Quá trình hydrocracking là quá trình có lợi nhuận cao trong nhà máy lọc dầu

Tiu lun mn ch bin du Mc lc
Chng 1: Gii thiu qu trnh hydrocracking ............................................................... 3 1.1: Mc ch. ..............................................................................................................3 1.2: Nguyn liu. ..........................................................................................................3 1.3: Sn phm. ..............................................................................................................3 Chng 2: Qu trnh hydrocracking ................................................................................5 2.1: Nhit ng hc ca qu trnh. ...............................................................................5 2.2: ng hc v tc phn ng. ..............................................................................7 2.3: Xc tc cho qu trnh hydrocracking. ...................................................................8 2.4: Xc tc lng chc. .............................................................................................. 9 2.5: C ch phn ng hydrocracking. ........................................................................14 2.5.1: Chc nng ca xc tc. .................................................................................14 2.5.2: C ch phn ng trn xc tc. ......................................................................14 2.6: Xc tc b mt hot tnh v ti sinh xc tc. ....................................................... 16 2.6.1: Xc tc b mt hot tnh. ...............................................................................16 2.6.2: Ti sinh xc tc. ............................................................................................ 18 2.7: Cc yu t nh hng ti qu trnh. ....................................................................18 2.7.1: nh hng ca nhit . ..............................................................................18 2.7.2: nh hng ca p sut v lng hydro s dng. ........................................19 2.7.3: nh hng ca nguyn liu. ........................................................................19 Chng 3: Cng ngh Hydrocracking...........................................................................21 3.1: Asphaltenic Bottom Cracking Process ( ABC Process). ....................................22 3.2: H-Oil Process. .....................................................................................................23
Phm Minh c KSTN HD K54 Trnh Quang Thanh KSTN HD K54
Tiu lun mn ch bin du

3.3: Qu trnh hydrovisbreaking. ...............................................................................25 3.4: Hyvahl-F Process. ............................................................................................... 26 3.5: IFP Hydrocracking Process. ................................................................................27 3.6: LC-Fining Process............................................................................................... 27 3.7: Uniflex Process. ..................................................................................................29 3.8: Veba- Combi-Cracking Proces. ..........................................................................30 Ti liu tham kho .........................................................................................................32
Chng 1: Gii thiu qu trnh hydrocracking

Hydrocracking l qu trnh b gy mch C - C vi s tham gia ca hydro v xc tc, sn phm cui cng thu c l cc hydrocacbon no. l s kt hp ca qu trnh cracking xc tc cc hp cht ban u v hydro ha cc hp cht khng no va c to ra.
1.1: Mc ch.
Cng nh cc qu trnh ch bin du m khc nh reforming xc tc, cracking, isomer ha, th qu trnh hydrocracing cng nhm ch bin cc phn ct ca du m thnh cc sn phm nhin liu, cc loi du bi trn v cc sn phm trung gian cho cng nghip tng hp ha du.
1.2: Nguyn liu.

Nguyn liu cho qu trnh hydrocracking rt a dng, n l mt phn on kh rng, t xng nng ti du nng, cc nguyn liu u c nhit si cao hn so vi nguyn liu trong cracking xc tc. l: Phn on xng sn xut kh ha lng. Phn on kerosene-diesel v distilat chn khng sn xut xng, nhin liu phn lc v nhin liu diesel. Sn phm cn ca cc qu trnh ch bin du. Du c hm lng lu hunh cao, mazut, gudron sn xut distilat hoc nhin liu t l vi hm lng lu hunh thp.
1.3: Sn phm.
c im ca sn phm ca qu trnh Hydrocracking so vi qu trnh Cracking thng thng l rt t olefin, aromatc v nhiu iso parafin. V d nh xng i t hydrocracking c ch s octan cao, n nh cao. Phn on Kerozen c chiu cao ngn la khng khi cao v diesel th c ch s xetan 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 nh my lc du. Nh vy sn phm chnh ca qu trnh hydrocracking l cc sn phm trng nh xng, kerosene, diesel t dng nguyn liu l phn nng.
Chng 2: Qu trnh hydrocracking

2.1: Nhit ng hc ca qu trnh.
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. Cc phn ng chnh trong qu trnh hydrocracking nh: Hydro ha cc hp cht d nguyn t. Hydro ng phn ha alkane. Hydro ha vng thm. Hydro phn vng naphtene. Ct mch cc paraffin v mch nhnh alkyl. Ct vng naphten. Bo ha hydro cc lin kt khng no mi c to ra.
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: Hydro deankyl ho aromatic. Phn ng HDS, HDN. Phn ng cc ho.
Phn ng hydrocracking l phn ng ta nhit v t c s thay i th tch. Nhng n c tin hnh di p sut hydro rt cao vi mc ch l no ha cc sn phm, trnh s ngng t to thnh cc lm gim hot tnh xc tc. Hiu ng nhit trung bnh ca cc phn ng c trnh by bng di y.

