Chng I: VI NT V CNG NGH CH BIN DU M 1.1 GII THIU CHUNG V DU M Du m l mt hn hp phc tp gm hng trm cu t khc nhau.

Mi loi du m c trng bi thnh phn ring, song v c bn chng u cha cc Hydrocabon l thnh phn chnh, chi ng lng trong du cn li l cc cht cha xi, lu hunh, nit, cc phc kim loi. Trong du m cn cha cc kh tr nh- He, Ar Nhn chung du m cng cha nhiu Hydrocabon v cng t cc thnh phn d nguyn t th cht lng cng tt v l loi du c gi tr cao. Hydrocabon l thnh phn chnh ca du m, chng c chia thnh cc nhm: parafin, naphten, aromat, hn hp naphen-arcomat. Hydrocabon thm thng gp l loi mt vng v ng ng ca chng (benzen, toluen, xyren) cc cht ny thng nm trong phn nh l cu t lm tng kh nng chng kch n ca xng. Du m mun ng dng c th phi tin hnh phn chia thnh tng phn on. Du m khai thc ln t cc m du trong lng t l mt cht lng c snh s dng c. Trong hn hp du th ly t m du ln c cha nc, mui khong v cc tp cht khc. Trc lc em du th vo chng luyn ngi ta phi tin hnh tch nc, mui khong v cc tp cht khc. Qu trnh chng luyn trc tip phn chia du th thnh tng cc phn on nh c khong nhit si hp hn. u tin khi khai thc du c s gim p nn phn on kh c tch ra thng t C 1 n C 4 . Ngoi ra cn mt lng t C 5 , C 6 bay theo. Sau tu thuc vo gii hn nhit si m ta thu c cc phn on sau: - Phn on xng: nhit nh hn 180 0 C bao gm cc thnh phn t C 5 n C 10 , C 11 . - Phn on Kerosen: nhit si t a cc thnh phn t C 16 n C 20 , C 21 Phn on Gudron vi nhit si trn 500 0 C gm cc thnh phn c s nguyn t Carbon t C 41 tr ln Cc phn on trn c ng dng trong nhiu mc ch khc nhau nhng ch yu c dng lm nhin liu cc sn phm ho hc. 1.2. XNG V CC PHNG PHP NNG CAO CHT LNG XNG Vi khong nhit si hn 180 0 C, phn on xng bao gm cc Hydrocabon t C 5 n C 10 , C 11 . C ba loi Hydrocabon Parafin, naphtenic, aromatic u c mt trong phn on xng. Tuy nhin thnh phn, s lng cc Hydrocabon rt khc nhau, ph thuc vo ngun gc du th ban u. Chng hn t h du parafinic ta thu c xng c cha parafin. Cn t du naphtenic ta thu c xng c nhiu cu t vng no. Ngoi Hydrocabon, trong phn on xng cn cha hp cht S, N 2 v O 2 . Mt trong nhng tnh cht quan trng nht ca xng l phi c kh nng chng li kch n. c trng gi l tr s octan. Tr s octan c o bng phn trm th tch ca izooctan (2,2,4 - trimetyl pentan) trong hn hp chun vi n - heptan (n C 7 H 16 ) tng ng vi kh nng chng kch n ca nhin liu iu kin tiu chun. S dng thang chia t - heptan c tr s octan bng 0, cn izootan c quy c bng 100. C hai phng php xc nh tr s octan: - Phng php nghin cu (RON): s vng quay ca mt th nghim l 600 vng/pht. - Phng php mt (MON): s vng quay ca mt th l 900 vng/pht. Thng th tr s octan tnh theo RON thng cao hn tnh theo MON. Mc chnh lch phn nh: mt mc no tnh cht ca nhin liu thay i khi ch lm vic ca ng c thay i. Cho nn mc chnh lch

cn gi l nhy ca nhin liu i vi ch lm vic thay ica ng c. Mc chnh lch gia MON v RON cng thp cng tt. Mi loi xng khc nhau c kh nng chng kch n cng khc nhau. Cc hydrocarbon phn t nh nh- parafin mch nhnh, cc aromat ch chy c khi im ho ngha l loi ny c kh nng chng kch n tt. Cc n - parafin d dng chy ngay c khi mt la cha truyn ti gy ra s chy kch n. Kh nng chng kch n ca cc Hydrocarbon c sp xp theo th t gim dn: Hydrocarbon thm > Olefin mch nhnh > parafin nhnh > naphten c nhnh > olefin mch thng > naphten > parafin mch thng > parafin mch thng ln. 1. Cc phng php nghin cu cht lng xng Phn on xng ly trc tip du m c rt t izoparafin do tr s octan thp (kho u v tr s octan ca xng ng c phi ln hn 10. iu c ngha l xng ly trc tip t chng ct du th khng dng c cho ng c m ta phi s dng cc phng php ch bin ho hc, l hc bin i thnh phn ca xng nhm thu c xng c tr s octan cao tho mn yu