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Hydrodesunfurization (HDS)hay Hydrotreating l qu trnh xc tc ha hc ph bin s dng tch hn hp lu huznh t cc sn phm du m tinh ch ging nh xng du ,nhin liu my bay

ay phn lc ,xng,nhin liu diezen,nhin liu du. Mt mc ch loi b lu huznh l gim lng kh thi sulfur dioxide do s dng nhng nhin liu trong xe t, my bay, u my xe la, tu, hoc cc nh my in t du, l dn c v cng nghip, v cc hnh thc ca qu trnh t chy nhin liu. Mt l do quan trng loi b lu huznh t cc sn phm trung gian sui naphtha trong mt nh my lc du l lu huznh, thm ch nng rt thp, cht c cc cht xc tc kim loi qu{ platinumand rheni trong cc n v xc tc reforming m sau c s dng nng cp ca dng naphtha Hydro ha cc hp cht lu huznh kt qu trong vic hnh thnh khng mong mun, c kh hydrogen sulfide. Cc qu trnh hydrodesulfurization cng nghip bao gm c s vt cht cho vic lu gi v loi b cc kh hydrogen sulfide. Trong cc nh my lc du m, kh hydrogen sulfide c ri sau chuyn i thnh sn phm ph lu huznh. Trong thc t, phn ln cc 68.000.000 tn lu huznh c sn xut trn ton th gii trong nm 2010 l lu huznh sn phm ph t du m tinh ch v nh my ch bin kh t nhin.

Mc lc 1 Lch s 2 Cc qu trnh ha hc 2.1 Cc cht xc tc 3 Quy trnh m t 4 hp cht lu huznh trong nh my lc du HDS nguyn liu 5 ng dng khc 5.1 Hydrodenitrification 5.2 bo ha cc olefin 5.3 Hydro trong ngnh cng nghip thc phm 5.4 Ti liu tham kho

Mc d phn ng lin quan n hydro xc tc ca cc cht hu c c bit n trc khi nm 1897, c tnh ca niken chia nh xc tc c nh ca hydro trn hydrocarbon lin kt i (v d, nh trong etylen v benzene) c pht hin bi nh ha hc ngi Php, Paul Sabatier. ng pht hin ra rng hydrocarbon khng bo ha trong giai on hi c th c chuyn i thnh cc hydrocacbon bo ha bng cch s dng hydro v mt kim loi xc tc. Cng vic ca ng l nn tng ca qu trnh hydro xc tc hin i. Ngay sau khi lm vic Sabatier, mt nh ha hc ngi c, Wilhelm Normann, thy rng hydro xc tc c th c s dng chuyn i khng bo ha glixerit trong pha lng thnh cc hp cht bo ha. ng c trao bng sng ch ti c vo nm 1902 v Anh vo nm 1903, l khi u ca nhng g by gi l mt ngnh cng nghip trn ton th gii.

Vo gia nm 1950, cc kim loi qu xc tc qu trnh reforming u tin (qu trnh platformer) c thng mi ha. ng thi, cc hydrodesulfurization xc tc ca cc ngun cp d liu naphtha cc phan xng reformng nh vy cng c thng mi ha. Trong nhng thp k sau , qu trnh hydrodesulfurization xc tc c quyn khc nhau nh mt trong nhng m t trong qu trnh s s di y c thng mi ha. Hin nay, hu nh tt c cc nh my lc du trn ton th gii c mt hoc nhiu n v HDS. n nm 2006, thu nh cc n v HDS c pht trin x l nhin liu my bay phn lc sn xut nguyn liu sch tng hp hydro cho pin nhin liu. n nm 2007, iu ny c tch hp vo mt h thng pin nhin liu hot ng nh. Ha hc qu trnh Hydro l mt loi phn ng ha hc c kt qu trong vic b sung hydro. Qu trnh thy phn l mt loi hydro c kt qu trong phn ct ca lin kt CX ha hc, trong C l mt nguyn t cacbon v X l lu huznh, nit v oxy nguyn t. Kt qu ca mt phn ng thy phn l s hnh thnh ca CH v HX lin kt ha hc. Do , hydrodesulfurization l mt phn ng thy phn. S dng ethanethiol (C2H5SH), mt mn qu hp cht lu huznh trong mt s dng lc du, nh mt v d, phn ng hydrodesulfurization c th c th hin nh: Ethanethiol + Hydrogen Etan + Hydrogen Sulfide C2H5SH + H2 C2H6 + H2 S

cht xc tc C Nhiu kim loi xc tc phn ng HDS, nhng n l nhng kim loi gia ca dng kim loi chuyn tip hot ng nht. Ruteni disulfide (RuS2) dng nh l cht xc tc tch cc nht, nhng kt hp nh phn ca coban v molypden cng rt nng ng.