Cc loi phn ng 1. Hydrocrracking - Parafin: RH + H2 R1H + R2H - Naphten: + H2 + RH 10-12 0.45-0.54 11-14 0.49-0.625 Nhit phn ng (trung bnh) Kcal/mol Kcal/H2
- Hydrocacbon thm: + H2 RH 2. Hydro ha - Olefin: CnH2n + H2 CnH2n+2 RHa + H2 naphten a. Dn xut cha S: - Mercaptan: R-SH + H2 RH + H2S - Thioete: R-S-R + H2 RH + H2S - Thiofen: 13.5-17 12.5-17 27-31 48-52 1.2-1.4 0.71-0.77 10-11
0.45-0.49
16.25-16.7 +H2 H2S + RH - Desunfua: R-S-S-R + H2 RH + H2S + RH b. Cc hp cht cha Nit: R-NH2 + H2 RH + NH3 19 14
Bng 1: Hiu ng nhit ca phn ng

T s liu ca bng trn ta thy, cc phn ng bo ha hydro thng l cc phn ng ta nhit nhiu hn so vi phn ng hydrocracking. Hiu ng nhit ca qu trnh vo khong 0.55 - 1 kcal/lit H2. Cc phn ng bo ha lin kt thng l cc phn ng ta nhit nhiu hn. Do l phn ng ta nhit, v vy qu trnh thch hp nhit thp. Nhng nu nhit qu thp th tc phn ng s gim, do nhit c xem nh l tc nhn duy tr hot tnh xc tc. Thng thng i vi ch hot ng nh th nhit ca qu trnh dao ng t 6500F - 8500F.
2.2: ng hc v tc phn ng.

S bin i c trng trong qu trnh phn ng va mang tnh ni tip, va mang tnh song song. Th t phn ng (tc phn ng) hon ton ph thuc vo bn cht ca hp cht vi nhng mc nng lng lin kt khc nhau, ph thuc vo hot ng ca xc tc c s dng v iu kin tin hnh qu trnh hydrocracking. Hiu sut cc i ca cc sn phm c ch c m bo bi s chn la xc tc ph hp, bng cch hn ch su bin i ca nguyn liu v tun hon phn nguyn liu cha b bin i. t c hiu qu bin i cao, xc tc ca qu trnh hydrocracking cn c kh nng thc y mnh qu trnh cracking c th m bo bin i c cc cu t kh chuyn ha nht ca nguyn liu. ng thi xc tc phi c kh nng izomer ho cao tng t l gia izo-parafin v n-parafin trong sn phm cui. Hn na xc tc hydrocracking cn phi c hot tnh hydro ha nht nh no ha cc phn t nh to ra trong qu trnh phn ng. Do vy gia chc nng cracking v chc nng hydro ha nn chn mt iu kin ti u nht phn ng cracking khng nn qu mnh, qu nhanh so vi s hydro ha cc sn phm ca cracking. Nu khng ngay trn b mt ca xc tc s xy ra s ct mch tip cc olefin to kh hay ngng t cc bm trn xc tc.
Tiu lun mn ch bin du 2.3: Xc tc cho qu trnh hydrocracking.

i nt v lich s pht trin: u tin xc tc c s dng l W/t st. Xc tc ny c hot tnh tt v s dng c hiu qu trong qu trnh hydro ha xng. Song c nhc im l rt nhanh b mt hot tnh khi c mt cc cht nit. Nm 1937 hng Esso ch to xc tc sunfit W/t st c b sung HF. Nm 1939 nhn c xng c kh nng chng kich n cao, chu u dung xc tc hai chc nng: Hydro ha v cracking (Fe/t st c b sung HF). Cho n ngy nay xc tc Ni, Pt, Pd mang trn aluminosilicat v nh hnh hoc oxyt nhm, zeolit l nhng xc tc rt ph bin. Cht xc tc s dng c chc nng acid c to ra bi thnh phn aluminosilicat, cn chc nng hydro ha c to ra bi cc kim loi. Cc trnh hydrocracking thng thng l tinh th aluminosilicat c mang cc kim loi t him. y l xc tc lng kim loi t him thng c s dng ch yu l Pt, Pd, Ni-Mo, Ni-W. Cc kim loi ny lm xc tc cho c hai qu trnh hydro ha v dehydro ha. Cc cht mang thng s dng l cc zeolite tinh th v aluminosilacat v nh hnh. 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 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, ammoniac s lm gim chc nng acid ca xc tc, chc nng hydro ha ca kim loi s b bin mt bi cc kim loai 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. Khi xc tc trng thi c nh th thng xy ra s ngng t cc v qu nhit cc b do vic to dng qua lp xc tc. Cn xc tc tng si c nhiu u im hn v mt truyn nhit v truyn khi.
Tiu lun mn ch bin du 2.4: Xc tc lng chc.

