Chng 7.

Ph gia nhin liu Hoa Hu Thu

Nhin liu du kh NXB i hc quc gia H Ni 2007. Tr 107 120. T kho: Ph gia nhin liu, nhin liu sch, ph gia cho xng, ph gia chng kch n, ph gia ty ra, ph gia chng c. Ti liu trong Th vin in t H Khoa hc T nhin c th c s dng cho mc ch hc tp v nghin cu c nhn. Nghim cm mi hnh thc sao chp, in n phc v cc mc ch khc nu khng c s chp thun ca nh xut bn v tc gi.

Mc lc
Chng 7 PH GIA NHIN LIU ...................................................................................2 7.1 Phn loi cc loi ph gia nhin liu........................................................................2 7.1.1 Cc ph gia ty ra v chng ng c............................................................2 7.1.2 Cht ph gia tng cng chy rt................................................................2 7.1.3 Cc ph gia km hm oxi ho, n mn v lo ha ............................................2 7.1.4 Ph gia khng ch pht thi, khi v gip s chy ......................................3 7.1.5 Cc ph gia chng kch n ...............................................................................3 7.1.6 Cc ph gia chng tch in, dit khun, mu v ph gia nh ho....................3 7.2 Ph gia cho xng .....................................................................................................3 7.3 Nhin liu sch........................................................................................................4 PH LC 1........................................................................................................................7 PH LC 2........................................................................................................................9

Chng 7 PH GIA NHIN LIU

7.1 Phn loi cc loi ph gia nhin liu

7.1.1 Cc ph gia ty ra v chng ng c

a) b) c) d) e) f) Cht ty ra cacbuarat a chc nng, nh: Polioxipropylen este v trimetylen iamin naphtenat. Ankylaryl photphat este v N-oleiyl-1,3-propileniamin. Cc mu i photphat este amin... b) Cht ty ra cacbuarat: cc cacbamat, ur mt ln th, poliamin... Cht ph gia chng ng c: hexylen glycol, polihiroxiancol + cc amin bo, polihiroxyancol + N-(phenylsteryl)-1,3-propileniamin. Cc cht ty ra trn c s PBSA: Cc hn hp vi mu i amin ca axit sunfonic v poliete... Cc hn hp vi glycol v ete glycol... Tc nhn ty ra khng tro: ankyl nitroamin, ankyl hiroxylamin. Cc tc nhn ty ra s hnh thnh tro: Este sucxinat - mu i kim loi. Este ca glixerin.

7.1.2 Cht ph gia tng cng chy rt

- Polime trn c s etylen. - ng polime este vinyl. - Cc polime v ng polime khc.

7.1.3 Cc ph gia km hm oxi ho, n mn v lo ha

a) b) c) 2 Km hm oxi ho: dn xut aminoguanidin, cc hp cht isoindoline, tetraxianoetylen. Tc nhn n nh nhit: ter-polime: etylen - propilen - ien + Cc aryl - photphat. Tc nhn km hm n mn:

d)

bis-(1,3-ankylamino)-2-propanol v cc dn xut arylphotphat. Cc amin bo v amin. Tc nhn chng lo ho: iete ca ietylen glycol.

7.1.4 Ph gia khng ch pht thi, khi v gip s chy

a) Khng ch khi: 2-Etylhexamat kim loi. BaCO3 + imetylete ca etylen glycol. 4,4-benzylien (bis-(2,6-iterbutyl phenol). amylphenol bi-poliankoxi ho.

b) Khng ch pht thi v gip s chy:

7.1.5 Cc ph gia chng kch n

Tetraetyl ch. Tetrametyl ch. Cc hp cht khc ca ch. Cc ph gia khng cha kim loi. Cc ph gia c cha oxi trong phn t (cc hp cht oxigenat).

7.1.6 Cc ph gia chng tch in, dit khun, mu v ph gia nh ho

a) Ph gia chng tch in: mu i photphat ca poliamit v naphtenat kim loi. b) Ph gia dit khun: Cc imin vng, naphtanyl imidazolin, ... c) Cht mu: cht mu xanh, cc hp cht azo, ... d) Nhin liu c nh ho: S nh ho bng kim loi. Nhin liu cacbon.

7.2

Ph gia cho xng

Trong cc ph gia ca xng th cc ph gia chng kch n l quan trng nht. Trc y, trn th gii ngi ta thng dng cc hp cht c ch nh tetraetyl ch, tetrametyl ch hay hn hp etylmetyl ch v nhiu hp cht c kim khc. Do tnh c hi ca cc kh thi ng c cha ch nn hin nay xu hng dng xng khng ch pht trin mnh. Cc ph gia dng lm tng ch s octan ca xng khng ch l: Metanol, CH3OH. 3

Etanol, C2H5OH. Tec-butyl ancol, (CH3)3C-OH. Metyl tec-butyl ete, MTBE. Tec-amyl metyl ete, TAME.