Trong thc t, hu ht cc n v HDS trong nh my lc du s dng cht xc tc da trn disulfide molypden coban bin i (MoS2) cng vi mt lng nh cc kim loi khc. Bn cnh nhng MoS2 cht xc tc, niken v vonfram cng c s dng, ty theo tnh cht c np vo. V d, nickel-wolfram (Ni-W) cht xc tc c hiu qu hn cho hydrodenitrification (HDN) m cng mong mun trong nhiu n v HDS. Kim loi sulfua c h tr trn cc vt liu vi din tch b mt cao. Mt in hnh h tr cho HDS cht xc tc l nhm. S h tr cho php cc cht xc tc t tin hn c phn phi rng ri hn, dn n mt phn ln hn ca MoS2 l xc tc hot ng. m t qu trnh Trong mt n v hydrodesulfurization cng nghip, chng hn nh trong mt nh my lc du, phn ng hydrodesulfurization din ra trong mt l phn ng c nh nm nhit cao t 300 n 400 C v p sut cao khc nhau, 30-130 bu kh quyn ca p sut tuyt i, in hnh l trong cc s hin din ca mt cht xc tc bao gm mt c s tm coban v molypden. Hnh nh di y l mt m t s cc thit b v quy trnh dng chy trong mt nh my lc in hnh HDS n v:

Ngun cp d liu lng ( pha di bn tri trong biu ) c bm ln n p sut cao yu cu v c s tham gia ca mt dng kh giu hydro ti ch . Hn hp lng kh kt qu c lm nng trc bi chy qua b trao i nhit. Ngun cp d liu nng trc sau chy qua l si t nhin liu m ngun cp d liu l hon ton bc hi v un nng n nhit cao cn thit trc khi vo l phn ng v chy qua mt chic ging c nh ca cht xc tc m phn ng hydrodesulfurization din ra. Cc sn phm phn ng nng c lm mt bng mt phn chy qua b trao i nhit ni ngun cp d liu l phn ng c lm nng trc v sau chy qua b trao i nhit lm mt bng nc trc khi n chy qua b iu khin p sut (PC) v tri qua mt p lc gim xung khong 3-5 bu kh quyn. Kt qu l

hn hp ca cht lng v kh i vo bnh tch kh ti khong 35 C v 3-5 bu kh quyn ca p sut tuyt i. Hu ht cc kh giu hydro t bnh tch kh gas ti ch m c nh tuyn thng qua mt contactor amin loiai5 b cc sn phm phn ng c cha kh hydrogen sulfide (H2S). Kh hydro giu H2S min ph sau c ti ch li ti s dng trong phn l phn ng. Bt kz kh d tha t cc bnh tch kh tham gia kh chua (tc l kh c cha H2S) t l striping sn phm phn ng .. Cht lng t cc bnh tch kh c chuyn qua mt thp chng ct stripper reboiled. Sn phm y t thp stripper l sn phm lng desulfurized cui cng t cc n v hydrodesulfurization. Kh chua trn nh thp cc stripper c cha hydro, metan, etan, hydrogen sulfide, propane v c l mt s butan v cc thnh phn nng hn (v d, cc thnh phn trng lng phn t cao hn). l kh chua c gi n nh my ch bin kh trung tm ca nh my lc du loi b cc sunfua hydro trong chnh amin kh n v x l ca nh my lc v thng qua mt lot cc thp chng ct thu hi propan, butan v pentan hoc cc thnh phn nng hn. Hydro cn li, methane, ethane v propane mt s c s dng nh nhin liu kh nh my lc du. Sunfua hydro loi b v thu hi cc n v x l{ kh amin sau c chuyn thnh lu huznh trong mt n v qu trnh Claus. Lu { rng cc m t trn gi nh rng cc ngun cp d liu n v HDS khng cha olefin. Nu ngun cp d liu c cha olefin (v d, ngun cp d liu l mt naphtha c ngun gc t mt nh my lc du cracker xc tc (FCC) n v), sau kh trn nh t cc stripper HDS cng c th cha mt s ethene, propene, butenes v pentenes hoc olfins nng Cng cn lu rng cc gii php amin n v i t kh contactor ti ch n t v c tr li cho chnh kh amin ca nh my lc x l{ n v. Cc hp cht u unh trong nh my lc du HDS nguyn liu Nh my lc du HDS nguyn liu (naphtha, du ha, du diesel v du nng) c cha mt lot cc hp cht lu huznh hu c, bao gm thiol, thiophenes, sulfide