Nh bit xc tc cho qu trnh hydrocracking l h xc tc hai chc nng vi thnh phn xc tc bao gm cc tm hot ng axit, tm hot ng kim loi v cht xc tin. Tm hot ng acid: Ngy nay xc tc cho qu trinh thng s dng l zeolite: zeolite alumina silica, zeolite Y. Hu ht cc cng ngh gn y u x dng zeolit Y vi nhiu c tnh ni tri. Zeolit Y: Trong cu trc zeolit dng Y, c hnh bt din ct c sp xp theo tinh th kim cng. Mi nt mng ca zeolit Y u l cc bt din ct v mi bt din ct li lin kt vi 4 bt din ct khc 6 mt cnh thng qua lin kt cu oxy. S mt 6 cnh ca bt din ct l 10, do vy lun tn ti 4 mt, 6 cnh cn trng ca mi bt din ct trong zeolite Y. S t din SiO4 hoc AlO4 trong mi t bo c bn ca zeolite Y l 192 v s nguyn t oxy l 348 nguyn t. Cng thc ha hc ca mt t bo c s loi zeolite ny nh sau: Na56[(AlO2)86.(SiO2)136].260H2O T s Si/Al ca zeolit Y l 2. Vi ng knh ca zeolit Y l 12,7Ao

Tm hot ng kim loi: Chc nng kim loi c th nghim i vi cc kim loi nh Pt, Pd, Ni-Mo, NiW. Kim loi, oxit kim loi, sunfua kim loi, hoc mt s kt hp ca nhng hp cht ny c th cung cp chc nng kim loi ca cht xc tc. Yu cu quan trng cho chc nng kim loi l n phi kch hot cc hydro v l cht xc tc kh v hydro ha phn ng. Cc chc nng kim loi c s dng ph bin nht cho cc cht xc tc hydrocracking l s kt hp gia nhm kim loi VI A (Mo, W) v nhm VIII A (Co, Ni) sunfua. u im chnh ca s kt hp ny ca sulfua kim loi l n chu c lu hunh, tuy nhin, n ch hot ng mc va phi so vi Pd hoc Pt. S kt hp thuc nhm VI A v Nhm VIII A kim loi sulfide c c im ni bt hn trong phn ng hydrocracking. Nhm VIII A kim loi tr xc tc tng tc h tr vi nhm kim loi sunfua VI A to ra mt s gia tng ng k vo cc hot ng. Trong phn ng hydrocracking c hai phn ng chnh: phn ng cracking v phn ng hydro ha-dehydro ha. Phn ng cracking din ra trn tm acid trong khi phn ng hydro-dehydro ha din ra trn tm kim loi. Do xc tc hydrocracking phi l xc tc lng chc. Trong cc xc tc hydrocraking hin nay, phn ng hydrocracking c h tr bi cht mang c tnh acid nh alumina, alumina silicat v nh hnh, zeolite hoc hn hp ca cc cht mang ny. Hot tnh cracking ca ba cht mang ny c sp xp theo th t gim tnh acid: Zeolite > Alumina silicat v nh hnh > alumina chn lc phn on naptha cng theo th t ging nh trn. Do vi s quan trng ln v chn lc naptha ti u, ngi ta s s dng mt xc tc cha 80% thnh phn l zeolite. Ngoi ra tng hiu sut distillate th ta phi gim thnh phn zeolite xung. Vi cc xc tc chn lc distillate, thnh phn zeolite chim thnh phn rt thp, t 0-10% v n c trn ln vi cht mang chnh c thnh phn l alumina silicat v nh hnh v alumina. Ly 1 v d, xc tc thng mi alumina silicat v
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nh hnh c s dng cho qu trnh hydrocracking nghim ngt ti u sn phm distillate trung bnh hoc chuyn ha thnh du nhn. Cht mang Alumino silicat v nh hnh Zeolite ng dng Xc tc hydrocracking c chn lc phn ct Xc tc hydrocracking c bn cao Tnh acid Cao Rt cao
Bng 2: Cc cht mang thng s dng trong qu trnh hydrocracking Phn ng hydro-dehydro ha xy ra trn b mt cc kim loi qu nh platinum (Pt) hoc palladium (Pd) hoc cc kim loi thng thng khc nh vonfram (W) hoc molybdenum (Mo) vi cht xc tin l nickel (Ni). Xc tc hydrocracking c chc nng hydro ha tt s gip cho cht lng distillate tt hn, t kh sinh ra v n nh hn. Tuy nhin, chc nng cracking v hydro ha phi c cn bng v t l gia tm acid v tm kim loi phi c iu chnh sao cho c hot tnh v chn lc ti u. Hot tnh v chn lc l hai trong bn tiu ch nh gi phn ng hydrocracking: hot ha c tnh bng nhit cn thit t c sn phm mong mun. n nh, c tnh bng tc gia nhit gi c qu trnh chuyn ha mong mun. chn lc sn phm, c tnh bng kh nng xc tc cho phn ng to sn phm chnh. Cht lng sn phm, c tnh bng cc ch tiu cht lng nh nh git, chiu cao ngn la khng khi v ch s cetane.
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Mt xc tc hydrocracking c xem l hiu qu khi c s chuyn phn t cc nhanh gia tm kim loi v tm acid trnh cc phn ng khng mong mun xy ra. Vic chuyn phn t cc nhanh xy ra khi tm kim loi nm rt gn tm acid.
Bng 3: nh hng ca t l gia tm kim loi/tm acid vi phn ng hydrocracking. Cc xc tc kim loi qu nh platinum hoc palladium th c hot tnh cho phn ng hydro ha ln hn xc tc Ni/W v Ni/Mo. Mt s khc bit ln gia xc tc kim loi qu v xc tc kim loi thng thng l cc xc tc kim loi qu cn phi gi trng thi kh duy tr hot tnh xc tc v kim loi qu b u c khi c lu hunh trong . iu ny tri ngc vi cc xc tc kim loi thng v chng c hot ha dng mui sulfide. nng sulfur cao, xc tc kim loi thng thng khng b hao ht khi hot ng. Hin nay, hu ht cc quy trnh hydrocracking u s dng xc tc kim loi thng thng ch c mt s t nh my vn s dng xc tc kim loi qu v s dng xc tc kim loi qu c hot tnh cao nht v sn phm naptha c cht lng tt hn. tng thch vi xc tc kim loi qu, thit b hydrocracking c thit k c bit vn hnh trong mi trng khng c hp cht lu hunh hu c hoc H2S. Khng nhng
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phi loi b hu ht lu hunh trong nguyn liu m cn phi loi ht H2S trong kh tun hon. Tuy nhin k c khi thit b hydrocracking c thit k hot ng trong mi trng khng c acid, xc tc kim loi qu vn c th b u c bi cc hp cht lu hunh. iu ny dn n sn phm s c nng lu hunh cao hoc c nhiu H2S trong kh tun hon. Nu s dng xc tc kim loi thng thng, s nh hng ny s mc thp nht. Khi ta xc nh c vn th thit b c vn hnh bnh thng m khng gy hi cho xc tc kim loi thng. Tuy nhin, nu xc tc s dng l kim loi qu th s bin i nh c th u c cc tm kim loi v lm gim tui th xc tc. S hp ph lu hunh ca platinium c th l thun nghch hoc bt thun nghch. i khi, lu hunh c th c gii hp khi cho kh hydro nhit cao sc qua. Tuy nhin khi lu hunh lin kt cht vi kim loi, s hp ph l bt thun nghch. iu ny dn n gim hot tnh v tui th xc tc. Vic s dng xc tc kim loi thng c hot ha dng sulfide gip cho xc tc bn hn khi hot ng vi nguyn liu nng hn, hm lng lu hunh cao hn. Kim loi Co-Mo Ni-Mo ng dng chnh HDS HDN, hydrocracking HDN, hydrocracking Hydrocracking Kh nng hydro ha Trung bnh Cao Rt cao Cao nht
Ni-W Pd, Pt
Bng 4: Cc tm hot ng kim loi thng dng trong qu trnh hydrocracking Pd v Pt b u c bi lu hunh v ch c th s dng trong mi trng c nng H2S thp.
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Trong thit b hydrocracking xc tc tng c nh, xc tc ngoi kh nng gip cc phn ng mong mun xy ra th n cn phi c din tch b mt ln v bn vt l tt chng li s va p do tc ng ca dng nhin liu chy tc cao v do trng lng bn thn xc tc . Mt tng xc tc c th cha n vi trm tn xc tc. Phn ng ha hc xy ra cc l xp nh thng thy trn b mt xc tc. thu c phn on gas oil nng v gas oil nh th bn knh l xp xc tc phi t 75Ao n 85Ao. Vi bn knh l xp t 150Ao n 250Ao ta s thu c phn on cn residue.
2.5: C ch phn ng hydrocracking.

