I. GI I THI U CHUNG I.1.

1. Khi ni m Qu trnh hydro ha cng nh qu trnh hydro ha c bit t rt lu, c ng dng nhiu trong cc qu trnh Lc - Ha du. C th nh ngha qu trnh hydro ha, hydro ha nh sau: Qu trnh chuyn ha m trong c s tch nguyn t H ra khi hp cht hu c c gi l qu trnh hydro ha. Qu trnh chuyn ha m trong c s tc dng ca phn t H 2 c gi l qu trnh hydro ha. Mt s c im: Phn ng hydro ha c th tin hnh trong pha lng cng nh trong pha rn. V d: Hydro ha du thc vt thnh m tin hnh trong pha lng . Hydro ha nitryl thnh amin tin hnh trong pha hi: R CN + 2H 2 R CH 2 - CH 2 Mt s qu trnh tin hnh ngay trong thit b cao p 200 o C, p sut 50 bar. Hydro l cht kh to gii hn n vi khng kh 4% v 74% th tch, do vy cn phng v ngn nga kh nng ny. I.2. ng d ng I.2.1. ng d ng trong lnh v c Ha d u Trong cng nghip ha du, qu trnh hydro ha c ng dng tng hp cht hot ng b mt, tng hp cc monome c gi tr nh Butadien_1,3; styren; formaldehyd; aceton; anilin...; cn qu trnh hydro ha th c ng dng chnh trong lnh vc Lc du.

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I.2.2. Qu trnh hydro ha Mt cch s b theo phm vi ng dng, c th chia qu trnh hydro ha thnh 3 qu trnh sau: X l bng H 2 Mc ch: Lm mm nhm n nh cc sn phm du m . Loi b tp cht ca cc sn phm du m nh S, N, O, halogen, vt kim loi...

Bo ha cc hydrocacbon thm Mc ch: Nng cp du nhin liu: tng ch s x etan, gim nht, tng ch s nht... Ci thin nguyn liu cho qu trnh Cracking xc tc: vng khng no thnh vng no. V d:

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 Hydrocracking. Mc ch : nhm ch bin nguyn liu l cc phn on du lng bt k thnh sn phm l kh hydrocacbon, xng, kerosen, diesel hoc nguyn liu 400 o C); p sut cao (50 200 at) v xc tc lng chc Pt, Ni../ Al 2 O 3 , zeolit.. trong :

Pt, Ni... : chc kh thc hin cc phn ng hydro ha . Al 2 O 3 , zeolit... : chc acid thc hin cc phn ng cracking .

I.2.3. Q u trnh hydro ha Trong cng ngh Lc du, qu trnh hydro ha ch yu c ng dng trong qu trnh Reforming xc tc thu xng c hm lng hydrocacbon thm cao, tc l xng c ch s octan cao.Phn ng dehydro ha thng c ng dng trong cc qu trnh sau: Kh hydro ca ru, sn xut c andehit v xeton. Kh H 2 ca etyl benzen, sn xut styren (xc tc oxit). Kh hydro ca parafin, n xut butadien (xc tc oxit). Hydro ha lm sch du nh hydrodesunfua, hydrodenito. Hydro ha du bo thnh du m, qu trnh c ng dng rng ri trong cng ngip. V d: C 17 H 33 COOH Axit oleic Hydro ha hp cht nitril thnh amin: R-CN hp t si: CN(CH 2 ) 4 -CN NH 2 -(CH 2 ) 6 -NH 2 Ngy nay, qu trnh hydro ha cn s dng lm sn phm du m, nh hydro ha lm sch du nhn, hydro ha kh hydrocacbon thm nhm gim lng cc cht ny trong nhin liu phn lc , nhin liu izen. c bit trong bi cnh bo v mi trng, cc tiu chun v nhin liu
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I.2.4. M t s ng dng khc trong cng nghip

C 17 H 35 COOH axit stearic

RCH 2 NH 2

Phn ng ny cn dng iu ch diamin, l bn nguyn liu cho tng

ngy cng c tht cht th qu trnh hydro ha nhm kh benzen c trong xng l mt trong nhng phng php lm gim benzen xung cn di 1%, p ng tiu chun ASTM.Qa trnh kh aromatic thng c thc hin 370-400 0 C vi p sut hydro l Psi (10,3MPa). II. CC NGUN CUNG CP HYDRO 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. II.1. Ngun hydro t Reforming Ngun hydro s dng cho cc qu trnh hydrotreatingch yu c cung cp t qu trnh Reforming, vi qu trnh reforming lin 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. II.2. Ngun Hydro t jhis 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