hu c v disunphua, v nhiu th khc. Cc hp cht lu huznh hu c l sn phm ca s suy thoi ca lu huznh trong s hnh thnh t nhin ca du th du kh. Khi qu trnh HDS c s dng desulfurize mt nh my lc du naphtha, n l cn thit loi b cc tng lu huznh xung n phn triu phm vi hoc thp hn ngn nga nhim c cc cht xc tc kim loi qu trong cc xc tc reforming tip theo ca naphthas. Khi qu trnh ny c s dng kh lu huznh cc loi du diesel, cc quy nh mi trng mi nht ti Hoa Kz, Chu u v cc ni khc u quyn cho nhng g c gi l ng c diesel lu huznh cc thp (ULSD) yu cu hydrodesulfurization rt su. Trong u nhng nm 2000, cc gii hn quy nh ca chnh ph cho ng cao tc xe ng c diesel c trong phm vi t 300 n 500 ppm theo trng lng ca tng s lu huznh. n nm 2006, tng hn mc lu huznh cho ng cao tc ng c diesel l trong khong t 15 n 30 ppm theo trng lng. cc ng dng khc Phn ng thy phn c bn c mt s ng dng khc hn hydrodesulfurization. Hydrodenitrification

Phn ng thy phn cng c s dng lm gim hm lng nit ca mt dng du kh v, trong trng hp , c gi l Hydrodenitrification (HDN). n quy trnh cng ngh cng ging nh cho mt n v HDS. Trong thc t, cc n v c th c thit k cho c hydrodesulfurization v hydrodenitrification, v nhiu ngi c thit k nh vy. S dng pyridin (C5H5N), mt hp cht nit c trong mt s sn phm chng ct phn on du m, l mt v d, phn ng hydrodenitrification c mc nhin cng nhn nh xy ra trong ba bc sau: Pyridine + Hydrogen Piperdine + Hydrogen Amylene + Hydrogen Pentane + Ammonia C5H5N + 5H2 C5H12 + NH3 C5H11N + 2H2 C5H11NH2 + H2

v phn ng tng th c th c th hin nh: Pyridine + Hydrogen Pentane + Ammonia C5H5N + 5H2 C5H12 + NH3

bo ha ca olefin Phn ng thy phn cng c th c s dng bo ha hoc chuyn i olefin (anken) vo parafin (ankan). Qu trnh s dng cng ging nh cho mt n v HDS. V d, s bo ha ca cc olefin, pentene, c th c th hin nh] Pentene + Hydrogen Pentane C5H10 + H2 C5H12

Mt s n v thy phn trong nh my lc du hay nh my ha du c th c s dng ch duy nht cho s bo ha ca olefin hoc h c th c s dng ng thi kh lu huznh cng nh olefin kh Nit v bo ha mt mc . Hydro trong cng nghip thc phm Ngnh cng nghip thc phm s dng hydro hon ton hoc mt phn bo ha cc axit bo khng bo ha trong du thc vt lng v cc loi du chuyn i chng thnh cht bo rn hoc na rn, chng hn nh trong b thc vt v rt ngn. ti liu tham kho J.H. Gary and G.E. Handwerk (1984), Petroleum Refining Technology and Economics, 2nd Edition, Marcel Dekker, ISBN 0-8247-7150-8. W.L. Leffler (1985), Petroleum Refining for the Nontechnical Person, 2nd Edition, PennWell Books, ISBN 0-87814-280-0. Sulfur (January 2011), from the website of the U.S. Geological Survey (USGS). Comptes Rendus de l'Acadmie des Sciences (C.R.Acad.Sci), 1897, 132, 210.

Process for Converting Unsaturated Fatty Acids or their Glycerides into Saturated Compounds. British Patent: GB 190301515 (A), November 26, 1903, granted to Wilhelm Normann. Microchannel Device for De-Sulfuring Military-Grade Fuel, March 2006.

Federal Ultra Low Sulfur Highway Diesel, Final Rule, last updated on August 10, 2006. R.R. Chianelli, G. Berhault, P. Raybaud, S. Kasztelan, J. Hafner and H. Toulhoatf (March 8, 2002), Periodic trends in hydrodesulfurization: in support of the Sabatier principle, Applied Catalysis A: General, Vol. 227, Issue 1-2, pp. 83-96.

Kinetics and Interactions of the Simultaneous Catalytic Hydrodenitrogenation of Pyridine and Hydrodesulfurization of Thiophene, John A. Wilkens (August 1977), PhD Thesis, Massachusetts Institute of Technology (MIT).

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