2.5.1: Chc nng ca xc tc.
Tm kim loi: To olefin hoc cyclo olefin qua phn ng dehydro ha Tnh Acid: To ion carbenium t olefin nh qu trnh chuyn proton. B gy ion carbenium Chuyn proton vo ion carbenium to thnh olefin Tm kim loi: No ha olefin nh phn ng hydro ha.
2.5.2: C ch phn ng trn xc tc.

S to thnh olefin: Phn ng din ra trn tm kim loi hot ng, to thnh olefin v kh hydro. Paraffin sau khi c isomer ha trn tm acid thnh i-paraffin, n s c hp ph ln tm kim loi. Ti y s din ra phn ng dehydro ha to thnh olefin.
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S to thnh ion tertiary carbenium: Phn ng din ra trn tm acid. Tm acid c 2 loi l acid Bronsted v acid Lewis. Olefin s tham gia phn ng vi tm acid ca xc tc to thnh ion carbenium.
Phn ng isomer ha v cracking: Cc ion carbenium thng thng c isomer ha thnh cc ion tertiary carbenium bn hn. Phn ng cracking ion carbenium din ra theo quy tc (ct mch v tr so vi carbon mang in tch).
Phn ng hydro ha olefin to thnh: Phn ng cracking s dng li khi ion carbenium loi b proton trn tm kim loi to thnh olefin v cc olefin to thnh tin hnh phn ng hydro ha trn tm kim loi thu c cc paraffin tng ng.
Phn ng cracking v hydro ha 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.
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Phn ng cracking s to ra v cung cp olefin cho qu trnh hydro ha v ngc li, phn ng hydro ha 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 isomer ha lun din ra ng hnh cng vi phn ng cracking. Trong qu trnh isomer ha xy ra trc, sau cc lin kt C-C s b b gy bi qu trnh cracking.
Hnh 1 : C ch phn ng Hydrocracking
2.6: Xc tc b mt hot tnh v ti sinh xc tc. 2.6.1: Xc tc b mt hot tnh.