Ph gia ph bin nht cho xng khng ch hin nay l MTBE. Tng sn lng MTBE trn th gii hin nay vo khong 17 18.106 tn. Khong 95% sn lng MTBE c dng lm ph gia cho xng. Ngoi ra MTBE cn c dng diu ch iso-buten tinh khit theo phn ng sau: (CH3)3C-O-CH3 xc tc

(CH3)2C=CH2 + CH3OH

Ngoi ph gia chng kch n, trong xng cn c thm cc ph gia khc nh: Ph gia chng oxi ho, n mn. Ph gia ty ra. Ph gia khng ch pht kh thi v khi. Cc phm mu.

Vit Nam n gia nm 2001 loi b ht cc xng c ch v dng xng khng ch cho cc ng c xng. Do MTBE c tc ng khng tt ln sc khe cng ng, xu hng hin nay, ngi ta thay MTBE bng ancol etilic. Ancol etilic v ang tr thnh ph gia l tng cho xng ng c. c bit, trong nhng nm gn y, ngi ta dng ancol etilic lm nhin liu cho my bay cnh qut trong ngnh nng nghip Braxin.

7.3

Nhin liu sch

Trn th gii hin nay, cc lut v mi trng t ra yu cu bt buc phi sn xut nhin liu sch hn. V th, cc nh my lc du ang phi chu nhiu p lc t th trng v cc quy tc mi trng ca cc quc gia. Ni chung, cc quy tc mi trng i vi nhin liu u yu cu cc sn phm du phi gii hn hm lng lu hunh v thnh phn xng sao cho khi pht thi h thp c hm lng SOx, NOx, CO, CO2 v c bit phi h thp hm lng cc ht rn x thi vo mi trng. Nhng yu cu ny l bt buc v lm thay i hn hp sn phm du v cht lng sn phm. Cc quy tc cho nhin liu sch. Mc d cc quy tc v nhin liu sch vn cha c p dng trn ton th gii, nhng cc quy tc nhin liu sch hin nay thng p dng cho 2 lo i nhin liu c tiu th nhiu nht, l xng v du iezen. Cc yu cu c th l lm gi m hm lng lu hu nh n thp nht, gi m hm lng aromat, c bit l benzen, gi m hm lng olefin, cc cht d bay hi v cc dn xut cha oxi ca cc hirocacbon. V d, cc tiu chun ca M v hm lng lu hunh trong xng i vi cc nh my l c du n i a, xng nhp khu v cc nh my l c du t nhn nh sau:

Hn p dng Cc nh my lc du t nhn, hm lng lu hunh trung bnh, ppm Cc nh my thuc cc tp on ln, hm lng lu hunh trung bnh, ppm Xng nhp ni, 1 galon, hm lng lu hunh trung bnh, ppm

1/1/2004 120 300

1/1/2005 30 90 300

1/1/2006 30 80

Cc tiu chun lu hunh cho du DO ca M i vi cc nh my lc du ni a, DO nhp khu v nh my lc du t nhn n 1/1/2006 l 15ppm cho 1 galon, ch s xetan t i thiu l 40, ti a 35% aromat theo th tch. Cc tiu chun Chu u i vi xng nh sau:
Nm Hm lng lu hunh, ppm Hm lng aromat, % th tch Hm lng benzen, % th tch 2000 150 45 1 2005 50 35 ~

Tiu chun Chu u i vi du iezen:

Nm Hm lng lu hunh, ppm Hm lng aromat a vng, % th tch Ch s xetan ti thiu 2000 300 11 51 2005 50 ~ ~

Chnh v th cc nh my lin hp lc ha du ang tn ti v sp xy mi u phi cp nht cc phng php cng ngh mi tha mn cc yu cu ny. Hu ht cc xng c hm lng lu hunh thp ngy nay u c sn xut t crackinh FCC naphta. t c hm lng lu hunh di 30 ppm trong hn hp xng, cc nh my lc du phi tp trung vo x l hoc nguyn liu u cho FCC, hoc l crackinh ngay phn on naphta. Nh vy, trong cng ngh xng, cn c cng on v thit b x l bng hiro nguyn liu u cho FCC. T c th la chn cc bin php cng ngh: Kt hp x l nguyn liu u bng hiro vi x l naphta ca FCC (hu x l). Tng cng thit b tin x l vi hirocrackinh du dng (khng c hu x l). Ch dng hu x l (x l lm sch).