cu v k thut ca ng c chy bng xng. Mt s phng php ph bin a. Phng php ph gia Mc ch ca phng php ny l dng mt ho cht cho vo xng nhm hn ch qu trnh oxi ho ca cc hydrocarbon khng gian trc bung la khi chy trong ng c. C hai nhm ph gia: + Ph gia ch: bao gm cc cht nh- tetrametyl ch (TML), tetraetyl ch (TEL) c tc dng ph hu cc tp cht trung gian hot ng do gim kh nng chng kch n dn n tr s octan ca xng tng ln. + Ph gia khng ch: ch l mt ph gia khi cho vo xng lm tng tr s octan ln nht (t 6 n 12 n v octan) nhng nu dng xng c pha ch th lng ch trong khi thi ca cc ng c chy bng xng (xe my, t) nh hng rt xu ti mi trng v ch l mt cht gy ng c i vi con ngi. Chnh v s c hi ca xng pha ch m hin nay nhiu quc gia trn th gii trong c Vit Nam khuyn khch mi ngi s dng xng khng ch (unlead petrol). C mt s gii php hu hiu t ti tr s octan cao hn khi khng s dng ch: - Pha trn xng c tr s octan cao (nhxng alkyl ho, izome ho) vi nhin liu c tr s octan thp. - Nng cp v a thm cc thit b lc du sn xut hn hp xng c tr s octan cao. - S dng cc cht ph gia khng cha ch nh- cc hp cht cha oxi: etanol, MTBE, TAME b. Phng php ho hc Bin php tng tr s octan ca xng bng vic s dng ph gia ch l bin php tm thi. Gii php lu di l phi tm cch ch bin ho hc mi kinh t nht tng hiu sut ca xng. Nguyn tc chung ca cc phng php ho hc l chuyn ho cc hydrocarbon mch thng thnh mch nhnh hoc thnh hydrocarbon vng no, vng thm c tr s octan cao hn. Cc phng php ho hc c bn - Cracking nhit: l qu trnh phn hu di tc dng ca nhit thc hin iu kin nhit t t guyn liu cho qu trnh cracking nhit l phn on xng nng n cn, ch yu hay dng l gasoil v cn. Sn phm ca qu trnh ny l xng cracking nhit chim hm lng ln hydrocarbon thm v olefin hn so vi xng chng ct trc tip. Tr s octan nm trong khong gia ch c th tng s octan cao hn xng thu c t chng ct trc tip nhng vi tr s octan nh- vy cha p ng c yu cu cht lng ca xng ng c. t i hi xng c tr s octan t

t hydrocarbon olefin nn xng cracking nhit c n nh ho hc km nn di tc dng ca nh sng, nhit oxi s b ngng t, oxi ho v trng hp to thnh nha nht l i vi s c mt ca olefin cha 2 ni i. S c mt ca nha v polyme to thnh trong xng lm cho xng cracking nhit d to mui trong ng c khi lm vic. iu ny nh hng khng tt ti my. Hm lng lu hunh trong xng cracking nhit c th cha t ng lng, cao hn g n so vi hm lng lu hunh cho php theo quy chun ca xng ng c. Lu hunh tn ti trong xng dng H 25 v Mecaptan. Lm sch xng cracking nhit khi H 25 thng s dng kim ra. Ni chung xng cracking nhit khng m bo cht lng cho yu cu ca xng t v hiu sut t khng cao nn cc qu trnh cracking xc tc, hydro cracking, reforming xc tc pht trin v thay th qu trnh ny. Cc qu trnh ny va m bo cht lng va m bo tng hiu sut xng p ng yu cu ngy cng kht khe ca xng. Ngoi sn phm l xng th qu trnh cracking nhit cn thu c cc kh nh CH 4 , C 2 H 6 , C 3 H 8 v cc sn phm lng gasoil. - Cracking xc tc Trong cng ngh ch bin du m; cc qu trnh c mt xc tc ng mt vai tr quan trng. Lng du m ch bin bng cracking xc tc chim tng i ln. Nm 1965 lng du m th gii ch bin c 1500 tn/ngy th cracking xc tc chim 800 tn (tc 53%). Qu trnh cracking xc tc c xem l mt qu trnh ch yu sn xut xng t. Nguyn liu l phn on xng Kerosen - xola ca qu trnh chng ct trc tip, phn on gascoil ca qu trnh ch bin th cp, phn on gasoil nng c nhit si t n phm chnh ca qu trnh cracking xc tc l xng cracking xc tc, hiu sut xng cracking xc tc thng dao ng trong khong t 30 lng nguyn liu em cracking. Hiu sut v cht lng xng ph thuc vo cht lng nguyn liu, xc tc v ch cng ngh. c trng ca xng cracking xc tc + T tr s n ho h i l naphten v izoparafin. tng tr s octan ca xng cracking xc tc ngi ta c th pha thm