S tch t cc: Cc hnh thnh l mt sn phm ph trong qu trinh cracking. Lp cc trn cht xc tc l mt hin tng nhit sau thi gian di tip xc hoc nhit phn ng cao hn nhit cht xc tc c th chu c, n lm gim chc nng hot ha ca xc tc. Qu trnh bt u vi hp ph mt lng cht cao phn t, qu trnh xy ra vi s mt mt tip theo ca mt hm lng hydro, kt qu l tch t cc. Lp cc ny c th
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bao quanh cc tm hot ng hoc ngn chn hay gy tc nghn cc l mao qun. Cc gy u c vnh vin. Cht xc tc c ngng hot ng do cc lng ng c th ti sinh tng i d dng. u c thun nghch Cht xc tc b u c ch yu l kt qu ca qu trnh hp th ha hc ca cc tp cht hot ng trn xc tc. Loi u c ny hi phc c khi tc nhn kh hot tnh c ly ra, tc ng chc nng dn o ngc. Trong mt s trng hp, nng cao nhit cht xc tc c th cn bng chc nng nh hng. Tuy nhin, nng cao nhit lm tng t l lng ng than cc. Mt v d ca qu tnh thun nghch u c l carbon monoxide m n c th lm gim cc phn ng hydro ha bng u tin ht bm ln cc tm hot ng. Mt v d khc l H2S nng trung bnh n nng cao c th lm gim t l kh lu hunh lin tc. Trong trng hp ny, vic loi b H2S t h thng ti ch kh gii quyt vn . S thiu kt ca cc thnh phn hydro Mt hnh thc phc hot tnh cht xc tc l s thiu kt ca cc thnh phn hydro ha ca cht xc tc. N c th c gy ra bi cc iu kin hot ha km cht xc tc, trong mt phn l s kt hp ca p sut cao mt phn l nc v nhit cao c th tn ti trong mt thi gian di. Ti sinh c th khi phc li cc hot tnh ban u ca cht xc tc. Cc kim loi tch t Tch t cc kim loi gy u c v xc tc khng th hon nguyn c. Cc kim loi c th i vo bn trong xc tc qua cc cht ph gia, chng hn nh cc hp cht silicon c s dng trong cc lm gim cht to bt, hoc cc cht gy nhim nguyn liu nh Pb, Fe, As, P, Na, Ca, Mg... hoc l cc hp cht hu c kim loi trong nguyn liu ch yu c cha Ni v V. S lng ng ca Ni v V din ra ti li vo cc tm hot ng hoc gn b mt ngoi ca cht xc tc, to ra mt lp "v" ngn xc tc tip xc vi nguyn liu. Kim loi lng ng c th gy hi tm acid, cc trung tm kim loi, hoc c hai.
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Cht xc tc h tr qu trnh thiu kt y l mt l do khc v s mt mt ca hot tnh cht xc tc v n cng l khng th phc hi c. iu ny cng l mt kt qu ca nhit cao v c bit l trong nc vi p sut ring phn cao. Trong trng hp ny, cht xc tc h tr cho nguyn liu c th b mt din tch b mt t mt s sp ca cc khe rng (bn trong xc tc), hoc t s gia tng ng knh cc khe rng v khi lng cn li khng i.
2.6.2: Ti sinh xc tc.

Cc thng c ti sinh bi qu trnh t chy trong mt dng oxy pha long hoc khng kh, mc d cc hn hp hi nc hoc hi nc-khng kh cng c s dng trong qu kh. Khi t, cc c chuyn i thnh CO2 v H2O. Trong trng hp khng c oxy d, CO cng c th hnh thnh. Ngoi tr cc cht xc tc kim loi qu, cc cht xc tc hydrocracking cha lu hunh, cc kim loi tn ti dng sulfua. Trong qu trnh ti sinh, lu hunh c to ra nh SO2. Nhn chung sunfua oxit pht thi nhit thp hn CO2. Ti sinh xc tc c th thc hin ti ch hoc chuyn v. Phn ln ca ti sinh cht xc tc trong thng mi c thc hin chuyn v v vn mi trng cng nh xc tc ti sinh tt hn. C mt s cng ty thc hin chuyn v ti sinh bng cch s dng thit b t chy cc khc nhau.
2.7: Cc yu t nh hng ti qu trnh.

