan trong axit sulfuric, phn khc ngng t v to thnh cht ging asphanten, phn th ba to thnh sulfoaxit. Tt c cc dng ny u chuyn vo gudron. Axit trung bnh c ng dng trong sn xut du nhn truyn ng v du nhn trng trong hon nguyn du nhn s dng, ng thi cng lm sch parafin, s dng trong cng nghip thc phm v trong sn xut protein.Trong lm sch bng axit sulfuric t phn on du nhn loi c hydrocarbon khng no v cht nha- asphanten. Dng phn ng ph thuc vo nhit , thi gian tip xc di, chi ph, nng ca axit sulfuric v trnh t tin hnh.

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4. Lm sch bng NaOH

Lm sch phn on du bng dung dch kim c ng dng loi cc cht cha oxy (axit naphten, phenol) v mt s hp cht cha lu hunh (hydrosulfur, mercaptan) v trung ha axit sulfuric v sn phm tng tc ca n vi hydrocarbon (sulfoaxit, eter ca axit sulfuric) cn li sau khi lm sch bng axit sulfuric. Dung dch kim trong nc phn ng vi hp cht axit to mui ha tan trong nc. Mt phn trong cc hp cht ny c cha sn phm du v chng s b loi ra bng cch ra nc. Mui kim ca axit naphten cng nh phenolat khi ha tan trong nc thy phn v to thnh axit hu c, phenol v kim. Do axit v phenol ha tan tt trong sn phm sch, nn thc t sn phm ny khng loi sch axit v phenol. Mc thy phn ca mui kim ca axit naphten v phenolat ph thuc vo nng kim v nhit : tng nng thy phn gim, cn tng nhit thy phn tng. Do trung ha tin hnh vi dung dch kim c (10 15%) nhit khng cao. Khi lm sch distilat du nhn s dng dung dch hydroxyt natri long (1 3%) v qu trnh din ra nhit cao trnh to nh tng kh ph hy. Cc mui ca axit naphten v sulfoaxit c kh nng to thnh nh tng. Do trong distilat sng c cha hp cht lu hunh mt phn axit v phenol phn ng vi kim v c th c tch ra. Mt trong cc hp cht ny l hydrosulfur. H2S hin din trong distilat nh dng dung dch, ng thi cng to thnh lu hunh nguyn t khi tng tc vi hydrocarbon parafin v naphten v khi phn hy hp cht lu hunh c nhit si cao trong qu trnh chng ct du th hoc crackinh phn on du. Hydrosulfur phn ng vi dung dch hydroxyt natri to thnh sulfur natri khi d kim v to hydrosulfur natri khi thiu kim: 2 NaOH + H2S Na2S + 2 H2O NaOH + H2S NaSH + H2O Mercaptan phn ng vi hydroxyt natri to thnh mercaptid: RSH + NaOH RSNa + H2O Ngoi ra, cng din ra phn ng oxy ha mercaptan to thnh disulfur khi c oxy khng kh: 4 RSH + O2 2 RS-SR + 2 H2O
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Mc oxy ha mercaptan tng khi tng nhit v cng khuy trn hn hp. Disulfur to thnh khng ha tan trong nc v d dng ha tan trong distilat sch, dn ti tch mercaptan gim. Hp cht lu hunh trung ha (sulfur, disulfur, tiophen, tiophan) khng phn ng vi kim. Nh vy, x l distilat du th bng dung dch hydroxyt natri loi c hydrosulfur v mt phn mercaptan, axit naphten v phenol.
4.1 Lm sch distilat du nhn bng dung dch kim.

Distilat du nhn c lm sch bng dung dch kim theo s sau.

H thng s cng ngh nguyn tc ca cm lm sch distilat du nhn bng kim di p sut. 1- Thp thi kh, 2- trao i nhit; 3- l nung; 4,6- my khuy trn; 5-b lng; 8, 9- my lnh; 1013- my bm. I- Du cha lm sch; II- dung dch kim; III- du nhn kim ha; IVkim thi; V- nc ra; VI- khng kh. Distilat du nhn c my bm 10 bm vo khng gian gia cc ng ca trao i nhit 2, trong n c nng nhit n 40 50oC nh nhit ca distilat kim ha n t b lng 7. T trao i nhit distilat c a vo l nung 3 c p sut d 0,6 1 MPa, trong n c gia nhit n 150 170oC; sau vo thit b trn 4, dung dch hydroxyt natri 1,2 2,5% cng c my bm 12 bm vo. Trong thit b trn din ra qu trnh kim ha distilat dn nhn. Hn hp du nhn vi dung dch kim t thit b trn 4 vo b lng 5, trong du nhn c c tch ra khi cht thi kim (x
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phng naphten v kim). Cht thi kim ly ra t y b lng, c lm lnh n 70 80oC trong my lnh 8 v i vo b cha tch axit naphten. T trn b lng 5 du nhn kim ha vi nhit 130 140oC c a i ra trong thit b trn 6, trong nc vi nhit 60 65oC c my bm 13 bm vo. Sau khi c ra trong thit b trn hn hp du nhn vi nc c a vo b cha 7. Nc ra t y b lng c lm lnh trong my lnh 9 n nhit 70 80oC v i tip vo b cha tch axit naphten. Du nhn kim ha v ra vi nhit 90 100oC t trn b lng 7 c a vo khng gian gia cc ng ca trao i nhit 2, c lm lnh n 70 80oC v i vo thp lm kh 1, trong lm kh bng khng kh nn. Du nhn kim ha c my bm 11 bm vo cc b cha.
4.2 Lm sch distilat nhin liu bng dung dch kim vi cht tng cng.

Ch bin du lu hunh v du lu hunh cao ngy cng tng nn khng th iu ch c nhin liu cht lng cao m khng c lm sch c bit cc hp cht lu hunh hot tnh, trong c mercaptan. Mc d loi lu hunh su cc nhin liu distilat nh c th t c ch nh lm sch bng hydro nhng cc nc cn ng dng cc phng php lm sch khc. Mercaptan c loi b bng cch chuyn ha (oxy ha xc tc) thnh dng t c hn nh disulfur. Mt trong nhng phng php ph bin c ng dng trong loi mercaptan l qu trnh tin hnh vi xc tc hp cht kelat kim loi. Cc hp cht ny di dng oxy ha xc tin oxy ha mercaptan nhit thng v to disulfur theo phn ng sau: 4RSH + O2 2RSSR + 2H2O Xc tc c s dng di dng dung dch nc hoc trn cht mang rn. Trong s trn xng c a vo l phn ng 1, trong dung dch kim c cha xc tc Merock c my bm 7 bm vo. Nh loi mercaptan phn t lng thp ra khi nhin liu. Xng sch t nh l phn ng 1 c a vo l phn ng loi mercaptan 5, trong n tng tc vi khng kh v lng dung dch xc tc Merock b sung ( chuyn ha mercaptan phn t lng cao thnh disulfur). Sau hn hp c phn tch trong b lng 6, t trn b lng xng sch (VII) c ly ra, cn t di thp ly dung dch

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Merock tun hon (VI). Dung dch Merock cng mercaptan c ly ra t y l phn ng 1 qua l phn ng 2, trong n c trn vi khng kh, vo thp phn ring 3. T trn thp phn ring khng kh d c ly ra, cn t y dung dch Merock. T trn b lng 4 disulfur c ly ra, cn t y dung dch Merock hon nguyn, c ti s dng trong l phn ng 1.

S Merock 1- L phn ng loi mercaptan; 2- l phn ng oxy ha dung dch Merock s dng; 3- thp phn ring; 4- b lng tch disulfur; 5- l phn ng oxy ha mercaptan thnh disulfur; 6- b lng tch dung dch Merock; 7,8 my bm. I- Xng lu hunh; II- khng kh; III- dung dch Merock; IV-khng kh d; V-disulfur; VI-dung dch merock tun hon; VII- xng sch. Disulfur li trong phn on sch m khng lm gim tnh ng dng ca nhin liu.

5. Tch cc hp cht cha lu hunh

Vi mc ch tch cc hp cht lu hunh trong phn on nhin liu nhn c trong ch bin du lu hunh. Mt trong nhng nhim v trong lm sch lu hunh trong nhin liu l ci thin mi ca sn phm. Vi mc ch ny c mt s phng php x l, trc tin l lm sch mercaptan trong xng. Trong cc qu trnh ny cn phi hoc loi mercaptan ra khi nhin liu hoc chuyn ha n thnh cht c mi t kh chu hn (nh disulfur). Nhiu mercaptan cha trong xng c phn ng yu v c th loi ra bng cch ra
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bng dung dch kim trong nc. ha tan ca mercaptan trong dung dch kim c th tng nu thm axit hu c v cc hp cht khc. Ra kim l phng php n gin v c hiu qu cao lm sch cc phn on nhin liu. chuyn ha mercaptan thnh disulfur trong cng nghip hin nay s dng qu trnh Merox (oxy ha mercaptan). Hin nay trong cng nghip ng dng cc cng ngh x l hp cht lu hunh vi xc tc tng c nh ca Hng Gulf nh Gulf HDS, VOP-RCD, Chevron RDS Isomax v qu trnh ca Shell; cc qu trnh vi xc tc tng si nh H-Oil. Cc qu trnh nhm th nht ng dng x l nhin liu tng i nh nh mazut vi hm lng lu hunh 3 5% (k.l.), di 90 phn triu niken v vanady. Sn phm cha 0,6 1% lu hunh. Theo license ca Hng Gulf s cng nghip u tin c xy dng vo nm 1970 x l mazut ti nh my Nyppon Mining. Trong s c hai l phn ng vi cng sut tng l 1,7 triu tn/nm. Trong cc l phn ng xc tc c xp thnh lp v hydro lnh c a vo gia cc lp xc tc ly bt nhit. Hot xc tc c duy tr nh gi nhit cao: u chu k l 360oC v cui chu k nhit cao hn khong 60 70oC. Hm lng lu hunh sau khi x l l 1% (k.l.), ng thi cng gim hm lng kim loi v hp cht nit. Mt hng khc ca Nht Toa Oil xy dng s cng sut ln (3.300 m3/ngy) ha kh v loi lu hunh trong cn chn khng hm lng lu hunh cao theo qu trnh Flexcoking thu c nhin liu t l cha di 1% lu hunh. Mt s cng sut 43,5 ngn m3/nm lm vic theo hai giai on: trong giai on th nht bng qu trnh cc ha nguyn liu (gudron) thu c gasoil v cc; trong giai on hai cc c ha kh v kh, gasoil thu c t giai on I c loi lu hunh. Trong qu trnh ny nhn c hiu sut nhin liu t l l 80%. Qu trnh Flexcoking c ng dng ch bin nguyn liu khng thun li nht. a gudron vo l phn ng, trong nh chuyn ng ca dng kh xc tc trng thi tng si, cc c gia nhit trong thit b gia nhit, mt phn cc c a i tun hon cho l phn ng, phn d c ha kh bng khng kh v hi trong thit b khc. S liu v ch bin gudron c nhit si u 565oC, hm lng lu hunh 3,6% v kim loi 890 ppm (phn triu) nh sau:
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Hiu sut, % k.l. Kh n C4 Gasoil cc ha, oC si u 160 160 524 Kh t kh ha cc Cc 13 10 44 32,5 1,5