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II.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. Sn phm hydro thu c t qu trnh ny c tinhkhit khong 90 n 95%. II.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. III. XC TC C th phn thnh 3 nhm xc tc chnh: 1.Cc kim loi thuc nhm VIII (Fe, Co, Ni, Pt, Pd) v nhm Ib (Cu, Ag) v cc hp kim ca chng. 2.Cc oxyt kim loi: MgO, ZnO, Cr2O3, Fe2O3... 3.Cc oxyt phc hay sulfid (sulfua): CuO.Cr2O3, ZnO.Cr2O3, CoO.MoO3, NiO.WO3, WS2(y l xc tc ra i rt sm, c hot tnh cao nhng d mt hot tnh nn hin nay t dng). Cc xc tc ny c bit l xc tc kim loi thng c phn b trn cc cht mang xp v b sung vo l cc cht kch ng nh l kim loi khc, oxyt khc.

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Ngy nay, trong cc qu trnh hydroprocessing, ngi ta thng s dng xc tc kim loi. C hai dng thng c s dng nh sau: Xc tc Co- Mo l loi xc tc rt tt cho qu trnh Hydrodesunhua v n nh cc olefin, n c u im hot ng ch mm v t tiu tn nhin Hydro. Xc tc Ni- Mo l loi xc tc c hot tnh rt cao i vi cc phn ng

Hydrodenitro v n nh cc hp cht aromaric. IV. HA HC CA QU TRNH HYDROTREATING C ch ch yu ca cc qu trnh hydrotreating l s dng lng hydro b gy 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. IV.1. Qa trnh loi Lu hunh (Hydrodesunfua) Kh lu hunh xy ra thng qua vic chuyn i sang H2S ca cc hp cht lu hunh hu c c trong nguyn liu. Lu hunh c tm thy trong sut khong si cc phn phn on du kh di hnh thc hng trm hp cht lu hunh hu c khc nhau, c th phn loi v mt trong su loi lu hunh sau y: mercaptan, sulfide, di-sulfide, thiophenes, benzo-thiophenes, v di-benzo-thiophenes. Phn ng c trng cho tng loi hp cht lu hunh c hin th di y.

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Di y l mt bng xp hng ca su loi lu hunh xp hng trn c s d dng loi b: D dng nht loi b kh khn nht loi b: Mercaptan Sunphua Disunphua Thiophenes Benzo-thiophenes Dibenzo-thiophenes IV.2. Qa trnh loi b Nit (Hydrodnitro) Nit c trong du th vi hm lng nh hn lu hunh 5 20 ln. Tc hi: - C kh nng lm mt hot tnh ca xc tc mt cch nhanh chng (Nit s trung ha cc tm axt ca xc tc). Cc hp cht ca nit c kh nng to mu v nha trong qua trnh tn tr v s dng. 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. Nit c loi tr ra khi nguyn liu bng cch chuyn n thnh dng NH3 di tc dng ca hydro. R N + 2H2 RH + NH3

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IV.3. Qu trnh loi b Oxy (Hydrodeoxygen) Qu trnh hydrodeoxygen l qu trnh tch loi oxy 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

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nhiu hydro. Lng hydro cn cho qu trnh hydrodeoxygen gp khong hai ln so vi qu trnh hydrodesunfua.

Bo ha olefin Olefin khng c tm thy trong du kh, nhng c hnh thnh t cc qu trnh ch bin du. Ni chung, phn on c cha olefin l khng n nh v do phi c bo v khi tip xc vi oxy trc khi x l bng hydro ngn chn s hnh thnh ca polymer. iu c bit ng i vi cc nguyn liu c ngun gc t cracking nhit nh than cc v sn xut ethylene. Phn ng bo ha olefin in hnh c hin th di y:

Phn ng bo ha olefin rt nhanh v ta nhit rt ln. Nu khng quan tm

ng mc, trong qu trnh hot ng n c th dn n cc vn c kh nh cc qu mc dn n s sp p hoc phn b dng chy cht lng ngho thng qua cc lp cht xc tc (s). Diolefins c th d dng hydro ha olefin nhit thp (<400F, hoc t hn khong 200C).