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
2.7.1: 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.
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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.
2.7.2: 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 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. 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.
2.7.3: nh hng ca nguyn liu.

Xc tc hydrocracking phi lm vic vi nhiu nguyn liu khc nhau, trong c nhiu nguyn liu nng cha nhiu hydrocacbon cha phn t lng cao, cc hp cht lu hunh, nit hu c, oxit v kim loi khin cho qu trnh s kh khn hn, hot v tui th xc tc gim. Trong trng hp ch bin nguyn liu nng s hin hin ca asphanten v kim loi trong hp cht hu c c nh hng xu n hot xc tc.
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Chng 3: Cng ngh Hydrocracking

Mt s k hiu trong bi vit HDM: hydrodemetallization loi b metan bng hydro HDS: hydrodesunfurzation. Qa trnh Hydrocracking l qu trnh b gy mch c s tham gia ca hydro. La chn phng n x l cho qu trnh Hydro cracking ph thuc vo nguyn liu cng nh yu cu sn phm. Qu trnh ny c th minh ha n gin bng h thng 1 bc hoc 2 bc
Hnh 2: Qu trnh hydrocracking
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Qui trnh mt giai on c th c s dng sn xut xng nhng thng c s dng sn xut sn phm chng ct Qu trnh hai giai on c pht trin ch yu sn xut sn lng xng cao t du kh v giai on u tin c th thc s l mt bc lm sch loi b c cha lu hunh (cng nhcha nit) v vt liu hu c. Vi nhng loi nguyn liu khc nhau, ta c cc qu trnh Hydro cracking khc nhau, trong bao gm:
3.1: Asphaltenic Bottom Cracking Process ( ABC Process).

Asphaltenic Bottom Cracking Processc th c s dng sn xut sn phm chng ct (Bng 5), HDM, b gy asphaltene, v v HDS va phi, cng nh hn ch kh nng to than cc v lng ng kim loi s dng nguyn liu vi cht xc tc c nh
Bng 5: Thnh phn nguyn liu cho ABC Process
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Trong qu trnh ny, nguyn liu c bm ln n p sut phn ng v kt hp vi hydro. Hn hp ny c un nng n nhit phn ng trong l sau khi trao i nhit v a vo cc l phn ng. Trong l phn ng, HDM v cracking vi HDS trung bnh din ra ng thi trong iu kin tng t nh HDS nguyn liu nng. Kh thi l phn ng c lm lnh, lm sch,, trong khi cht lng tch ra c chng ct thnh phn chng ct chn khng v nguyn liu nng ltip tc phn tch bng loi b asphalt . Trong trng hp ca ABC v HDS kt hp, cht xc tc ABC t cao hn cc cht xc tc HDS v c th hot ng ti mt nhit cao hn so vi cc cht xc tc HDS di
3.2: H-Oil Process.

H-Oil Process (Speight, nm 2007; Speight v Ozum, 2002) l mt qu trnh xc tc c s dng mt mt giai on, hai giai on, hoc ba giai on l phn ng tng si trong , trong qu trnh phn ng, hydrocracking din ra ng k(hnh 5.2). Qu trnh ny c thit k cho hydro ha nguyn liu nng v nguyn liu cao khc trong mt l phn ng lp xc tc tng sig sn xut sn phm du m nng cp Qu trnh ny c th chuyn i tt c cc loi nguyn liu cho cc sn phm chng ct cng nh loi b lu hunh v loi b metan. Mt s thay i ca qu trnh H-oil process chuyn i sn phm chng ct si cao thnh sn phm chng ct trung bnh v du ha Mt lot cc ty chn qu trnh c th c s dng vi qu trnh H-oil ty thuc vo cc hot ng c th. Trong mi trng hp, mt h thng l phn ng tng si xc tc c s dng kh nng chuyn ha t hiu qu. H thng ny m bo phn b ng u ca cht lng kh hydro giu, v xc tc lun chuyn lin tc. Nhit phn ng c dng a dng nguyn liu ln nhit cn thit
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Hnh 3: Qu trnh H-oil Thng s dng nguyn liu s dng vi qu trnh
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Bng 6: Thnh phn nguyn liu ca H-Oil Process
3.3: Qu trnh hydrovisbreaking.

Bng cch thu hi , visbreaking l mt qu trnh tng i n gin,bao gm mt l si ln nguyn liu cho khong 450- 500o C ti mt p sut vn hnh khong 140 psi( 965 kPa). Thi gian phn ng trong l c gii hn mt cch cn thn. Nguyn liu vo l c duy tr p sut cao cho php b gy cc phn t ln nhng hn ch s hnh thnh than cc . T khu vc phn ng ,cht lng qu trnh c lm lnh ( ngui ) c ch thm s b gy vsau a vo mt ct chng ct tch thnh cc thnh phn . Qa trnh Visbreaking thng chuyn i khong 15% nguyn liu naphtha v du diesel du v sn xut nht thp hn nhin liu cn st li.
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Tm li, cc hydrovisbreakingprocess ( qu trnh HYCAR ) l mt qu trnh khng xc tc tin hnh trong iu kin tng t nh visbreaking( Chng 2). S hin din ca hydro dn n sn phm n nh hn hn sn phm c th thu c vi visbreaking ,c ngha l t chuyn i cao hn, to ra mt sn phm gim nht. Qu trnh HYCAR bao gm c bn ca ba phn: (i) (ii) (iii) visbreaking , HDM hydrocracking .
Trong visbreaking, nguyn liu nng l i tng b gy do nhit . Du visbroken c a vo l phn ng demetallization trongs c mt ca cht xc tc.. Cc sn phm t qu trnh th hai a n l phn ng hydrocracking , ni desulfurization v denitrogenation din ra cng vi hydrocracking .
3.4: Hyvahl-F Process.