Hm lng lu hunh trong sn phm, % so vi tng lu hunh trong nguyn liu 25 2 38 35 -

Trong gasoil cc ha (160 524oC) cha 3,1% lu hunh v di 5 ppm (phn triu) vanady; trong cc c < 2% lu hunh v xp x 6% vanady. Bn cnh hydrodesulfur trc tip mazut c th ng dng h thng gin tip, trong mazut c chng ct chn khng v distilat sn phm c loi lu hunh v trn vi gudron. Sn phm cng c th loi asphaten v sau loi lu hunh cho deasphantizat. Trong hydrodesulfur ca c deasphatizat v mazut vanady s ct mch nhanh hn hp cht niken. Tng su loi lu hunh phn t lng ca sn phm to thnh gim v hm lng phn on trn 350oC tng. Hydrodesulfur distilat chn khng n hm lng lu hunh 0,2 0,4% c thc hin 5 10 MPa, xc tc c tui th trn 24 thng. Hiu sut nhin liu cha 0,7% lu hunh l 78%, chi ph xc tc < 0,2kg/tn sn phm. Nghin cu cho thy p sut thp loi lu hunh su ch yu nh hydrodesulfur hydrocarbon thm, cn p sut cao lu hunh c loi ra khng ch t cc cht thm v nha m c t asphanten. Gim p sut chi ph hydro gim, nhng tui th ca xc tc khng cao. Hng UOP xut qu trnh thc hin trong l phn ng vi nhiu vng khc nhau. Xc tc cha 4,1% km v 10,4% kim loi nhm VI (nh molibden) c mc gim hot thp trong ch bin nguyn liu cn lu hunh cao. Do cc xc tc truyn thng nh AKM v AHM c s dng trong giai on hai, cn xc tc Zn-Mo hoc Bi-Mo trong giai on th nht ca qu trnh loi lu hunh hai giai on.
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6. Tch hydrocarbon thm a vng ngng t sn xut du gc

Du bi trn c ng dng rng ri trong cc lnh vc k thut khc nhau. Hin nay trn th gii hng nm sn xut trn 30 triu tn du bi trn. Mt trong nhng xu hng pht trin l tng thi gian s dng ca du bi trn v gim chi ph cho dch v k thut. Theo phng php lm sch v tc cht s dng trong lm sch du bi trn c chia thnh nhm axit-kim, axit-tip xc, lm sch la chn, lm sch hp ph v du bi trn ca cc qu trnh hydro ha (lm sch bng bng hydro, hydrocracking...). Du bi trn l hn hp hydrocarbon cha 20 60 nguyn t carbon c phn t lng 300 750, si trong khong 300 650oC. Qu trnh c bn trong sn xut du bi trn l chng ct mazut trong chn khng, trong thu c distilat du nhn v gudron. Tt c cc giai on tip theo l loi cc nha-asphanten, hydrocarbon thm a vng vi mch nhnh ngn, parafin phn t lng cao, cc hp cht lu hunh, nit, hp cht cha oxy, l nhng cht lm xu tnh cht ng dng ca du bi trn, ra khi cc sn phm ny. Ph thuc vo thnh phn v tnh cht ca nguyn liu trong c ti 80% sn phm khng mong mun cn loi b, do n phi c x l bng cc phng php khc nhau v vi su tch loi khc nhau. Vic la chn nguyn liu ti u v chi ph cho lm sch quyt nh cc ch s k thut kinh t c bn trong sn xut du bi trn. Sau khi lm sch ta nhn c du gc l thnh phn c bn sn xut du bi trn thng phm. Du thng phm l hn hp pha trn ca cc thnh phn distilat, cn v thm mt s ph gia. Trong distilat du nhn v cn nhn c trong chng ct chn khng mazut c cha parafin (cu trc thng v nhnh); hydrocarbon naphten c cc vng nm v vng su vi mch nhnh parafin vi chiu di khc nhau; cc hydrocarbon thm (n v a vng) v hydrocarbon naphten - thm vi nhnh parafin; cht nha - asphanten; cc hp cha lu hunh, oxy v nit hu c. Loi b parafin v hydrocarbon vng vi mch nhnh di, kt tinh khi h nhit nhm thu c du bi trn c nhit ng c thp. Parafin so vi cc hydrocarbon khc c nht cao nht v tnh nhit nht tt nht v c ch
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s nht cao nht. Do khi loi parafin s lm gim tnh cht nhit- nht ca du bi trn. Cc hydrocarbon naphten-parafin trong du bi trn chim 50 75% ph thuc vo ngun nguyn liu. Naphten vi lng ti u l thnh phn mong mun trong du bi trn. Cc hydrocarbon thm hu nh lun c trong du bi trn thnh phm. Loi hydrocarbon thm (ch yu l thm a vng, mch nhnh ngn) ra khi du bi trn nguyn liu trong cc qu trnh lm sch la chn v lm sch hp ph, hoc chuyn ha chng thnh hydrocarbon naphten v parafin trong cc qu trnh hydro ha. c im ca hydrocarbon vng (naphten v thm) l c nht cao hn nhiu so vi parafin, l ch s quyt nh tnh linh ng ca du bi trn nhit thp. Do thu c du bi trn c tnh cht nhit thp tt cn phi loi parafin rn v hydrocarbon thm a vng mch nhnh ngn (c ch s nht thp). Nh nhn c du c tnh cht nhit-nht tt (ch s nht cao). Tuy nhin loi hon ton cc hydrocarbon ny lm xu cc tnh cht khc ca du nhn, th d bn oxy ha. su lm sch ti u bng dung mi la chn ph thuc vo thnh phn nguyn liu du. Cc cht nha-asphanten nm trong cc phn on si cao v gudron l chnh. Chng thuc nhm hp cht a vng bn cnh carbon v hydro cn cha oxy, lu hunh, nit v i khi c cc kim loi khc nhau. Cc cht nha-asphanten l cc cht khng mong mun v c loi ra trong qu trnh loi asphanten (lng nh cng c loi trong lm sch bng dung mi la chn v lm sch hp ph). Trong trng hp khng loi b hon ton cht nha-asphanten hiu qu lm sch bng dung mi la chn gim, bi ca dung mi so vi nguyn liu tng, gy kh khn trong hp ph v lm sch bng hydro du bi trn, lm xu tnh cht ng dng v s tip nhn ph gia ca du bi trn.

7. X l bng dung mi la chn

lm sch v phn tch nguyn liu du ng dng rng ri cc qu trnh da trn s ha tan cc thnh phn ca nguyn liu trong cc dung mi khc nhau. Trong lm sch la chn tch cc cht khng mong mun, c nh hng xu n tnh ng dng ca sn phm du ra khi nguyn liu (nhin