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Bo ha Aromat Bo ha aromat ci thin cc tnh cht ca sn phm du m v d im Cht thm c tm thy trong khong si ca naphtha c mt, hai, v ba vng

khi, ch s ng c diesel, vv. thm, thng c gi l mono, di, v tri. Phn ng in hnh c hin th di y:

IV.4. Loi b kim loi (Demetallation) Chng c mt nh cc hp cht hu c kim loi. Cc kim loi thng xy ra nht l asen t ngun du th, thy ngn t

condensates nht nh v silicon t tc nhn chng to bt c s dng trong visbreakers v cokers. Cc hp cht ny phn hy trong cc hydrotreater v cc kim loi c lng R-Me + H2S R-H2 + MES Sau khi lng ng, cc kim loi ny gp phn vo vic v hiu ha cht xc tc Demetallation nguyn liu l mt mc tiu quan trng ca ch bin v cht xc v khng ging nh than cc n khng c loi b bng cch ti sinh. tc demetallation c bit c s dng cho mc ch . ng trn cc cht xc tc di dng ca sunfua kim loi nh hnh di y.

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Demetallation xy ra trc khi kh lu hunh v bt k cc qu trnh chuyn

i ca cc nguyn liu s din ra. IV.5. Loi b Halogen Halogenua hu c, chng hn nh clorua hoc bromua, c th c mt trong phn du mc vi lng. Trong iu kin ca qu trnh Hydrotreating, halogen hu c ch yu chuyn i sang cc hydrocarbon tng ng v hydro halogen. Phn ng in hnh c hin th bn di.

V. CC I U KI N CNG NGH V.1. Nhi t Ph n ng hydro ha: l ph n ng to nhi t thu n l i nhi t th p t = 100 350, 400 0 C. Ph n ng hydro ha: l ph n ng thu nhi t thu n l i nhi t cao t = 200 600, 650 0 C. nhi t th p th ng x y ra hydro ha lin k t khng no m ch h . Nhi t cao lm cho qu trnh chuy n ha su hn v s x y ra hydro ha lin k t i trong vng benzen ho c nhm ch c. V.2. Kh nng h p ph xc tc Ng i ta th y r ng cc xc tc kim lo i nh Pt, Pd, Ni khng c kh nng ho t ha cc phn t phn c c v nhm ch c, v v y cc xeton khng no, axit h u c, d n xu t hydrocacbon thm hydrocacbon c hydro ha lin k t C=C v gi nguyn nhm ch c phn c c. V d :

+ H2
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Mt khc cc xc tc oxit li c kh nng hp ph cc nhm chc v vy trn xc tc ny s xy ra hydro ha vi s bo ton lin kt C=C. v d: xc tc oxit H2O V.3. Th i gian ti p xc i v i qu trnh hydro ha: + chuy n ha: trn 90%. + Th i gian ti p xc: t ph n trm pht n vi gi . i v i qu trnh dehydro ha do tnh thu n ngh ch cao nn: + chuy n ha: 20-40%. + Th i gian ti p xc: t ph n trm giy n vi giy. V.4. p su t Ph n ng hydro ha v dehydro ha ph thu c r t nhi u vo p su t. Dehydro ha l qu trnh tng th tch nn p su t th p s t o i u ki n cho chuyn ha tng. Cn hydro ha l ph n ng gi m th tch, ln ph i ti n hnh p su t cao hn v nhit th p t 100-350 o C. Ph n ng hydro ha v dehydro ha ph thu c r t nhi u vo p su t( v l ph n ng gi m p su t v tng th tch), iu ch ra hnh XI.1 v XI.2.