Qu trnh ny c s dng hydrotreat kh quyn v chn khng dng nguyn liu nng chuyn i nguyn liu thnh naphtha v sn phm chng ct trung bnh Cc tnh nng chnh ca qu trnh ny l h thng cht xc tc kp ca n v c nh lp xc tc v khi nim l phn ng xoay. C hai h thng cht xc tc s dng ging c nh c hiu qu hn v khng tiu hao nng lng di chuyn xc tc . Thit k l xoay phn ng cho php thc hin phc hi , ti sinh xc tc, ng thi c th cho dng nguyn liu tip tc phn ng. Hn 50% kim loi c loi b t dng nguyn liu trong thit b ny Trong qu trnh ny, cc nguyn liu lm nng trc vo mt trong hai l phn ng, ni mt t l ln cc nickel v vanadium c hp th v chuyn ha cc thnh phn trng lng phn t ln bt u. Trong khi , l phn ng xc tc th hai di i mt qu trnh phc hi v sau c t ch ch. T cc l phn ng , cc nguyn liu chy qua mt lot cc l phn ng HDM v loi b hon ton cc kim loi v bt u chuyn i nguyn liu
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Giai on x l tip theo, HDS, l ni m hu ht lu hunh, mt s nit, v kim loi c loi b. Mt s lng hn ch ca chuyn i cng din ra. T l phn ng cui cng, pha kh c tch ra, hydro c ti tun hon phn ng, v cc sn phm lng c gi n mt phn phn on thng thng tch thnh naphtha, sn phm chng ct trung bnh, v dng nng hn.
3.5: IFP Hydrocracking Process.

Qu trnh ny c mt h thng hai cht xc tc: cht xc tc u tin l cht xc tc v nh hnh. N hot ng loi b lu hunh v nit v vng thm. Cht xc tc th 2 l zeolit kt thc s hydro ha v thc y s hydrocracking phn ng Trong qu trnh hai giai on, nguyn liu v hydro uc un nng v a n thit bi8j phn ng, s chuyn i cc sn phm din ra. Cc dng ra khi l phn ng uc lm lnh v phn tch, dng giu hydro uc nn v cho hi lu. Cht lng uc em i chng tip, thnh cc phn on, cac sn phm nh uc a n thng cha, cc sn phm c nhit si cao, uc a n l th 2, sau khi x l cho quay li hi lu Trong qu trnh mt giai on, cc dng t l phn ng trc tip n l th 2, tip theo l tch v cc phn on
3.6: LC-Fining Process.

LC-Fining proces l qu trnh hydrocracking x l lu hunh, metan v nng cp phn nguyn liu nngbng cch m rng lp phn ng. M rng din tch lp phn ng cho php ch bin nguyn liu nng, chng hn nguyn liu nng chng kh quyn, nguyn liu nng chng chn khng, du hoc nha ung. L phn ng uc lm vic iu kin gn ng nhit, v nhit phn ng uc hp th bi cc dng nguyn liu lnh ngay lp tc uc trn u vo l phn ng Trong qu trnh ny nguyn liu v hydro c un nng ring bit v sau ln trong l phn ng hydrocracking qua mt lp m rng ca cht xc tc Sn phm l phn ng chy vo thp tch nhit cao p sut cao. Hi nc thi t phn tch c cho xung bi p lc v sau i n trao i nhit v sau n mt phn dnh cho
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vic loi b cc sn phm ngng t, v thanh lc. Cht lng gim p lc v ti chs bng ra. y l mt phn quan trng nht ca qu trnh chuyn i
Hnh 7: LC-Fining process Cht lng hi lu c iu chnh theo khong si thch hp quay li l phn ng. Bng cch ny, nng y l phn ng,v vic phn phi cc sn phm, c th c kim sot. sau khi tch.. Cc sn phm t pha trn ca thp ra i tip n phn on chng ct v phn nng uc x ra y.Thi gian phan ng ti cc l phn ng c iu chnh cung cp cc mc chuyn imong mun . Cc ht cht xc tc lin tc rt khil phn ng, ti sinh v ti s dng vo l phn ng, trong c kh nng linh hot x l mt lot cc nguyn liu nng nhkh quyn v cn chng chn khng, cht lng c ngun gc than , vbitum. Thnh phn dng nguyn liu v sn phm ca qu trnh uc th hin bng dui
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Bng 8: Thnh phn v nguyn liu ca qu trnh LC-Fining
3.7: Uniflex Process.