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liu, du nhn v cc sn phm khc). Cc cht khng mong mun gm hydrocarbon thm a vng, hydrocarbon naphten-thm vi mch nhnh ngn, hydrocarbon khng no, hp cht lu hunh, nit v nha. Nguyn liu cho qu trnh lm sch la chn l distilat du nhn v deasphantizat v cc phn on nhin liu diesel. Qu trnh lm sch la chn c bit c ngha i vi lm sch du nhn, do n lm tng hai tnh cht s dng quan trng ca du nhn: bn chng oxy ha v tnh cht nhit-nht. Sn phm lm sch (rafinat) c trng lng ring, nht, axit v c bit l cc thp hn so vi nguyn liu v nhit ng c cao hn; trong sn phm hm lng hp cht lu hunh v nhum mu thp hn. su lm sch la chn v phn tch cht mong mun v khng mong mun ph thuc vo la chn v kh nng ha tan ca dung mi v bi hi lu ca n so vi nguyn liu, nhit lm sch... iu kin tin quyt ca lm sch la chn l tn ti h hai pha - pha nh (dung dch rafinat) v pha nng (dung dch chit), nn gii hn nhit trn ca qu trnh lm sch c xc nh bi nhit ti hn ha tan (CTS), trn gi tr ny bt c t l no ca dung mi v sn phm ha tan to thnh h mt pha. La chn nhit lm sch da vo nhit ti hn ha tan v tin hnh lm sch nhit di gi tr ny 10 15oC. Theo kh nng ha tan hydrocarbon cc dung mi hu c v v c c chia thnh hai nhm chnh. Trong nhm th nht gm cc dung mi, m nhit thng c th trn ln vi cc cht lng ca nguyn liu mi t l, s ha tan ca cc cht rn trong cc dung mi ny tun theo qui lut chung. Cc dung mi ny l hp cht khng phn cc - cc hydrocarbon parafin lng phn t lng thp, kh ha lng v hp cht vi moment lng cc khng ln - tetraclo carbon, etyl eter, cloroform... Dung mi nhm th hai l cc hp cht c moment lng cc cao nh phenol, phurphurol, xeton aliphatic, dietylenglicol... S ha tan ca cc thnh phn ca du th trong cc dung mi ny ph thuc vo t l ca chng v nhit . Cc dung mi c kh nng ha tan khc nhau i vi cc cht khc nhau trong du nguyn liu, nn c gi l dung mi la chn. ha tan ca cc thnh phn nguyn liu trong dung mi nhm hai ph thuc vo thnh phn ha hc v bn cht ca dung mi. Khi iu kin khng
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thay i cc cht phn cc trong nguyn liu (nha v cc cht phi hydrocarbon khc) s ha tan tt nht. Cc hydrocarbon ca nguyn liu l hp cht khng phn cc v ha tan trong dung mi phn cc nh tng tc ca phn lng cc ca phn t dung mi vi lng cc qun tnh ca hydrocarbon. Bn cnh bn cht ha hc cu trc phn t ca hydrocarbon cng nh hng n nhit ti hn ha tan. Khi tng s vng trong hydrocarbon nhit ti hn ha tan gim mnh v tng khi tng chiu di mch alkyl. Ngha l, trong dung mi phn cc hydrocarbon thm a vng s ha tan trc tin. i vi naphten v parafin ch s ny khng ln do phn cc ca cc hp cht ny nh. Do nhit xc nh cc hydrocarbon ny ha tan trong dung mi phn cc ch yu di nh hng ca lc phn tn. ha tan ca cc nguyn t trong du nguyn liu nhm hai ph thuc c vo bn cht ca dung mi. Khi nh gi nh hng ca yu t ny n ha tan cc cht cn tnh n hai tnh cht ca dung mi: kh nng ha tan v la chn. Kh nng ha tan l kh nng ha tan hon ton cc cht cn loi ra. la chn ca dung mi c trng cho kh nng tch mt cht ny ra khi cc cht khc trong nguyn liu.Thng thng, moment lng cc cng cao kh nng ha tan cng cao. Cc nhm chc c nh hng n la chn ca dung mi c sp xp theo th t sau: NO2 > CN > CHO > COOH > OH > NH2. Trong cng nghip tng kh nng ha tan thng s dng cc dung mi hu c khng phn cc - benzen v toluen. Khi thm chng vo anhydrid, phurphurol, phenol, xeton lm tng mnh kh nng ha tan v gim nhit ti hn ha tan. Trong cc hydrocarbon ca phn on du nhn hydrocarbon rn nhm parafin, naphten, thm v naphten-thm vi mch alkyl thng, di t ha tan trong dung mi nht. Nu thm vo dung mi benzen hoc toluen, c th chn c hn hp, trong nhit xc nh hydrocarbon trong du nhn khng b ha tan cn tt c cc hydrocarbon cn li b ha tan. Tng chiu di radical hydrocarbon trong phn t dung mi, ha tan tt c cc hp phn ca du nhn tng. Nhng ha tan ca cc cht lng tng nhanh hn nhiu so vi hydrocarbon rn, ngha l c th t c ha tan hon ton cc cht
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lng nhit thp, l iu kin khng thun li cho ha tan cht rn. Cc dung mi ny l xeton cao (metyl-n-propyl xeton, metylbutylxeton...). Tng chiu di radical hydrocarbon ca xeton lc lng cc ca dung mi tng, do khng cn thm benzen hoc toluen vo xeton phn t lng cao. Thm dung mi th hai vo dung mi khng phn cc, th d propan ha lng, c th iu chnh kh nng ha tan ca dung mi th nht. Th d, thm metan, etan v mt s alcohol khc vo propan kh nng ha tan ca n gim. Butan, pentan, cc ng ng ca metan, olefin v mt s dung mi phn cc lm tng kh nng ha tan ca propan. Cc ph gia lm tng kh nng ha tan ca propan l phenol, crezol, furfurol v cc dung mi khc. Nh vy, s dng dung mi hn hp lm sch v phn tch du th nguyn liu cho php iu chnh kh nng ha tan v la chn ca chng . C nhiu dung mi c ng dng trong thc t. Trong cc s lm sch la chn hin i cc dung mi c s dng chnh l phenol, phurphurol v dung mi hn hp - hn hp phenol v phurphurol vi propan. u th ca phenol so vi phurphurol l c kh nng ha tan cao i vi hydrocarbon thm a vng, nha v hp cht lu hunh, c bit quan trng trong lm sch phn on si cao v cn. Bi s ca phenol thng thp hn phurphurol. Tuy nhin phenol km phurphurol v la chn, dn ti vi chi ph nh nhau hiu sut rafinat trong lm sch bng phurphurol cao hn phenol. lm sch phn on du nhn v deasphatizat t du lu hunh phenol c u th hn; phurphurol hiu qu hn trong trng hp do nhit ti hn ca dung dch vi nguyn liu (phn on si thp v phn on giu hydrocarbon thm) thp nn khng th s dng phenol. Dung mi hn hp s dng trong trng hp tin hnh ng thi qu trnh deasphanten v lm sch la chn. Phurphurol c ng dng lm sch distilat du nhn v cn loi aspaten ly t chng ct chn khng du c hm lng nha thp hoc trung bnh. i khi n cng c s dng lm sch nhin liu diesel ct trc tip v gasoil ca crackinh xc tc. Phurphurol c ha tan thp v tng ha tan cn tng nhit . Lm sch bng phurphurol thng thc hin nhit t 60 n 150oC. Trong iu kin ny khng gp kh khn khi lm sch nguyn liu c nhit ng c cao, lm tng s tip xc v phn tch
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rafinat v phn chit. C nc trong phurphurol lm gim kh nng ha tan v la chn ca n, do hm lng nc trong phurphurol khng c qu 1%. Khi lm sch nhin liu diesel c s dng phurphurol khan cn phi h nhit chit do h c nhit ti hn ha tan thp. S dng phurphurol c cha nc khng lm gim hiu qu lm sch, ng thi, tng nhit ti hn ha tan, cho php tin hnh lm sch nhit 30 50oC. Bi ca phurphurol so vi nguyn liu ph thuc vo nht ca nguyn liu v hm lng ca cc cht khng mong mun. Phenol c s dng lm dung mi la chn trong lm sch distilat du nhn v deasphantizat. N ha tan tt hydrocarbon thm mch nhnh ngn, c bit l hydrocarbon a vng v nha trong phn t giu vng thm. Hp cht nit chuyn hon ton sang phn chit. Ph thuc vo cht lng nguyn liu v iu kin lm sch hm lng lu hunh sau khi lm sch bng phenol gim 30 50%. Do kh nng ha tan ca phenol cao nhit ti hn ha tan ca hn hp phenol vi nguyn liu tng i thp, nn vic ng dng n trong lm sch distilat du nhn c nht thp gp kh khn, do nhit chit thp b hn ch bi nhit kt tinh cao ca phenol. Trong cc nh my kh nng ha tan ca phenol gim khi thm nc vo phenol v la chn cng gim.Tng m ca phenol lm tng lng rafinat nhng cht lng ca n gim. Thm nc vo phenol cng lm gim nhit nng chy ca n. gim kh nng ha tan ca phenol cng c th thm cc dung mi khc c kh nng ha tan thp nh etanol, etylen glicol..., nhng phng php ny khng ng dng trong cng nghip. Chit nguyn liu bng phenol tin hnh trong thp m, li hoc thp mm. tch cc cht khng mong mun tt hn cn phi iu chnh chnh lch nhit gia nh v y thp. Chnh lch nhit ny l 10 15oC trong lm sch phn on distilat v 15 20oC khi lm sch deasphantizat. Nhit chit ph thuc vo nguyn liu v thng trong khong 45 115oC. Chi ph phenol cho cc nguyn liu khc nhau nh sau: trong lm sch phn on distilat bi phenol i vi nguyn liu l 1,52 : 1 (khi lng), trong lm sch deasphantizat l 2,53,5 : 1. Khi ch bin du bi trn c ch

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s nht cao bi phenol so vi nguyn liu t 2,53,5 : 1 i vi nguyn liu distilat v 3,54,5 : 1 cho nguyn liu cn. Lm sch nguyn liu du bng dung mi la chn gm: chit cc thnh phn ca nguyn liu bng dung mi, to h hai pha trong thit b hot lin tc, hon nguyn lin tc dung mi t dung dch rafinat v dung dch chit bng cch nung nng, chng ct dung mi ra khi dung dch, lm khan nc dung dch.

S nguyn tc h lm sch la chn. 1- Thp chit; 2,5 l nung gia nhit rafinat v dung dch chit; 3,4- thp chng ct dung mi t dung dch rafinat; 6,7- thp chng ct dung mi t dung dch chit; 8- thp ct dung mi t nc; 9- b cha dung mi. I- Nguyn liu; II- rafinat; III- phn chit; IV- dung mi khan; V- hn hp nc v dung mi; VI- nc; VII- hi nc. Nguyn liu I c x l bng dung mi trong thp chit 1. Dung dch rafinat c gia nhit trong l nung 2 v trong thp 3 phn ln lng dung mi khan c tch ra khi rafinat; phn dung mi cn li trong hn hp vi nc c ct tip trong thp bay hi 4. Dung dch chit c gia nhit trong l nung 5. Phn ln dung mi c ct ra khi phn chit trong thp bay hi 6, phn cn li - ct ra trong thp bay hi 7, t thp ny thu c dch chit III. Dung mi khan t nh thp 3 v 6 sau khi c ngng t i vo b cha 9, t n li c a vo thp chit 1. Trong cc thp 4 v 7 dung mi
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c bay hi hon ton ra khi rafinat v phn chit nh hi nc. Hn hp hi dung mi v nc thot ra t nh thp c a vo cm lm khan, trong dung mi c tch ra khi nc. Dung mi kh IV i vo b cha 9, nc VI vo knh hoc vo thit b x l hi sn xut hi v li quay v thp bay hi.

8. Tch sp (Dewax)
Mt trong cc yu cu i vi sn phm l linh ng ca n nhit thp. S mt linh ng ca nhin liu v du nhn c gii thch l do kh nng kt tinh ca cc hydrocarbon rn (parafin v serezin) trong dung dch phn on du nhit thp, to thnh h cu trc, lin kt vi pha lng. thu c du nhn c nhit ng c thp trong cng ngh sn xut s dng cng on loi sp (deparafin) vi mc ch l loi hydrocarbon rn. Cc hydrocabon rn cng l nguyn liu sn xut parafin, serezin v nhiu sn phm c ng dng rng ri. Thnh phn ha hc ca hydrocarbon rn ph thuc vo gii hn nhit si ca phn on. Trong cc phn on du nhn nhit si thp c cha cc parafin rn cu trc thng. Tng gii hn si hm lng n-alkan gim, cn hm lng isoparafin v hydrocarbon vng, c bit l naphten tng. Thnh phn chnh ca cc hydrocarbon rn (serezin) tp trung trong cn chng ct mazut, l naphten vi mch nhnh c cu trc phn nhnh v lng nh parafin v hydrocarbon thm vi mch alkyl di. Tng nhit si ca phn on hm lng hydrocarbon rn tng v nhit nng chy tng. Bn cht ca qu trnh loi sp l tch hydrocarbon rn ra khi pha lng, i vi qu trnh ny hnh dng v kch thc tinh th ng vai tr quan trng. Tinh th parafin ln nht v c cu trc lp. Naphten v c bit l hydrocarbon thm c tinh th kch thc nh v c s mt hnh thoi nh. Loi sp c th thc hin bng mt s phng php: kt tinh hydrocarbon rn nh lm lnh; kt tinh hydrocarbon rn khi lm lnh dung dch ca nguyn liu trong dung mi la chn; to phc vi carbamid; chuyn ha xc tc hydrocarbon rn thnh sn phm nhit ng c thp; hp ph phn tch nguyn liu thnh cc cht c nhit ng c cao v thp; tc dng sinh hc. Phng php c s dng rng ri nht l s dng dung mi la