ph gia ch (TEL). Xng dng cho my bay pha thm c ch cho 1 kg xng v tr s . Tuy nhin pha thm ch ch c li v mt k thut nhng li c hi v mt mi trng. Ni chung xng cracking xc tc mc d c tr s octan cao nhng vn cha p ng c v yu cu k thut ca xng ng c. - Qu trnh alkyl ho alkan Qu trnh ny cng nhm to ra xng c tr s octan cao. Bn cht ca qu trnh ny l a thm gc R vo phn t cht hu c. Xng thu c t qu trnh alkyl ho (hay cn gi l qu trnh alkylat) c cha rt t olefin v hydrocarbon thm, thnh phn ch yu l izo - alkan (izooctan). Thng s dng xng alkylat pha vo xng khc nhm nng cao cht lng ca xng. - Qu trnh Reforming xc tc y l qu trnh quan trng nht trong cc nh my ch bin du m hin i. Mc ch ca qu trnh ny l thu c xng c tr s octan rt n xut cc loi hydrocarbon thm (benzen, tuluen, xyren) lm nguyn liu cho cng ngh ho du. Ngoi ra ta cn thu c kh H 2 l ngun thu nhiu v r ti n so vi cc phng php khc. Trong cc mc ch trn th mc ch tng tr s octan ca xng l ht sc quan trng. Chng hn nh- khi tng tr s octan ca xng t 66 ln 88 th chi ph ca xng cho mt nm gim i

22%, s t yu cu thc hin mt cng vic gim i 12%. Qu trnh Reforming xc tc cho ta sn phm xng c tr s octan rt cao. Xng Reforming xc tc thng c dng pha vi cc xng khc nng cao cht lng ca xng. 1.3 VAI TR CA QU TRNH REFORMING V CRACKING TRONG CNG NGH CH BIN DU M Nh- ta bit du m khai thc c t cc m du khng trc tip s dng c. Mun s dng c cc sn phm trong du m th ta phi ch bin chng bng nhiu cng on khc nhau. du m sau khi khai thc ln s c tch nc mui v chng ct trc tip thu c cc phn on c nhit si khc nhau. Cc phn on ny s c bin i tip nh nhng qu trnh ch bin du m to ra cc sn phm p ng yu cu k thut. Trong cc qu trnh ch bin du m th Reforming v cracking l 2 qu trnh quan trng nht. Reforming xc tc l mt trong nhng qu trnh quan trng ca cng nghip ch bin du m. Vai tr ca qu trnh ny khng ngng c tng ln do nhu cu v xng c cht lng xng v nguyn liu cho tng hp ho du ngy mt nhiu. Qu trnh ny cho php sn xut ra cc cu t c tr s octan cao cho xng, cc hp cht hydrocarbon thm (B, T, X) cho tp hp ho du v ho hc. Ngoi ra qu trnh cn cho php nhn c kh hydro k thut (hm lng H 2 ti 85%) vi gi r nht so vi cc qu trnh iu ch H 2 khc. Sn phm hydro nhn c t qu trnh Reforming xc tc cung cp cho cc qu trnh lm sch nguyn liu, x l hydro cc phn on sn phm trong khu lin hp lc ho du. Qu trnh Reforming thng dng nguyn liu l phn on xng c tr s octan thp, khng tiu chun i vi nhin liu xng cho ng c. l xng ca qu trnh chng ct trc tip du th, hay t phn on xng cracking nhit, cc ho V ngha tng tr s octan ca xng ca qu trnh Reforming xc tc c th theo di s tng t l gia cc cng sut ca cc h thng Reforming xc tc vi cng sut h thng chng ct trc tip M. Bng 1 Nm T l cng sut cc h thng Reforming xc tc vi chng ct trc tip (%) Tr s octan ca xng (theo phng php nghin cu) Tr s octan trung bnh ca xng thnh phm Loi thng Loi c bit 1955 16 90 98 92,4 1960 18 92 99 94,0 1965 19 93 99,5 95,0 1970 22 94 100 96,5 Song song vi qu trnh Reforming xc tc l qu trnh cracking m c bit l cracking xc tc. N chim mt v tr tng i quan trng trong ngnh cng nghip ch bin du m. Lng du m c ch bin bng qu trnh cracking xc tc chim tng i ln so vi tng lng du c ch bin. V d nh- M tng s lng du m ch bin vo thng 1/1965 l 1500tn/ngy th h thng cracking xc tc chim ti 800tn/ngy tc 53%. Mc ch ca qu trnh cracking xc tc l bin i cc phn on du m c nhit si cao (c trng lng phn t ln) to thnh cc cu t xng c cht lng cao. Ngoi ra cn thu thm c 1 s sn phm khc nh- gasoil nh, gasoil nng, kh bo (kh hydrocarbon cu trc nhnh). Tm li ni n ngnh cng nghip ch bin du m hin i khng th khng k n qu trnh Reforming v cracking. y l 2 qu trnh c