Qu trnh Uniflex (trc y l qu trnh hydrocracking CANMET) ph hp chuyn i du nng, du siu trng, nha ng , nguyn liu nng chng kh quyn, v nguyn liu nng chn khng , s dng cht ph gia c ch s hnh thnh than cc, t c chuyn i ca hydrocarbon im si cao vo sn phm nh hn. Dng lng v kh hi lu uc gia nhit trong thit b ring bit, vi lu lung dng kh nh v 1 lung va xc tc trong thit b un nng. Dng ra t hai thit b ny uc a xung y ca l phn ng Dng ra uc a qua thit b phn tch, phn nh uc a quay li hi lu vo thp phn ng, phn y uc dn ra thp chng, thu uc cc sn phm nh xng, diesel, VGO, v phn cn nng
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Trung tm ca qu trnh l l phn ng hot ng nhit 815-880 F, p sut 2000 psi Qu trnh Uniflex s dng mt c quyn, kch thc nano xc tc rn c pha trn vi thc n ti a ha chuyn i ca cc thnh phn nng v c ch s hnh thnh than cc. Yu cu cht xc tc c th ph thuc vo cht lng nguyn liu v mc sn phm yu cu. Cht xc tc l hai chc nng, vi chc nng chnh ca n l thc hin phn ng hydro nh cho s n nh ca sn phm khi b gy trong khi cng hn ch s bo ha ca vng thm.
Hnh 8: Uniflex Process
3.8: Veba- Combi-Cracking Proces.

Qa trnh Veba-Combi Cracking l mt qu trnh hydrcacking nhit .qu trnh hydro ha chuyn i nguyn liu nng . Qa trnh da trn nn tng ca cng ngh
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BErgiusPier, s dng cho hydro ha than c ti nm 1945. Dng nguyn liu nng uc hydro ha s dng xc tc thung mi v pha lng dro trong l phan ng nhit 440-485 C v p sut 2175-4350 psi.Dng sn phm t thp phn ng uc a n thp tch nng nhit thp hn nhit l phn ng. Tip tc uc dn vo thp chng chn khng. Nhit cao, p sut cao cng vi yu cu cung cp Hydro l mt vn ln v kinh t Vi qu trnh ny , dng nguyn liu nng uc to huyn ph vi mt lung nh ca ph gia dng bt vi hydro v kh hi lu truc khi uc gia nhit. Phn ng oc iu chnh ch d upflow . Trong sut qu trnh phn ng, chuyn ha lun t > 95%. Nhit phn ng uc iu chnh bi dng kh hi lu Dng t thp phn ng uc a n thp tch nng, y kh v lng uc tch . 1 thp chng chn khng uc s dng tch nt dng y ca thp tch nng Phn nh thp tch nng, cng vi phn hi lu thp chng ct,i vo l phn ng hydro kh, nhit phn ny uc iu chnh nh phn phn ng hydro lng, v cha lp xc tc thung mi cho qu trnh hydrotreating. Nhit phn ny khang 340-420 C Qa trnh ny khng ph hp vi 1 s lung ln nguyn liu nng
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Tiu lun mn ch bin du Ti liu tham kho

1: L Vn Hiu, Cng Ngh Ch Bin Du M, H Ni, 2006. 2: James Speight, Heavy and Extra-heavy Oil, 2013.
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Quá trình hydrocracking là quá trình có lợi nhuận cao trong nhà máy lọc dầu

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Quá trình hydrocracking là quá trình có lợi nhuận cao trong nhà máy lọc dầu

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Chng 1: Gii thiu qu trnh hydrocracking

1.2: Nguyn liu.

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Chng 2: Qu trnh hydrocracking

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Bng 1: Hiu ng nhit ca phn ng

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2.2: ng hc v tc phn ng.

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2.5: C ch phn ng hydrocracking.

2.5.2: C ch phn ng trn xc tc.

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Hnh 1 : C ch phn ng Hydrocracking

2.6: Xc tc b mt hot tnh v ti sinh xc tc. 2.6.1: Xc tc b mt hot tnh.

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2.6.2: Ti sinh xc tc.

2.7: Cc yu t nh hng ti qu trnh.

2.7.1: nh hng ca nhit .

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2.7.2: nh hng ca p sut v lng hydro s dng.

2.7.3: nh hng ca nguyn liu.

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Chng 3: Cng ngh Hydrocracking

Hnh 2: Qu trnh hydrocracking

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3.1: Asphaltenic Bottom Cracking Process ( ABC Process).

Bng 5: Thnh phn nguyn liu cho ABC Process

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3.2: H-Oil Process.

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Hnh 3: Qu trnh H-oil Thng s dng nguyn liu s dng vi qu trnh

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Bng 6: Thnh phn nguyn liu ca H-Oil Process