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chn; phng php t s dng hn l qu trnh loi sp bng carbamid, ng dng ch yu gim nhit ng c distilat nhin liu diesel.
8.1 Loi sp bng cch kt tinh c s dng dung mi

Qu trnh ny da vo ha tan khc nhau ca hydrocarbon rn v lng trong mt s dung mi nhit thp v c th ng dng cho nguyn liu du nhn vi thnh phn phn on bt k. Hydrocarbon rn ca phn on du nhn ha tan gii hn trong dung mi phn cc v khng phn cc. S ha tan ca cc hydrocarbon ny trong dung mi tun theo qui lut chung ca s ha tan ca cht rn trong cht lng v c c trng bi nhng tnh cht sau: ha tan hydrocarbon rn gim khi khi lng ring v nhit si ca phn on tng; i vi cc phn on si trong cng mt khong nhit ha tan ca hydrocarbon rn ca cng mt dy ng ng gim khi phn t lng tng; ha tan ca hydrocarbon rn tng khi tng nhit . ha tan ca hydrocarbon trong dung mi phn cc ph thuc vo kh nng phn cc ca phn t ca chng. Do kh nng phn cc ca cc phn t thp nn moment lng cc cm ng ca cc hydrocarbon rn khng ln, do s ha tan ca chng trong dung mi phn cc din ra di tc dng ca lc phn tn l chnh. ha tan ca cc cht cn li trong phn on du nhn l do tng tc ca lc cm ng v nh hng qui nh, tuy nhin tc dng ca lc phn cc cao hn, nn ngay nhit thp cc cht ny nm li trong trng thi dung dch. H nhit nh hng ca lc phn tn yu dn, trong khi nh hng ca lc phn cc mnh ln; dn n nhit thp hydrocarbon rn tch ra khi dung dch v nh c mch parafin di n gn nh kt tinh. Qu trnh loi sp c s dng dung mi la chn tin hnh lin tc v gm cc giai on sau: Trn nguyn liu vi dung mi X l nhit hn hp Lm lnh dn dung dch thu c n nhit cho trc; tch tinh th hydrocarbon rn ra khi dung dch Tch pha lng - lng Thu hi dung mi t dung dch du nhn loi parafin v sp.

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S cm loi sp c s dng dung mi la chn 1- My trn; 2- thit b gia nhit bng hi; 3- my lnh bng nc; 4thp kt tinh; 5- thp kt tinh bng amoniac; 6- my lc chn khng; 7- tch dung mi ra khi dung dch du nhn loi sp; 8- tch dung mi ra khi sp. I- Nguyn liu; II- dung mi; III- dung dch nguyn liu; IV- nh tng hydrocarbon rn; V- dung dch du nhn loi sp; VI- dung dch sp; VII- du nhn loi sp; VIII- hydrocarbon rn (sp). Nguyn liu I v dung mi vi t l cho trc trn ln nhau trong trong thit b trn 1 v c x l nhit trong thit b gia nhit bng hi 2. Nu nhit nguyn liu np vo s cao hn 60oC th khng cn x l nhit. Tip theo dung dch nguyn liu III c lm lnh trc tin trong my lm lnh bng nc 3, sau trong thp kt tinh 4, trong cht lm lnh l dung dch du nhn tch sp (filtrat) V v trong thp kt tinh bng amoniac 5 vi cht lm lnh l amoniac. Nu nhit sau khi lm lnh cn thp hn -30oC th s dng cht lm lnh l etan. Nh tng lnh ca hydrocarbon rn trong dung dch du nhn IV qua b cha (khng th hin trong hnh) vo my lc 6 tch pha rn ra khi pha lng. Cn hydrocarbon nng trn li lc c ra bng dung mi lnh II v i vo vt trn, trong cng b sung mt lng dung mi II to kh nng trn cn. Nh lc nhn c dung dch du loi sp V, c cha 75 80% dung mi, v dung dch hydrocacn rn VI vi hm lng du nhn nh. C hai dung dch c a vo thp phc hi dung mi 7 v 8.
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Du nhn loi sp sau khi thu hi dung mi VII c a i lm sch, cn sp rn c ch bin tip sn xut parafin v serezin. Dung mi hon nguyn quay tr li trn vi nguyn liu, ra cn, v mt lng nh a vo vt trn. Ph thuc vo thnh phn phn loi v thnh phn phn on ca nguyn liu dung mi c th c a vo trn ng thi hoc theo tng liu nhng v tr xc nh dc theo ng lm lnh nguyn liu.
8.2 Qu trnh loi sp bng dung mi lm lm lnh

Trong phn ln cc s loi sp v tch du s dng amoniac v propan lm cht lm lnh. S nguyn tc tch sp lnh s dng amoniac lm cht lm lnh c th hin trong s sau:

S nguyn tc tch sp v tch du lnh vi cht lm lnh amoniac. 1- Thp kt tinh; 2- thng tr; 3- thp tch lng; 4- my lm lnh; 5bnh cha; 6- thng trung gian; 7- tch du; 8- my nn. I- Amoniac hi; II- amoniac lng; III- nc. Hi amoniac tch ra t thp kt tinh 1, qua thng tr 2 i vo thp tch lng 3, sau nn bc I trong my nn hai bc 8 v di p sut 0,25 0,3 MPa c a vo thng trung gian 6, trong n c lm lnh nh bay hi amoniac lng II n t bnh cha 5. T thng trung gian 6 hi amoniac c a vo bnh p sut cao ca my nn 8, trong n c nn n p sut ngng t (1 1,2 MPa). Sau qua thp tch du 7, hi vo my lm lnh dng ng ng 4.
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Amoniac ngng t II chy vo thng cha 5, t vo thng trung gian, trong h nhit t 34 36oC (nhit ngng t) xung n 0 5oC nh bay hi amoniac cha trong thng. Amoniac lm lnh i vo bnh tr 2 v sau vo thng kt tinh 1, trong nh bay hi amoniac nh tng hydrocarbon rn trong du nhn c lm lnh. Amoniac lng t thng trung gian 6 np vo thng tr 2 qua van iu chnh mc. Nhit hn hp lnh ti ca ra khi thp kt tinh c iu chnh nh van gn trn ng x hi amoniac t thng tr.
8.3 Loi sp trong dung dch xeton - dung mi aromat

Trong cng nghip cc qu trnh loi sp trong dung dch xeton phn t lng thp (metyletylxeton hoc aceton) trong hn hp vi benzen v toluen c ng dng rng ri nht v trong thi gian sau ny ch s dng toluen. mt s ni s dng metylisobutylxeton. Vic s dng hn hp dung mi vi kh nng ha tan khc nhau i vi hydrocarbon lng v rn nh thay i t l xeton v aromat trong hn hp, c th loi sp nguyn liu vi nht v thnh phn phn on bt k nhit qu trnh khc nhau v thu c du nhn c nhit ng c bin thin rng. Hin nay qu trnh ny c tin hnh theo h hai bc, trong sp c ra trong qu trnh lc bc hai nhit cao hn. Vi s nh vy c th tng hiu sut du nhn loi sp v tc lc huyn ph, gim hm lng du nhn trong sp so vi qu trnh mt bc. S gm hai cm cng ngh: kt tinh, lc v thu hi dung mi t dung dch du nhn tch sp v sp. Nhit lc ph thuc vo nhit ng c yu cu i vi du nhn sn phm v tnh cht ca dung mi, c th l kh nng ha tan v la chn ca n. Di y dn ra nhit lc (oC) huyn ph ca nguyn liu distilat sn xut du nhn loi sp vi nhit ng c t -15 n -20oC. bc lc I Aceton-toluen Metyletylxeton (MEX)-toluen t -25 n -28 t -22 n -23 II t -15 n -16 t -12 n -13

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Trong qu trnh lc vi lc b nc v sp bt kn, do n c ra bng dung mi nng theo chu k. Thu hi dung mi t dung dch du nhn loi sp tin hnh trong 4 bc, cn t dung dch sp - ba bc.
8.4 Loi sp trong dung dch propan

Trong qu trnh loi sp trong dung dch propan ha lng c hai phng n lm lnh dung dch nguyn liu: cht lm lnh thng c s dng trong giai on lm lnh cui - amoniac v nh bay hi t dung dch ca chnh propan trong thit b ng hoc nm ngang hot ng lun phin. Tc lm lnh ca dung dch c iu chnh bng tc gim p sut. Do , trong thit b s bay hi ca propan ph thuc vo vic x hi propan, thc hin trong s s dng my nn kh. Bi ca propan so vi nguyn liu c gi c nh nh b sung lin tc propan b vo lng bay hi hoc thm propan lnh vo giai on lm lnh cui cng. u im c bn ca qu trnh ny l n gin v kinh t, do propan ng thi l dung mi v cht lm lnh. Ngoi ra, hi propan cn c s dng thi cn trong my lc. iu ny cho php b ng dn kh tr trong s . Trong qu trnh loi sp bng propan nh nht ca dung dch nh nhit thp, nn tc lm lnh cao hn nhiu so vi khi s dng xeton. Trong qu trnh lm lnh, c bit i vi nguyn liu cn, s kt tinh hydrocarbon rn v cht nha din ra ng thi dn ti to thnh tinh th ln, cho tc lc nhanh - t 600-1.000 kg/(m2.gi) theo nguyn liu, tnh trn ton b b mt lc. Loi parafin nguyn liu distilat c tc lc gim 10 15 ln do to thnh hydrocarbon rn cu trc tinh th nh. C th tng hiu qu ca qu trnh trong trng hp ny bng cch thm mt s ph gia to thnh tinh th ln hn. Do propan c ha tan cao nn bi ca n so vi nguyn liu khng ln - t 0,8:1 n 2:1 (th tch). Trong khi ha tan ca hydrocarbon rn trong propan cao i hi nhit deparafin thp c th tch hon ton cc thnh phn kt tinh.
8.5 Loi sp trong dung dch dicloetan-metylenclorua