Di y gii thiu mt s cng ngh hu x l i vi naphta FCC.

Cng ngh X l bng hiro Nh cung cp Nhiu cng ty Tnh trng thng mi lu hnh x Th nghim ang pht trin

thng thng Exxon Scanfining IFP Prime G X l hiro chn lc Exxon Octgain 125 Exxon Octgain 220 UOP ISAL Chng ct xc tc Hp ph Ankyl ha olefin CD Tech Phillips S Zorb SRT BP OATS Mobil Mobil x x x x Mobil x x x x

Vi cc phng php k trn, hm lng lu hunh trong xng t c < 10 ppm. Cc yu t nh hng n hm l ng lu hu nh trong xng FCC g m: Nguyn liu u (ngun du th, phn on du, ...) Cc iu kin ca qu trnh FCC Tnh cht xc tc ca qu trnh FCC S dng cc ph gia cho xc tc FCC nh ZSM-5.

Ni chung cc xc tc c lng axit cao (mt tm axit cao), lc axit mnh thun li cho phn ng truyn hiro, trng thi oxi ha ca kim loi trn b mt zeolit v c bit l ZSM-5 c tc dng lm gim hm lng lu hunh trong xng. ZSM-5 c tc dng b gy chn lc olefin khng cha lu hunh.

PH LC PH LC 1 Cc n v o lng ca Anh hay gp trong lnh vc nhin liu

1 inch = 2,54 cm Chiu di 1 foot = 1 ft = 12 inches = 30,48 cm 1 yard = 91,44 cm Din tch 1 inch vung = 6,4516 cm 1 inch khi =16,39 ml Th tch 1 foot khi = 28,320 cm = 28,32 lt 1 gallon (M) = 4550 cm (4,55 lt) 1 pound = 1 lb = 0,454 kg Khi lng 1 poad = 10 poa = 1000 centipoad 1 oz = 28,35 gram 1 Grain = 0,065 gam 1 BTU =
3 3 2

Nng lng

ca 1 pound nc t 320F ln 212F. 1 BTU = 1055 J = 252,0 cal 1 stock (st) = 10 m /s

4 2

1 180

nhit lng cn thit nng nhit

Cc n v khc

Bng chuyn i nhit

Loi nhit C C F R K

1,8 (C) + 32

1,8 (C) + 491,7

C + 273,2

F 32 1,8 R 491,7 1,8

K 273,2

F + 459,7

F 459,7 1,8 R 1,8

1

R K

F 459,7 1,8 (K) 459,7

1 1,8 K

+ o nhit

Ni chung c 4 thang nhit khc nhau vn c s dng ty tng quc gia, a phng l: 7

(1) Thang Fahrenheit (2) Thang Rankine (3) Thang Bch phn (4) Thang Kenvin (thang nhit tuyt i) * Thang Fahrenheit ly nhit si ca nc l 212F Nhit nng chy ca nc l 32F * Thang Centigrade ly nhit si ca nc = 100C Nhit nng chy ca nc l 0C * Thang Rankine ly nhit si ca nc = 672R Nhit nng chy ca nc l 492R * Thang Kenvin ly 0K (tuyt i) ti 273,1C. Ti nhit ny chuyn ng phn t b ngng li. ** M c 2 thang hay dng trong i sng hng ngy: Thang Farenheit c s dng thng thng trong i sng. Thang Rankine c dng bi cc k s.

Thang nhit C v K dng cho khoa hc.

+ Cch chuyn i (xem bng trn hoc bin i nh di y):

* Cng thc chuyn i t thang Farenheit sang thang C: F = 32 + * Cc thang khc: C =

5 (F 32) 9 9 C = 32 + 1,8 C 5

K = C + 273,2 * chuy n thang Fahrenheit sang thang Kenvin th ng i ta chuy n: F R C C K K

PH LC 2 ng cong chng ct ca sn phm du lng nh ngha: ng cong chng ct ca mt hn hp lng l ng cong biu th s thay i ca nhit theo phn trm distillat ly ra khi hn hp. i vi cc sn phm du l ng ngi ta thng quan tm cc im 10, 50 v 90%.