R CH= CH COH +2H2

R- CH=CH-CH2OH

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Dehydro ha l qu trnh tng th tch nn p su t s t o i u ki n cho chuy n ha tng. Cn hydro ha l ph n ng gi m th tch, ln ph i ti n hnh p su t cao hn v nhit th p t 100350 o C ( hnh XI.2). Trong cng nghi p ngi ta th ng ti n hnh ph n ng P=1,55 kg/cm 2 , T o =300400 o C. V i ph n ng hydro ha, m t y u t khc tng cng chuyn ha l d H 2 . V d : C 6 H 6 + 3H 2 C 6 H 12 N u t s mol l 1:3 th =95,7%; n u t s mol l 1:10 th =99,5%. V.5. L ng tu n hon Hydro Lng 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 hon ny c ngha quan trng i vi cc nguyn liu distillat nng cha nhiu resin v asphalten.

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VI.

S CNG NGH

M t s qu trnh tiu bi u trong nh my l c d u: Chng ta c th so snh m c nghim ng t c a cc qu trnh hydrotreating d a vo bi u sau:

Hnh 1: M c nghim ng t c a cc qu trnh hydrotreating

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VI.1. Naphtha hydrotreating

H2 makeup

H2 Rycycle Compres sor

100 F, 50 psig

H2 Purge H C
2 2

Gas H2, H2S,C2H6,C3H to Saturate Gas Plant H2S C2H6

8

Hydrotreating Reactor 700 F, 200psig

0

C3H8
Sour Water Stripper

Furnace

Naphtha Feed

Desulfurized Product
Hnh 2: S 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 c dn ti thit b stripping loi ht cc phn nh cn li, H2S v nc chua ra khi sn phm. iu kin phn ng hydrotreating naphta l khong 700oF v 200 psig, 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 50-250scf/bbl, v qu trnh ny phi cn n t 70-100scf/bbl tch ht 1% lu hunh ra khi sn phm.
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VI.2. Distillate ( light and heavy) hydrotreating H u h t cc phn on distillate u ch a lu hunh, v th c n ph i lo i chng ra m b o yu c u v ch t l ng s n ph m. Ngoi ra qu trnh ny cn gip n nh cc h p ch t olefin nng cao ch s cetan c a diesel.

H2 makeup H2 Rycycle Compressor

100 F, 50 psig

H2 Purge H2 C2H6 C3H8

Gas H2, H2S,C2H6,C H H2S C2H6 C3H8 Sour Water

Hydrotreating Reactor 800 F, 300psig Furnace Light DistillateFeed

0

Stripper

Desulfurized Product

Hnh 3: S Distillate ( light and heavy) hydrotreating Cc qu trnh hydrotreating cc phn o n distillate nh (Kerosen, jet fuel) tiu t n nhi u hydro hn so v i qu trnh hydrotreating naphta. i u ki n th c hi n cc ph n ng ny kho ng 600-800 o F, 300psig ho c cao hn. L ng hydro tu n hon kho ng 2000scf/bbl v tiu th kho ng 100400scf/bbl. i u ki n ph n ng ph thu c ch y u vo tnh ch t c a nh p li u v tnh nghim ng t c a cng ngh . VI.3. Gas oil hydrotreating Nh p li u cho qu trnh cracking xc tc (gas oil kh quy n, gas oil nh chn khng, gas oil thu t qu trnh deasphalt) th yu c u ph i x l r t nghim ng t nh m m c ch loi lu hunh, m vng thm, tch cc kim lo i.
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Xc tc Ni- Mo c xem nh xc tc ch y u v hi u qu nh t c s d ng cho qu trnh hydrotreating.

H2 makeup
Rycycle Compress H2

100 F, 50 psig

H2 Purge C2H6, C3H8

1200 psig
Hydrotreating Reactor #1

1200 psig
Hydrotreating Reactor #2

Gas H2, H2S, C2H6, C3H8, C3H6 to Catalytic Sour Wate r Stripper

Furnace

Heavy Distillate Feed

Hnh 3: S Gas oil hydrotreating

Desulfurized Product to Catalytic

Bnh ph n ng th ng c hai l p, do qu trnh ph n ng cc ph n ng hydro ha t a nhi t r t l n v c n ph i c b sung hydro v lm ngu i trung gian. Bnh tch p su t cao c nhi m v tch v tu n hon hydro, cn bnh tch p su t th p c nhi m v phn tch ph n nh . Nhi t lc ban u kho ng 650 o F, nhi t ny p su t hydro ring ph n s gip n nh v th c hi n qu trnh tch lu hunh ra kh i cc h p ch t d i d ng H 2 S.

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