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Qu trnh ny c tn gi l Di-Me, c ng dng sn xut du nhn v loi distilat v cn c nhit ng c thp. Dung mi c dng l dicloetan (50 70%) cht tr lng hydrocarbon rn v metylen clorua (50 30%) - l dung mi cho du nhn. Khi ng dng dung mi ny loi sp tin hnh nhit lm lnh cui v lc gn vi nhit ng c parafin ca du nhn, do tit kim c cht lm lnh. Bi chung ca dung mi so vi nguyn liu l 1:3 - 1:5 (t.t.). Loi sp mt bc c th thu c du nhn c nhit ng c -20oC v parafin vi hm lng du nhn 2 6% (k.l.). Khi s hot ng theo h lc hai bc cho php thu c parafin c hm lng du nhn di 2%. Mt trong nhng u im ca qu trnh l tc lc huyn ph ca hydrocarbon rn cao - n 200 kg/(m2.h) theo nguyn liu trn ton b b mt my lc. Dung mi khng to thnh hn hp n v khng phi l cht d chy, do trong s khng c h thng cp kh tr. Nhc im ca qu trnh ny l dung mi khng bn nhit 130 140oC, to thnh cc sn phm n mn. Deparafin trong dung mi dicloetan metylenclorur cng c tin hnh trong s nh ca qu trnh loi sp s dng dung mi xeton-dung mi aromat.
8.6 Loi sp su (nhit thp)

Deparafin su ng dng sn xut du nhn nht thp, nhit ng c thp. Qu trnh ny tin hnh trong dung dch xeton-toluen nhit lm lnh cui v lc huyn ph -62 -64oC. Nhit lm lnh thp nh vy khng th c c nu s dng cht lm lnh l amoniac, do trong qu trnh loi sp su trong giai on lm lnh cui s dng cht lm lnh l etan ha lng. Deparafin su ch tin hnh vi nguyn liu l rafinat ca phn on du nhn si thp, hydrocarbon rn ca n ch yu l n-alkan, to thnh tinh th ln, cho php lc hon ton pha rn ra khi pha lng v thu c du nhn c nhit ng c t -45 n -55oC. Kt qu ca qu trnh ny l ch s v cht lng du nhn loi sp thay i mnh hn so vi loi sp thng thng. Deparafin su thng c tin hnh lc hai bc, i khi lc ba bc, cho php tng nhit lc.

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9. Tch asphalten
Trong cn chng ct du (gudron, phn c c, semigudron) bn cnh hydrocabon phn t lng cao cn cha hm lng ln cht nha-asphaten. Nhiu trong s cc hydrocarbon k trn l thnh phn khng mong mun cho du nhn, do nhim v l phi lm sch cc phn on du ny. Hiu qu lm sch cn du khi cht nha bng dung mi la chn n cht l khng cao ngay c khi bi s dung mi cao. iu ny c th c gii thch l do khng phi tt c cc thnh phn ca nha ha tan tt trong dung mi la chn. V c bn cc cht nha-asphanten ha tan hoc phn tn trong nguyn liu c th c loi ra bng cch x l cn bng axit sulfuric, cng nh alkan phn t lng thp ha lng. Phng php loi asphaten bng axit sulfuric, c bit khi kt hp vi lm sch tip xc bng t st tip theo, ph hp sn xut du nh cn t phn c du th t nha. Tuy nhin, do chi ph axit sulfuric cao v to thnh lng ln axit gudron kh s dng khin cho phng php ny km hiu qu. Qu trnh tch asphaten gudron v phn c bng alkan phn t lng thp ha lng c ng dng trong sn xut khng ch du nhn nht cao, m c nguyn liu cho crackinh xc tc v hydrocracking. Dung mi c dng rng ri l propan ha lng, c bit trong sn xut du nhn, nhng trong mt s nh my cng s dng hn hp propan-butan. Vin du kh Bacu xut qu trnh tch asphanten bng phn on xng vi tn gi qu trnh Doben. nhit gn vi nhit ti hn ca propan (96,8oC), ha tan ca cc phn trong nguyn liu du nhn gim. iu ny din ra l do khi nhit dung dch gn ti vng trng thi ti hn ca dung mi th khi lng ring ca n gim mnh, dn ti tng mnh th tch mol. Ch s ny i vi hydrocarbon phn t lng cao thay i t. Do lc ko gia cc phn t dung mi v hydrocarbon gim lm gim ha tan. ha tan ca hydrocarbon ca nguyn liu du nhn trong propan trong vng nhit cao (75 90oC) gim khi khi lng ring v phn t lng tng. Nha v c bit l asphaten l nhng cht ha tan km nht trong propan lng; trn c s ny s dng propan lm dung mi cho qu trnh tch asphaten. Khi tip tc tng nhit cc hydrocarbon a vng phn t
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lng cao, cc hydrocarbon t vng vi mch alkyl di li trong dung dch. ha tan ca cc hydrocarbon a vng v nha nhit gn vi nhit ti hn ca propan gn n 0, cn ha tan ca hydrocarbon naphten v hydrocarbon thm nh tip tc gim. S ph thuc ny ca kh nng ha tan ca propan vo nhit (trong vng gn vi nhit ti hn ca propan) quan st thy p sut ng vi p sut bo ha ca hi propan nhit xc nh. Vic to p sut cao hn p sut hi bo ha ca propan dn ti tng khi lng ring v kh nng ha tan ca n. Do , nu hai nhit khi lng ring ca propan nh nhau (th d, 409 kg/m3), hiu sut v tnh cht ca cc hydrocarbon ha tan trong propan nh nhau. Thng thng qu trnh tch asphanten thc hin p sut cao hn i cht so vi p sut hi bo ha ca propan ha lng. Trn phn c vi propan (hoc butan), cc liu lng u tin ca n ha tan hon ton trong phn c. Lng dung mi cn bo ha nguyn liu ph thuc vo thnh phn nguyn liu v nhit . Trong nguyn liu cha cng nhiu cht nhaasphanten v hydrocarbon phn t lng cao th lng dung mi cn thit cho bo ha cng thp. Nhit cng thp, chi ph dung mi cho to hn hp bo ha cng cao. Khi tip tc thm propan ( nhit hn hp c nh) to thnh pha th hai gm propan v hydrocarbon ha tan. Nh trn ni, nhit gn vi nhit ti hn, propan ha tan mt lng hn ch hydrocarbon. Dung dch bo ha hydrocarbon trong propan to thnh bng cch ny (lp trn) cn bng vi dung dch bitum bo ha (lp di). phn tch tt nguyn liu trong hai pha (du nhn v bitum) bi propan so vi nguyn liu tng i cao - khng thp hn 3 phn th tch propan v 1 phn th tch nguyn liu. Do ha tan ca hydrocarbon phn t lng cao trong propan lng gii hn, tch cc thnh phn mong mun ra khi nguyn liu cn d nhiu dung mi. ng thi cng cn tin hnh tch naphten nhit cao khi ha tan ca hydrocarbon trong propan gim. y l c im ca propan so vi nhiu dung mi khc (phenol, furfurol v cc cht khc). nhit n ha (40 70oC) khi tng bi propan cht lng sn phn loi asphanten (deasphantizat) tng, nhng hiu sut gim. Sau khi t c ha long ti u hiu sut deasphantizat tng, nhng cht lng gim.
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nhit rt gn vi nhit ti hn ca propan khng c c bi ti u ca propan vi nguyn liu; chi ph propan tng. Bi cn thit ca propan i vi kt ta cc cht nha- asphanten ph thuc vo nng hydrocarbon mong mun trong nguyn liu. i vi nguyn liu t nha c hm lng parafin-du nhn cao cn c bi propan cao hn so vi nguyn liu giu nha- asphanten. Th d, loi asphanten trong phn c ca du t nha t l ti u propan : nguyn liu l 8:1 (theo th tch), cn khi loi asphanten trong gudron du nhiu nha cn t l 4 : 1. iu kin khc khng km phn quan trng l nhit qu trnh loi asphanten. Nn tin hnh qu trnh vng nhit tng i thp, khong 50 85oC, do di 40 50oC nha trung ha ha tan trong propan tuy khng nhiu, nhit 90oC, gn vi nhit ti hn ca propan (96,8oC), nhiu hydrocarbon mong mun khng ha tan trong n v b tch ra cng vi nha. Thng s chnh ca qu trnh loi asphanten khng ch l nhit , p sut v bi propan so vi nguyn liu, m c dng dung mi v sch ca n. Butan c la chn thp hn propan nhng cao hn etan. Metan v etan lm cho hi propan kh c ng trong my lnh. Vi nng etan trong dung mi khng ng k qu trnh loi asphanten din ra p sut qu cao, do trong propan k thut cha khng qu 7% (k.l.) cc hydrocarbon khc cng dy, trong khng qu 3% etan. S hin din ca propylen v butylen cng khng mong mun, do chng lm tng ha tan nha v hydrocarbon thm a vng. Hiu qu loi asphanten cng ph thuc vo mc loi phn on du nhn trong chng ct chn khng mazut - cha trong phn on gudron n 500oC. Nh trn thy, phn on phn t lng thp ca deasphantizat ha tan trong propan nhiu hn phn on phn t lng cao vng nhit gn vi nhit ti hn. Ngoi ra, do nh hng ca lc phn tn cc phn on phn t lng thp hot ng nh dung mi trung gian, lm tng ha tan ca cc phn on si cao v nha trong propan. iu ny khin cho vic phn tch chng s kh hn. Nguyn liu vi thnh phn phn on rng tch asphanten km hn nguyn liu loi phn on nh. Loi asphanten du nhiu du nhn, nhn c t nguyn liu c c (khng c phn on di 500oC), c cc v mu thp hn deasphantizat vi phn on si thp.
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Mc loi asphanten ra khi nguyn liu trong thp c nh gi trc tin thng qua cc ca deasphantizat, do nha v hydrocarbon a vng c cc cao. Sau khi loi naphten cc, khi lng ring, ch s khc x v hm lng kim loi (niken v vanady) gim; cc cht ny c c trong sn phm y - bitum loi naphten. Hm lng lu hunh trong deasphantizat thp hn trong nguyn liu, nhng loi lu hunh su khng din ra. Nha v c bit l asphanten c c trng l c kh nng nhum mu cao. Gudron vi khi lng ring ln c mu en, cn deasphantizat c mu t vng sng n xanh-xm ti. Tng mc lm sch, cng mu ca deasphantizat gim. Ph thuc vo c tnh ca nguyn liu, yu cu v cht lng v iu kin qu trnh hiu sut deasphantizat dao ng t 26 n 90%. Nhn chung, khi tng cc ca nguyn liu hiu sut deasphantizat nhn c trong qu trnh loi asphanten bng propan gim. Cc s cng ngh loi asphanten trong cng nghip c hai loi: mt bc v hai bc. Ch bin gudron theo s hai bc c th thu c deasphatizat c nht khc nhau; tng hiu sut ca chng cao hn deasphatizat thu c trong s mt bc. Hiu sut theo nguyn liu ca s thay i t vi trm n vi ngn tn/ngy. Trong cc s cng sut ln loi asphaten tin hnh trong hai thp hot ng song song. Trong s loi asphanten mt bc nguyn liu cn (gudron, phn c) nh my bm 17 bm qua thit b gia nhit bng hi 2 vo thp loi asphanten. Trong mt s s trc khi c gia nhit ngi ta a vo nguyn liu mt lng propan; trnh va p thy lc s dng thit b trn. S dng thp c hai hoc ba ca np nguyn liu v propan. Propan ha lng ly t b cha 7, nh my bm 18 bm qua thit b gia nhit bng hi 1 i vo phn di ca thp 3. Trong phn gia ca thp, propan trong dng i ln tip xc vi nguyn liu nng hn v dng tun hon ni.