Hnh 25. Thit b chng ct xc nh ng cong TBP

Trong lnh vc nhin liu, xc nh c cc im trn ngi ta tin hnh chng ct phn on du th hay mt sn phm du l ng. Trong qu trnh chng ct ngi ta cho dng sn phm chy lin tc thnh cc phn on. Cc phn on thu c (distillat) trc tip t du th, ni chung khng c tt c cc c trng cn thit c th c coi l cc nhin liu hon thin. 9

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Vic chng ct c thc hin trn 1 my trong phng th nghim (hnh 25) v thit lp chnh xc ng cong chng ct ca du th. ng cong ny c tn l T.B.P (True Boiling Point). Thit b chng ct c trnh by nh hnh trn: gm mt hnh cu bng thu tinh c t nng bng bp in. Ngi ta lp vo pha trn bnh mt ct phn on v c bc v cch nhit. H thng lm lnh c ngng t bng nc v ta thu cc phn on (distillat) trong mt bnh c chia . My c th c n i vi mt thit b chn khng ct di p sut thp. Cho 1 lt du th hay mt sn phm du l ng vo trong bnh cu, cm nhit k u ct ct theo di qu trnh sn phm i ra kh i ct. Nu i tng chng ct l du th, khi bt u t nng, s si bt u v nhit k ch 30C, hi bc ln qua sinh hn nhng khng b ngng t, hi ny c cha mt hm lng nh propan. Di y gii thiu cc sn phm thu c qua php chng ct chn lc trn thit b ny.
Kh ho lng: Ti nhit ny metan, etan v phn ln propan b lo i v hi cng cha butan. Nu mu n thu propan v butan nhit thng ngi ta phi tin hnh nn p sut cao. Thng thng iu ny c thc hin trong cng nghip, sn phm thu c g i l LPG.

Mt khc, nhng c trng sau y cng c n nh vi hn hp C3 v C4 dng cho t: Thnh phn: > 19% v < 50% theo th tch C3H8 v C3H6 p sut hi tng i 50C: 7,3 < p < 11,5 at

Nhng c trng ny tng i rng tng ng vi cc hn hp kh kh d dng xc nh c vi cc thit b tch n gin. Nu mun tch n-C4H10 ra khi iso-C4H10 phi dng cc thit b mnh hn v gi thnh s cao hn. Di y l cc c trng ca kh ho lng.
Quy nh Propan thng mi: Hn hp cc hirocacbon bao gm (90% C3H8, C3H6 v lng di etan, etylen, C4H10 v C4H8. c trng 0,502 kg/l 15C Butan thng mi: Hn hp cc hirocacbon bao gm ch yu C4H8, C4H10 v cha di 19% v th tch C3H8. c trng 0,559 kg/l 15C 6,9 at Di ngng pht hin bng Na2PbO2 1b cc i Khng pht hin c bng CoBr2 im si cui cng 152 Khng th tch c nc bng cch gn im si cui cng 1C

Mi Khi lng ring p sut hi tng i 11,5 < p < 19,3 (at) 50C Hm lng S < 0,005 % trng lng Cc hp cht ca lu hunh n mn tm ng Hm lng nc Ho hi

Hn hp C3 v C4 c nhng gii hn v sc cng hi ca chng 50C. Nu d mt lng nh propan trong butan s lm tng ngay sc cng hi vt qu 8,5 at. Ngi ta bit rng khi c mt C3H8, C2H6 v C2H4 trong hn hp, p sut hi ca chng tng rt nhanh, rt kh gi di nhng gii hn quy nh. Sc cng hi ca hn hp l rt cn thit v cc p lc ca cc chai ng kh da trn cc sc cng hi ny. 10

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Trong cc quy nh c trnh by bng trn, quy nh v hm lng nc l rt quan trng (trc ht l i vi propan). Khi propan lng c gim p bng cch cho bay hi, nhit ca n gim xung rt nhanh v nu nh c nhng git nc nh tn ti trong kh chng s chuyn thnh v bt rt nhanh ng thot kh. Cc l thot kh b hp li v kh khng th thot ra c na. iu ny lun lun xy ra nu propan khng kh. Nhng c trng ca propan C3H8 v butan C4H10 l nh sau:
Cc c trng Khi lng ring 15C (g/cm3) im si im ng c Nhit ti hn p sut ti hn (at) Nhit ho hi (cal/kg) Th tch kh cho 1 kg cht lng ( ktc) Nhit tr ca 1m3 kh ktc Nhit tr cho 1 kg Nhit tr cho 1 lt Gii hn thp ca tnh d chy (%) Gii hn cao ca tnh d chy (%) Ch s octan ca cht lng Propan 0,509 44,5C 189,9C 975C 45,56 107,14 0,53m
3

