Dau - Mo - Boi - Tron

Dng Vit Cng
Chng 1
Du bi trn
1.1 Tng quan Du bi trn l vt liu quan trng trong nn kinh t ca mi quc gia. Tt c cc my mc, thit b cc dng v cc kch c khc nhau s khng th thc hin c chc nng ca mnh hiu qu nu khng c cc loi du bi trn thch hp. Do c rt nhiu chng loi t du bi trn c cp cht lng thp n rt cao c dng nhm p ng cc nhu cu s dng t c bit n cc loi du a dng, dng rng r i trong nhiu lnh vc. Cc nc trn th gii sn xut du bi trn theo cc tiu chun, quy nh ring ph hp vi iu kin s dng my mc nc . Thng thng vic bi trn my mc phi s dng du do nh ch to ra chng quy nh. t nc ta sau nhiu nm i mi, cng vi xu th hi nhp quc t din ra nhanh chng, nn hin nay ang s dng rt nhiu my mc do cc nc khc nhau sn xut. Trong thc t, vic tun th cc quy nh v du bi trn m nh ch to ra l rt kh khn. V vy bi trn cc loi my mc, thit b do cc h ng ca nc khc nhau ch to, chng ta c th thay th bng cc loi du bi trn c cc tnh nng tng ng vi du m m cc h ng ch to quy nh. V vy, vic s dng vt liu bi trn ni chung, du m bi trn ni ring v quy trnh bi trn ph hp vi quy nh ca nh ch to thit b, s gp phn rt ln m bo cho my mc, thit b hot ng n nh, gim chi ph bo dng, nng cao tui th s dng v tin cy ca chng trong nn kinh t. - Du m bi trn c bn chc nng c bn, l : + L m gim ma st, gim cng m i mn, n mn ca cc b mt ma st nhm m bo cho ng c, my mc t cng sut ti a. + L m sch, chng tt c cc loi m i mn m bo tui th s dng ca ng c. + L m mt + L m kn Bi trn l bin php l m gim ma st n mc thp nht, bng cch to ra gia b mt ma st mt lp cht (cht bi trn). Cht bi trn c th dng lng (du nhn hay cn gi l du nht), dng c (m bi trn) hay dng rn...... Trong s chim a phn l cht bi trn dng lng, k n l cht bi trn dng c, sau cng l dng rn. Cht bi trn dng n y thng chim rt t v ch p dng trong mt v i trng hp ring bit nh bi trn cc trc c nhit rt cao hoc trong chn khng, nhng ni n y khng th dng du hay m bi trn c. BM. Lc Ha du
1
Sn phm du m & Ph gia
Dng Vit Cng

- m bo cho du bi trn c th thc hin tt cc chc nng nu trn, du bi trn phi c phm cht tt. C th l du bi trn phi c tnh bm dnh tt, phi c nht thch hp, phi c bn ho hc, c hc, sinh hc..., phi c dn nhit tt, khng gy n mn ho hc, ty ra phn tn tt cc cn, mui... sinh ra trong qu trnh s dng ng c, thit b. - Vic la chn, s dng du bi trn thch hp ng vai tr ht sc quan trng trong vic m bo cho du bi trn thc hin c cc chc nng ca mnh mt cch tt nht. C s quan trng la chn du bi trn thch hp l da v o nguyn l bi trn: + i vi cc chi tit l m vic c chuyn ng nhanh cn dng du c nht thp v ngc li. + Khe h gia cc mt tit l m vic c ng ln th du bi trn c ng cn c nht cao. + Nhit l m vic cao th dng du c nht cao. + S vng quay ln, p sut trn trc nh th dng du c nht thp. + p sut trn trc ln, s vng quay nh th dng du c nht cao. + Phm vi thay i nhit ln th dng du c tnh nhit nht tt (ch s nht cao) + Mi trng l m vic tip xc vi khng kh, kh chy nhit cao th dng du c tnh chng oxy ho v chng n mn. + Mi trng l m vic tip xc vi nc v hi nc th chn du c tnh chng to nh v chng to bt. + Thi gian s dng du lu, chn du c tnh chng oxy ho tt, tnh n nh cao. - Nguyn liu ch yu sn xut du m nhn l du m v du thc vt. Du gc c sn xut t du m thng qua cc qu trnh ch bin c gi l du gc khong v du c ngun gc t thc vt c tng hp qua cc qu trnh tng hp ha hc c gi l du gc tng hp. Th nh phn c bn ca du bi trn l du gc v cc ph gia c pha trn nng cao cht lng ca du bi trn. Bn cht ca du th v qu trnh ch bin s quyt nh tnh cht vt l v ho hc ca du gc to th nh. 1.2 Du gc Du gc khong c s dng pha ch du bi trn thch hp ch yu thu c t qu trnh chng ct chn khng sn phm y ca thp chng ct kh quyn. Du gc khong thng cha cc loi hydrocacbon sau y: - Parafin mch thng v mch nhnh; - Hydrocacbon no n v a vng (naphten) c cu trc vng xyclohexan gn BM. Lc Ha du
2
Dng Vit Cng