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S cng ngh mt bc loi asphanten trong gudron bng propan 1- Thit b gia nhit propan bng hi ; 2- thit b gia nhit nguyn liu bng hi; 3- thp loi asphanten; 4- thit b gia nhit ni bng hi; 5, 5a, 6- thit b ngng t propan; 7- b cha propan lng; 8, 9- thit b bay hi propan t dung dch deasphantizat; 10- l nung gia nhit dung dch bitum; 11- thit b tch hi propan t dung dch bitum; 12, 13- thp bay hi; 14- thit b ngng t; 15- my lm lnh deasphantizat; 16- my lm lnh bitum; 17- my bm nguyn liu; 18- my bm propan; 19- my bm deasphantizat; 20- my bm bitum; 21- my nn propan; 22- thit b lng git lng. I- Nguyn liu; II- propan; III- hi propan; IV- dung dch deasphantizat; Vdeasphantizat sn phm; VI- dung dch bitum; VII- bitum; VIII- hi nc; IXnc Dung dch deasphantizat cng lng ln propan c gia nhit trong vng gia nhit bng hi 4, lng v tch ra t trn nh thp. Sau khi gim p n khong 2,4 MPa dung dch ny i vo thit b bay hi nm ngang 8, c gia nhit bng hi nc p sut thp, sau vo thit b gia nhit 8. Mt phn propan chuyn sang trng thi hi nh gim p. Deasphantizat tch ra t thit b gia nhit 9 c cha lng nh propan (thng khng qu 6%), c ch bin tip trong thp bay hi 12 bng hi nc. T trn thp 12 hn hp propan v hi nc tch ra, cn t y thp thu c deasphantizat sn phm

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v n c my bm 19 bm qua my lm lnh 15, ri vo b cha. Mc loi hon ton propan c iu chnh theo nhit bt chy ca deasphantizat. Dung dch bitum ra khi y thp 3 c gia nhit trong ng xon ca l nung 10, trong phn ln propan c bay hi. Hi propan tch ra khi cht lng trong thp tch 11, lm vic di p sut nh trong thit b bay hi 9. Cn propan bay hi nh hi nc trong thp bay hi bitum 13. Bitum ca deasphantizat c bm ra khi y thp bng my bm 20. Hi propan p sut cao t thit b gia nhit 8 v 9 v thp tch 11 i vo thit b lm lnh 5 v 5a. Propan ha lng c thu gom trong b cha 7. Thp lng c s dng tch hi propan ra khi nhng git lng b hi cun theo. Trong thit b lm lnh 5 hi propan ngng t di p sut gn vi p sut trong thit b 9 v 11, ngha l 1,7 2,1 MPa. Hi propan p sut thp trong hn hp vi hi nc t cc thp 12 v 13 tch ra khi hi nc trong thit b ngng t 14, sau qua thp lng git lng 22, c nn bng my nn 21 v a vo thit b lm lnh 6. Lng propan mt mt c b sung vo b cha 7. Nu propan np vo thp 3 qua hai b phn phi th phn propan i vo b phn phi trn c gia nhit n nhit cao hn (th d, 75oC) so vi phn propan a vo b phn phi di. Mt phn hi propan nn c a quay tr li vng trn ca thit b ngng t 14, vi mc ch gi cho p sut trong khng thp hn p sut kh quyn v nh trnh khng cho khng kh thm nhp vo thit b v to thnh hn hp n. Trong nhiu s cn c thp lm sch propan bng dung dch kim. Loi kim ra khi propan tun hon trong s bng dung dch hydrosulfur, lm gim n mn thit b v ng dn. Di y l ch cng ngh ca s loi asphanten gudron nha thp: Nhit , oC: Nguyn liu vo thp 3 nh thp 3 y thp 3 Trong thit b bay hi 8 Trong thit b bay hi 9 p sut hot ng, MPa:
184

120130 75 85 50 65 80 85 150165

Trong b cha propan lng Trong thp 3 Trong thit b bay hi 8 Trong thit b bay hi 9 Trong cc thp 12, 13 (p sut tuyt i) T l propan:nguyn liu (th tch)

1,71,8 3,74,4 2,22,4 1,72,1 0,12 4:16:1

Trong bitum loi asphanten thu c trong s loi asphanten mt bc phn c v gudron cn cha nhiu thnh phn c ch nh parafin-naphten v hydrocarbon thm t vng. Tch chng ra khi bitum loi asphanten trong qu trnh loi asphanten bc hai c th tng ng k ngun nguyn liu cho sn xut du nhn cn nht cao. Ngoi ra, vic phn loi hai deasphantizat c nht khc nhau ( 100oC trong bc I nht t 18 n 23 mm2/giy, trong giai on II: trn 40 mm2/giy), cho php m rng chng loi du nhn cn thng phm. Do trong mt s nh my s dng qu trnh loi asphanten hai bc. Trong thp loi asphanten bc II c p sut v nhit thp hn trong thp loi asphanten bc I; bi propan so vi nguyn liu cao hn nhiu. vn chuyn dung dch bitum vo thp th hai khng cn dng my bm v p sut trong thp loi asphanten bc I cao hn. Propan t dung dch deasphantizat bc I v II c hon nguyn ring. Deasphantizat bc II cha lng ng k hydrocarbon thm. Du nhn t deasphantizat bc I sau khi lm sch bng phenol v tch parafin c ch s nht 80 90 v hm lng cc 0,3 0,4 %, du nhn t deasphantizat bc II c ch s nht 7 90 v hm lng cc 0,81,2 %. Mt mt propan trong s cng nghip loi asphanten mt bc l 2 3 kg/tn gudron c ch bin; trong s loi asphanten hai bc - cao hn. Chi ph nhin liu cho l nung (ph thuc vo cht liu nguyn liu, su loi asphanten, hm lng propan trong dung dch bitum, dng nhin liu) l khong 15 30 kg/ tn gudron. c trng ca ca s loi asphanten l c chi ph hi nc cao, chim 50% tng chi ph hot ng.

185

Chng 12

S PHT TRIN CA CNG NGH LC DU

1. Gii thiu
Ngy nay cc nh ch bin du phi i mt vi thch thc ln l du th ngy cng nng hn v chua hn. Mt thch thc khc l tiu chun cht lng ngy cng cao hn. Do vic nghin cu v ng dng nhng tin b cng ngh trong lc v ch bin du l i hi thc t v c y mnh. Cc tin b ny c ng dng trong cng ngh, xc tc v thit b ch bin. Cc qu trnh c ch ci tin nhiu nht l lm sch bng hydro, loi hp cht lu hunh v hydrocracking v tn dng phn nguyn liu nng. Du kh ngy nay tr thnh ngun ti nguyn thin nhin v cng qu gi, mang tnh chin lc quan trng, c th lm thay i v khi sc nn kinh t ca mt quc gia. B trng nng lng Anh tng ni D tr du m ca mt nc tht qu nh d tr vng v ngoi t vy. hn mt th k qua i v chc chn trong nhiu nm ti, du m v kh thin nhin vn c coi l ngun nhin liu, nguyn liu ch yu cho cng nghip ch bin ca nhiu quc gia trn th gii. Du kh khng ch c ngha to ln v mt kinh t m cn c ngha chnh tr x hi, to ra mt lng vt cht to ln gp phn n nh v pht trin kinh t, x hi, to kh nng ct cnh cho nhiu quc gia. S tng trng kinh t th gii dn ti nhu cu nhin liu distilat tng. Nhin liu diesel l nhin liu vn ti quan trng nht trong mt s nc kinh t pht trin v vng kinh t pht trin mnh vn chuyn hnh khch v hng ha. Tiu th nhin liu distilat trung bnh trong mt s nc pht trin d an tng vi %/nm trong nhng nm 2000. Trong giai on ti cc nh ch bin du phi i mt vi thch thc ln phi sn xut nhin liu sch hn i vi mi trng, tiu chun cht lng ngy cng cao hn. Mt khc cc nh ch bin du cn phi i mt vi xu th du th ngy cng nng hn v chua hn do nguyn liu du th nh v ngt trn th gii ngy cng cn dn. Hn na bin gii quc gia trong th trng du ngy cng xa nha, nn tiu chun ha theo chun quc t l i

186

hi thc t, to iu kin cho cnh tranh. Gi du th v sn phm du tng trn di 30 USD/thng t thng 5/2000 v vn ang tip tc tng. bang California, M cn s dng MTBE cho xng k t nm 2002 v p dng qui ch mi v xng reformat. Trong thi gian ti M s p dng tiu chun xng v diesel mi c hm lng lu hunh cc thp (150ppm i vi xng v 350 ppm i vi diesel) v gim hm lng aromat trong xng. Cc nh ch bin du Chu u i hi phi sn xut nhin liu diesel c hm lng lu hunh gim (50 ppm p ng tiu chun sn phm vo nm 2050). p ng yu cu ny cn c cng ngh HDS hiu qu nht. Hin nay, vic sn xut xng chy sch c tun th tt hn nhin liu diesel. Trong c nhng qui nh v hm lng ti a v ti thiu i vi mt s thnh phn cha trong xng. Tng cng sut sn phm distilat khin cc nh ch bin du phi i mt vi s d phn on nhin liu cn trong lc du v th trng du th nng gim. Cn nhin liu lu hunh s c s dng trong vn ti bin v sn xut nng lng. Trong bi cnh mt s nh ch bin du la chn phng n b sung thm cm hydrocracking chuyn ha v loi lu hunh trong phn cn cha chuyn ha. Trong khi cc nh ch bin du khc li chn s dng cn du vo sn xut nng lng kt hp sn xut in vi hydro thng qua xy dng nh my turbin kh. Xu hng th trng hin nay lm cho cch bit v gi gia nhin liu vn ti tt v du nhin liu lu hunh cao ngy cng ln. Vi gi du th tng khang 10$/thng nh hin nay cc nh lc du cn tng cng chuyn ha nha chng ct chn khng p ng nhu cu th trng.