n-C4H10 0,582 0,5C 136C 150,8C 38,83 96,71 0,44m

3

22.417 kcal 12.034 kcal 6.104 kcal 2,3 9,4 > 100

29.135 kcal 11.810 kcal 5755 kcal 0,9 8,4 > 100

Ngy nay, vic tiu th kh ho lng tng ln rt nhanh, ngi ta cho rng s tiu th kh ho lng cn tng hn na. Vic vn chuyn kh ho l ng bng ng bin c n gi n ho i rt nhiu cho php h gi thnh kh ho l ng. Cng tng t nh nhng g ngi ta thc hin vi cc kh thin nhin c ho lng vn chuyn trong cc tu bin. Ngy nay ngi ta vn chuyn propan v butan p sut thng bng cch gi chng nhit thp (50C i vi propan v 10C i vi butan). nhng nhit ny, cc kh b ho l ng c sc cng hi thp p sut kh quyn, bi vy khng c bt k mt bt tin no vn chuyn chng trn cc tu bin vi cc b cha bnh thng c trang b h thng lm lnh. S gi m nhit c thc hin bng cch ho h i cc kh b ho l ng v nn l i cc hi ny trong cc my nn nh c t ngay trn tu. Hin nay cc tu ch butan v propan c trang b nhng b cha ln bng thp c kh nng ti c rt ln cc kh ny p sut kh quyn v nhit 50C.
* Cc xng:

Xng thng: xng t Xng my bay 11

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Xng c bit chia thnh cc loi: A, B, C, D, E, F, G, H (theo tiu chun ca Php). Xng dung mi, xng thm (white-spirit) Du ho Nhin liu cho ng c phn lc (carburateur) Gazoin Nhin liu dn dng Du iezen nh dng cho ng c chy bin Du ng c Du cng nghip M bi trn Parafin, sp Bitum

* Ct di chn khng:

* Cc loi ng cong chng ct ca cc hn hp phc tp

1 - ng cong flash Nguyn l ca phng php nh sau: sn phm c t nng di p sut v sau c a vo mt bung p sut P1 v nhit T1 thnh mt pha hi V v mt pha lng L. o v tnh phn trm ca pha hi c sinh ra T1. Lp li phng php v lm gim p trong bung p sut P2 v nhit T2. Sau mt lot php o ta thu c ng cong T = f (% hi) - l ng cong flash.

ng cong flash ca mt hn hp phc tp Ti = Nhit si u tin; Tf = Nhit si cui cng

2 - ng cong ho hi lin tc n gin (VPS). 12

13

l php ch ng ct n thng thng trong phng th nghi m. 3 - ng cong chng ct l tng hay ng cong T.B.P (True Boiling Point). Nu s chng ct c thc hin trong mt thit b c nhiu a, ngha l thit b c chn lc tt tng ng vi sTc i t n c lp i lp li nhiu ln. Bng cch theo di nhit ca hi tu theo phn trm distillat, ta s thu c ng cong TBP hay ng cong ca cc im si thc. iu ny c ngha rng cc cu t lin tip chuyn lin tc thnh pha hi u ct ct, nhit si, p sut ca ct. V du th c qu nhiu cu t nn ng TBP c dng.
600

% th tch bay hi

ng TBP ca du th Ti = Nhit si ca cu t d bay hi nht; Tf = Nhit si ca cu t kh bay hi nht. 4 - ng cong ASTM (American Society for Testing Materials). Mt ng cong chng ct rt hay c s dng trong cng nghip l ng cong ASTM. ng cong ny thu c bng cch chng ct sn phm trong mt thit b chng ct n thng thng trong cc iu kin c chun ho nh tc t nng, tc ho hi, ... chn lc ca phng php chng ct ny l trung gian gia ng chng ct lin tc n gin v ng chng ct TPB. Cc ng cong chng ct ASTM cung cp nhng c trng chng ct ca cc sn phm du. N thun li l tng i nhanh trong khi chng ct TBP lu (24 gi). Dng ca ng chng ct ASTM:

13

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^
Nhit C
o

Nhit C

% th tch bay hi

ng ASTM

^
Nhit oC Nhit oC % th tch bay hi

Hnh 26. So snh cc ng chng ct Hnh 26 trnh by cc ng cong chng ct c gii thiu trn cho mt hn hp phc tp. Ta c th thy rng: 14 ng cong VPS t ng ng v i s ch ng c t khng ch n l c nht. ng cong TBP t ng ng vi s ch ng ct c ch n l c tt nht. ng cong ASTM tng ng vi chn lc trung gian gia hai ng cong trn. ng cong flash tng ng vi chn lc rt yu.

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y: chn lc ca s phn on l mc tch mt cu t quan tm trong qu trnh chng ct tch cc cu t ra khi hn hp ca chng. Thnh phn chng ct cng l mt trong nhng ch tiu k thut quan trng ca cc sn phm du lng ni chung v cc nhin liu lng ni ring.

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