2. Tin b v xc tc
Trc y cc nh ch bin du da vo cng ngh chit tch lu hunh v lm ngt nh Merox p ng cc tnh cht xng v diesel. Tuy nhin, ngy nay nhiu nh ch bin du quay sang ng dng lm sch bng hydro cho sn xut nhin liu giao thng vn ti lu hunh thp. Vi vic tip tc ci tin cng ngh v xc tc khin cho Merox tr thnh mt trong nhng qu trnh thnh cng nht ca UOP. Phn ng c trng cho cc qu trnh Merox l oxi ha mercaptan (RSH) thnh disulfur (RSSR) trong mi trng alkanamin. Trong thc t ngi ta tin hnh loi mercaptan trong cc nguyn

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liu nh nh kh, C3, C4, LPG v naphta, sau oxi ha bng xc tc Merox. Cc phn on hydrocarbon nng nh Naphta, kerosen, nhin liu phn lc v diesel cha cc dng mercaptan khng th chit ra khi hydrocarbon. Trong qu trnh lm ngt Merox vi lp xc tc c nh mercaptan oxi ha thnh disulfur khi c khng kh, xc tc Merox v trong mi trng kim, nhng hm lng lu hunh trong qu trnh ny khng thay i. Hn na xc tc Merox trong trng hp ny c s dng dng bt rt bt tin. Do , xc tc Merox th h th hai (Merox WSTM) ra i, c hat cao hn v d s dng, giao nhn hn. Xc tc Merox No8TM tng c nh s dng trong qu trnh lm ngt l xc tc Merox FB mang trn than hat tnh. Vi vic s dng xc tc No8 cc nh ch bin du khng cn tin hnh giai on tm xc tc trong dng (in situ) v nh xc tc tham gia vo phn ng nhanh hn. nh my ch bin du c th lm vic lin tc UOP pht trin kch hat xc tc Merox FB v to thnh xc tc Merox PlusTM. Cht kch hat trong Merox PlusTM gip cho cc tm xc tc khng b che ph trong qu trnh phn ng. V vy s dng Merox Plus thi gian lm vic ca xc tc s ko di, ph hp cho qu trnh FCC. ng dng xc tc dng mi trn c s zeolit, c ngha quyt nh i vi qu trnh cracking xc tc. Zeolit tng hp c ng dng rng ri lm cht hp ph v xc tc l do trong thnh phn ca n c cc kim loi c kh nng trao i ion trong mi trng nc, to ra cc thnh phn khc nhau. Zeolit Y vi t l mol SiO2:Al2O3 t 3,1 n 6 c s dng lm xc tc cracking. mt s nc zeolit X (c l mol SiO2:Al2O3 bng 2,5) tham gia trong thnh phn ca xc tc cracking cng nghp. Xc tc zeolit c hat , la chn cao v c kh nng chu c cht u c tt, bn vi hi nc. S dng zeolit to cc gim l do hiu sut sn phm kh thp. Trong cng nghip zeolit khng s dng dng thun ty m dng ph gia (t 3 n 15% k.l.) thm vo alumosilicat. Vic ng dng xc tc zeolit vo thc t ch bin du lm tng ch s kinh t - k thut ca qu trnh. Nhc im ca xc tc zeolit l chng c gi thnh cao v ch c ch s tt cho nguyn liu ct trc tip, khng cha aromat. Cracking gasoil khi c xc tc zeolit khng c u th.
188

Xc tc cracking c iu ch dng ht vi cu ng dng trong lp tng si v vin cu cho cracking trong lp tnh. Bi xc tc tun hon trong s fluid gim t 7 20 xung 6 11, cn trong s vi xc tc vin cu ch s ny tng t 1,5 2,2 ln n 3 6. Bn cnh s dng nguyn liu nh (distilat), hin nay ngi ta ch bin lng ln nguyn liu distilat nng, trong c c sn phm ca cc qu trnh th cp. Xc tc l mt trong nhng thay i then cht trong vic xc nh c tnh ca sn phm polypropylen (PP) v c im ca cc qu trnh h ngun. S tng trng sn xut polypropylen Chu - Thi Bnh Dng trong 50 nm qua l rt ng ghi nhn. S tng trng ny dn n tiu th xc tc cho sn xut polyolefin tng v yu cu i mi cng ngh. Tuy nhin vic sn xut PP dng nh c ti u ha v qui trnh, hiu qu v cng sut. Xc tc c kh nng tng tnh kinh t, iu khin vi cu trc polymer, do iu khin phn t lng ca PP. N cng iu khin i cu trc, hnh th v phn b pha ca copolymer v/ hoc bipolymer. Xc tc quyt nh loi sn phm g s c sn xut. Xc tc Etyl Benzoat (EB) s dng trong cng ngh sn xut PP c phn t lng ln. Xc tc Etyl Benzoat l xc tc th h ba c s dng EB lm cht cho lin kt. Xc tc Avant ZN etyl benzoat c mt s u im so vi xc tc EB cng nghip. Xc tc Phtalat l xc tc th h bn, c tui th di hn. Xc tc Avant ZN Phtalat l xc tc a tnh cht, c th sn xut cc sn phm khc nhau. Cc sn phm ny c ng dng trong sn xut film, si v cc ng dng khc. Xc tc dieter l xc tc th h th 5, n sn xut polymer c kch thc nano. Xc tc ny c kh nng sn xut cc vt liu dng lp mng.

3. Tin b v cng ngh

Cng nghip ch bin du thay i quan trng trong x l cn du th trong lch s 136 nm ca mnh. Trong nhng nm 1960 v 1970 cc nh ch bin du la chn phng php loi b cacbon tn dng cn du v y l cng ngh c chi ph thp nht. Tip theo cc qu trnh cc ha v Visbreaker
189

c la chn cracking nha trong mt s nh my. p ng lut mi trng mi cc cng ngh x l bng hydro c ng dng lm sch cc sn phm cracking sinh ra trong qu trnh cc ha v Visbreaker. Trong qu trnh cc ha mi tt c cc sn phm c lm sch bng hydro, nh lm thay i hnh nh kinh t ca cng ngh cracking nhit cn du. Lm sch bng hydro c la chn do ba yu t sau: Hydro gi thnh thp c sn xut t cm reforming xc tc; Gi du th tng t nhng nm 1970; Lut mi trng mi ra i. T nhng nm 1980 Hoa K, Chu u v cc nc Chu - Thi Bnh Dng la chn cng ngh x l bng hydro cn du trong 62% s d n. chuyn ha cn v loi lu hunh trong cc nh my ch bin du cng ngh lm sch bng hydro c thc hin theo hai phng n sau: Loi lu hunh cn chng ct kh quyn (ARDS), tip theo l cracking xc tc cn (RFCC) nhm tng ti a hiu sut sn xut xng. ng dng qu trnh chuyn ha s dng hydro H-oil (hydrocracking cn chn khng) ch bin cn chn khng kt hp vi FCC hoc hydrocracking.

S kt hp H-Oil v FCC IFP cng l cng ngh tuyt vi. Qu trnh Hyvahl tng c nh ph hp cho vic nng cp cn chng ct kh quyn v cn chn khng cha hm

190

lng kim loi thp sn xut FO lu hunh thp hoc nguyn liu cho RFCC.

S IFP S kt hp delayed cocker vi lm sch bng hydro cng l phng n cng ngh c la chn. Trong trng hp ny tt c cc sn phm lng cn c x l bng hydro trc khi sn phm cui c sn xut ra hoc i n cc qu trnh h ngun. Sn phm qu trnh cc ha cha hm lng lu hunh v nit cao v cc olefin, diolefin v hydrocarbon aromat cn c bo ha tha mn v bn v cht lng sn phm. Cng ngh c la chn p ng cc c tnh ca diesel l: Hydrocracking sn xut diesel v gim lu hunh. Nh my ch bin du vi cm hydrocracking l la chn tt nht sn xut diesel c hm lng lu hunh 0,005%k.l. m khng cn tng u t ng k. Tuy nhin Hoa K cm hydrocracking thng hat ng vi mc ch thu c xng nhiu nht. Vic chuyn sang sn xut diesel s lm gim li nhun. Sn xut diesel vi nguyn liu du nh (LCO- light cycle oil) t FCC cn phi thm giai on gim hydrocarbon aromat p ng yu cu hm lng ca n l 10%. X l bng hydro gim lu hunh. Hin nay mt s nh my ch bin du Hoa K c cm x l hydro diesel lu hunh thp. Qu
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trnh ny s sn xut trc tip diesel hoc phn on sn xut nhin liu diesel 0,005%k.l. lu hunh. Chi ph u t cho gim lu hunh bng x l hydro l 2 cent/gallon. Bo ha aromat gim hm lng aromat. sn xut c lng ti a diesel v xng cht lng cao ngi ta xem xt cc phng n cng ngh khc nhau, trong bao gm c hydrocracking v FCC/alkyl ha nh: Trng hp 1: Delayed coking thng thng Trng hp 2: Delayed coking, cng ngh Conoco Trng hp 3: FCC cn Trng hp 4: Hydrocracking nha kt hp vi coking Trng hp5: Hydrocracking nha kt hp vi loi asphanten bng dung mi Trng hp 5: Hydrocracking nha kt hp vi loi asphanten bng dung mi v coking Delayed coking trn c s cng ngh Conoco c thi gian thu hi vn ngn. sn xut xng cc i, trong nh my ch bin du chn phng n FCC kt hp vi alkyl ha m khng c hydrocracking. Loi sp ra khi rafinat chng ct cha sp l mt giai on quan trng, trong ton b parafin mch thng, parafin mch nhnh nh v mt s hydrocarbon mch vng vi nhnh alyfatic mch thng c tch ra khi nguyn liu. Phng php loi sp thng thng, trong sp, du snh trn vi dung mi lnh lng sp. Sp c tch ra v loi ra khi dung mi nh qu trnh lc. Phng php loi sp bng dung mi (SDW) ny l cng on t nht trong ct du nhn. Dung mi thng c s dng trong qu trnh SDW l hn hp etyl-keton (MEK)/toluen c kh nng ha tan du v loi sp tt. Loi sp bng phng php ha hc l qu trnh chuyn ha ha hc, trong din qua qu trnh cracking la chn v (hoc) ng phn ha phn t sp vi cc xc tc l vt liu dng ry phn t, nh zeolit, h nhit si ca sn phm (sn phm cracking) v to cu trc nhnh t parafin (ng phn ha). Hiu sut to du nhn v cht lng c iu chnh bng

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cu trc xp ca xc tc v t l gia hat tnh cracking v ng phn ha ca xc tc. Loi sp bng xc tc l phng php thay th cho loi sp bng dung mi do n c chi ph u t v chi ph sn xut thp hn nhiu so vi SDW. Hin nay trn th gii phng php xc tc c s dng trong 6% cc cm sn xut du nhn v t l ny tng gp i trong nm 2000. Qu trnh MLDW l cng ngh loi sp bng xc tc do Mobil ng dng vo nhng 1970, da trn xc tc zeolit ZSM-5. trong qu trnh ny ZSM-5 cracking la chn n-parafin mch nhnh, sinh ra naphta v LPG. So vi SDW qu trnh MLDW loi c nhiu parafin hn t c cng nhit vn c. Khi c thng mi ha vo nm 1981 qu trnh MLDW thay th thnh cng v c hiu qu SDW. Qu trnh MLDW d hat ng, chi ph lm vic thp, u t v yu cu nng lng thp nn n tit kim hn so vi SDW l 3-6$/thng nguyn liu. Ngy nay, qu trnh MLDW c bin i ph hp vi s a dng ca nguyn liu v c th ca ch bin du. Nguyn liu c th thay i t gasoil chn khng v rafinat ch bin bng dung mi n sn phm hydrocracking du nhn v cn hydrocracking nhin liu. Trong 14 nm hat ng ca qu trnh MLDW, nhiu xc tc v thit k c ci tin. Cu trc xc tc tin tin ko di chu k lm vic v tng cht lng sn phm. Mi xc tc c ci tin khin cho mm do ca qu trnh MLDW tng ln v n c th ch bin cc nguyn liu ngy cng kh hn. Sn phm hydrocracking thuc nhm nguyn liu cn c loi sp bng xc tc. Nguyn liu ny c hm lng hp cht sulfur, nit v cc thp so vi ngun nguyn liu ly t ch bin bng dung mi. tn dng li th ca ngun nguyn liu sch ny hng Mobil pht trin qu trnh MLDW v s dng zeolit c la chn cu trc cao hn so vi xc tc ZSM-5. Kim loi qu c tm ln xc tc MLDW to kh nng ng phn ha sp v ct mch la chn, dn n tng la chn ca qu trnh. MSDW c u th so vi loi sp bng dung mi v xc tc MSDW chuyn ha sp thnh du nhn thng qua hydroisomer ha. So vi MLDW, qu trnh

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MLDW sn xut ra nhiu distilat trung bnh (165 321oC) hn vi cng mc chi ph naphta, C5 v C4. Qu trnh MWI, bao gn hydrocracking n ha v ng phn ha, c pht trin chuyn ha nguyn liu giu sp. Qu trnh MWI cho hiu sut du nhn v sn phm nht cao hn cng chuyn ha sp cho trc. MWI c th ng dng cho cc nguyn liu khc nhau sn xut du nhn cht lng cao. Cng ngh sn xut du nhn khng ngng c hon thin, trong bao gm c thit k cc s phc hp. H thng phc hp gm vi s cng ngh v sn xut mt s sn phm khc nhau. Vic thay th cc s c lp bng khu phc hp lm gim u t v chi ph sn xut, gim din tch xy dng v cng nhn, tng cng sut lao ng. Tng hiu sut sn xut du nhn t c bng cch hon thin v tng cng cc qu trnh ring r.

4. Tin b v thit b
Vic a qu trnh chit du cn trn ti hn (Residium Oil supercritical Extraction ROSE) vo ng dng trong nhng nm 1970 to kh nng xy dng s loi asphanten cng sut ln, hiu qu cao v tit kim nng lng. Vi s tin b ca cng ngh qu trnh loi asphaten bng dung mi tr thnh phng php ch bin du su c hiu qu. Ngy nay cng ngh trn ti hn c ng dng sn xut nguyn liu cho qu trnh FCC (Fluid catalytic cracker), du nhn nh, nguyn liu du loi asphanten cho cm cng ngh x l bng hydro v hydrocracking, c bit l nha v nhin liu nng. S tin b trong thit k thp tch trn ti hn dn ti s pht trin mi trong cng ngh loi asphanten kt hp vi qu trnh ROSE do Kellogg xut. Cng ngh phn ring mi cho php tng ng k cng sut ca cm ROSE v h chi ph u t v chi ph hat ng cho nh my ROSE tng lai. C hai s cng ngh ROSE c xy dng vo nhng nm 1970, mt l qu trnh loi asphanten bng dung mi propan sn xut du nhn sng v cc thnh phn pha trn asphanten; cm ROSE th hai dng cho sn xut nguyn liu cho FCC v thnh phn pha trn asphanten. Ngy nay cc cm cng ngh ROSE c ci tin theo ba hng:

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 Hon thin thit b phn ring Ti u ha thit b trao i ROSE Tng kh nng phn tch cc tnh cht ha l ca sn phm du Theo hng th nht, trong thp tch asphanten nguyn liu cn chng ct chn khng tip xc vi dung mi parafin nh v sau tin hnh hon nguyn dung mi iu kin trn ti hn trong thp tch DAO. iu kin trn ti hn, phn du ha tan trong dung mi tch ra khi du m khng cn ng dng cc phng php nng lng mnh nh ha hi bng flash. Do chi ph nng lng thp cho hon nguyn dung mi trong qu trnh ROSE nn vi t l dung mi: nguyn liu cao cho php c c hiu qu phn tch cao v cht lng sn phm cao nht. Cc thit b phn tn c ng dng trong tng thp tch to ra hiu qu cao trong hat ng ca thp. Nguyn liu nha c pha long trong dung mi tun hon trc khi i vo thp tch qua b phn phn b y thp.

5. nh hng ca s tin b v cng ngh n cht lng ca sn phm lc du

Lut s dng Naphta lu hunh thp ra i i hi cc nh lc du tm cch gim lu hunh trong sn phm vi chi ph thp. Mc d ton b hydrocarbon trong dy si ca Naphtan c th c x l bng hydro, nhng trong qu trnh ch s octan gim v chi ph hydro tng. Do xu hng ci tin l chia nh naphtan thnh phn on nh v phn on nng. Khi phn on Naphta nh c phn tch trong s chit lng - lng Merox iu kin n ha. Cn phn on nng, cha nhiu hp cht lu hunh c a i loi lu hunh th d trong qu trnh ISALTM. Trong s ISALTM phn on naphta nng c no ha olefin tip tng tr s octan. Bng cch ny c th loi trn 95% lu hunh trong phn on naphta nh trong s chit lng - lng Merox m khng lm gim tr s octan. Nh vy, bng cch ct Naphta thnh cc phn on hp l c th loi lu hunh ti a trong phn on FCC nh. Do Tiophen c nhit si l 65oC, nn cn ct phn on naphta sao cho tiophen c gi li trong phn on naphtan FCC nng.

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Ngy nay yu cu hm lng lu hunh trong cc sn phm du ngy cng thp hn. Bn cnh cng vi nhng thnh tu t c trong nhng nm qua trong lnh vc cng ngh, thit k l phn ng, xc tc, iu chnh thnh phn hydrocarbon v thit b iu khin to iu kin sn xut nhin dliu diesel lu hunh cc thp (ultra low sulphur diesel- ULSD). C ba vn then cht trong sn xut ULSD l: c im nguyn liu v qu trnh S tin b ca xc tc lm tng tnh kinh t ca qu trnh sn xut ULSD Cng ngh thit k l phn ng tng hiu sut ca s lm sch bng hydro Cc xc tc loi lu hunh truyn thng l CoMo. Nhng vi vic ng dng xc tc ny hm lng lu hunh trong diesel khng thp. Vi yu cu sn xut ULSD vi hm lng lu hunh 50ppm, cn chn cc xc tc c hiu qu hn. Mt khm ph c tnh cha kha l xut ra xc tc mi CENTINEL ca Criterion Catalysts & Technologies (Criterion). Xc tc CENTINEL c hat v bn cao. Ngy nay, nhiu qu trnh lm sch bng hydro distilat s dng xc tc CENTINEL sn xut diesel vi hm lng lu hunh 5-50 ppm, c thi gian lm vic 2-3 nm. Tip tc pht trin Criterion cho ra i xc tc th h mi cho cng ngh reforming vi tn gi cng ngh CENTINEL GOLD vo thng 3 nm 2004, to iu kin cho cc nh my ch bin du mm do hn v c th ci to iu kin qu trnh. Hai trong cc xc tc reforming nguyn thy l CENTINEL GOLD DC-2318 v DN-3330, l xc tc CoMo v NiMo mi nht ca Criterion cho qu trnh x l hydro distilat. Xc tc CENTINEL GOLD DC-2318 c hat bng 150% so vi xc tc hin ang s dng trn th gii. Xc tc CENTINEL GOLD DC-2318 gip gim chi ph u t nh gim kch thc l phn ng v cc chi ph khc (nh lm sch hydro). Xc tc CENTINEL GOLD DC-2318 cng c hat tnh HDN rt cao. Vi hat HDN cao xc tc CENTINEL GOLD DC-2318 c th s dng vi p sut ring phn hydro cao hn so vi p sut ti u khi s dng xc tc CoMo th h trc trong sn xut ULSD. u th ny cho php s dng xc tc 100%

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CoMo t c hat HDS cc i vi mc tiu th hydro thp nht so vi khi s dng xc tc NiCo. Ngy nay vi s pht trin ca CENTINEL GOLD Criterion a ra cng ngh xc tc mi vi tn gi ASCENT, s dng iu ch xc tc mi cho cng ngh x l hydro cho distilat p sut thp n trung bnh. Cng ngh tng phn tn ca pha hat ng nh s dng cng ngh mang mi. Xc tc u tin trong h ny l ASCENT DC-2531. y l xc tc rt tt cho qu trnh x l hydro distilat p sut thp.
Cht lng ca sn phm du ngy nay

Cht lng ca nhin liu vn ti, c bit l xng v diesel thay i mnh trn tan th gii trong thp nin qua. Chu v Nht Bn hm lng lu hunh trong xng cn phi xung n di 10 ppm(k.l.). Hoa K vo nm 2006, hm lng lu hunh trong xng cn thp hn 30ppm [1]. Hin nay du Diesel phi c hm lng lu hunh cc i l 0,05% k.l, tr s xetan ti thiu l 40 v trong mt s nhm cng nghip i hi tr s xetan l 50 v hm lng hydrocarbon aromat l 20% [2]. gim hm lng hydrocarbon aromat t 34% xung n 10% (t.t.) cn chi ph 10-15 cent/gallon [2]. Chi ph cho vic gia tng tr s xetan t 40 ln n 50 l 2- 2,5 cent/gallon. iu ny c th thc hin c nh thm ph gia hoc tng cng qu trnh hydrocracking du.

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