vi mch nhnh parafin. - Hydrocacbon thm n vng v a vng ch yu cha cc mch nhnh ankyl. - Cc hp cht cha vng naphten, vng thm v mch nhnh ankyl trong cng mt phn t. - Cc hp cht hu c cha cc d nguyn t, ch yu l cc hp cht cha lu hunh, oxi v v nit. Cc parafin mch thng, d i l loi sp rn nn h m lng chng trong du bi trn phi gim ti mc ti thiu, c bit l i vi du bi trn s dng nhit thp. Trong khi , cc parafin mch nhnh li l th nh phn rt tt cho du bi trn v chng c n nh nhit v tnh nhit nht tt. Mch nhnh c ng d i th c tnh n y cc th hin r r ng hn hn i vi cc parafin mch nhnh. Tng t nh vy i vi hydrocacbon vng no v vng thm. C th ni rng cc tnh cht mong mun n y cng c c cc hydrocacbon vng naphten v vng thm, l nhng loi c t l s vng trong phn t thp nhng mch nhnh li d i v mang tnh parafin. S vng ngng t c ng nhiu m mch nhnh parafin c ng ngn th tnh cht nhit nht ca cc hydrocacbon c ng km v c ng khng thch hp l m du bi trn. p ng yu cu v nng cao cht lng ca du gc, du gc cn c ch bin su khi thu c t cc phn on ca thp chng ct chn khng nh cc qu trnh: chit, tch, hydrotreating.... nhm loi b cc cu t khng mong mun khi du gc. Vic la chn du gc pha ch du bi trn ph thuc v o nht, mc tinh ch, n nh nhit v kh nng tng hp vi cc cht khc nhau (cht ph gia) hoc vt liu m du bi trn s tip xc trong qu trnh s dng. Cng ngh sn xut du gc bao gm cc bc sau: - Chng ct chn khng - Tch nha, asphalten - Tch aromatic - Tch parafin - X l bng hydro Nhn chung, du gc khong l th nh phn ch yu dng pha ch du bi trn, tuy vy cc tnh cht ca du gc khong khng cung cp tnh nng bi trn thch hp cho tt c cc loi ng c, my mc, thit b. V du gc khong v c bn c th nh phn ha hc tng t nhau, iu n y l m hn ch cc tnh cht bi trn ca du gc khong trong nhng iu kin l m vic khc nhau. u v nhc im ca du tng hp so vi du gc khong:
BM. Lc Ha du
Dng Vit Cng

u im: - Cho php iu ch ra cc loi du gc c cc tnh cht nh nh trc v chng c tng hp bng phn ng ha hc t cc cht c phn t lng nh hn. - Cho php to ra cc cht c tnh cht u vit nht dng l m du gc cho du bi trn, v so vi du gc tng hp, du gc khong d c dng nhiu phng php phc tp (x l bng hydro) cng khng th tch c ht cc cu t khng mong mun ra khi hn hp du gc. V vy du gc khong ch c s dng sn xut cc loi du nhn c cc yu cu bi trn trung bnh i din cho cc thuc tnh chnh ca du. Du gc tng hp cn c th to ra cc tnh cht ring bit m du gc khong khng c nh: ho n to n khng chy, ha ln vi nc - Du gc tng hp c khong nhit l m vic rng hn nhiu so vi du khong, khong t 550C n 3200C. Nhc im: - Nhc im ln nht ca du gc tng hp l i hi nhiu cng on tng hp ha hc phc tp, do gi th nh du gc cao. - Khng sn xut c vi mt s lng ln nh du gc khong d ngun nguyn liu ln hn nhiu so vi du gc khong. - Khng c cc tnh nng a dng nh du gc khong v trong hn hp ch c mt ca mt s cu t thc hin mt loi chc nng ring bit n o . Th nh phn ca du gc tng hp ch yu bao gm cc phn sau: - Hydrocacbon tng hp nh: Oligome olefin, cc polyme, copolyme, cc ankyl ca hydrocacbon thm, polybuten, cc hydrocacbon no mch vng - Este hu c: ch yu l cc este diaxit, este polyol ca axit bo - Polyglycol: Ch yu l cc polyme ca etylen, propylen oxit c trng lng phn t cao hoc c hai. - Este photphat: ch yu l cc este ankyl/aryl photphat 1.2.1 Chng ct chn khng Giai on th nht trong cng ngh sn xut du gc l tch ly cc phn on ring bit c nht khc nhau. Bc u n y l qu trnh chng ct chn khng phn cn cn li ca qu trnh chng ct kh quyn. Do , mc ch ca bc n y l iu chnh nht v nhit chp chy ca du gc. Chng ct chn khng nhm iu chnh nht v nhit chp chy ca du gc.
BM. Lc Ha du
Dng Vit Cng

LVGO Gasoil chn khng nh
Thp chng ct chn khng
MVGO Gasoil chn khng trung bnh
Cn kh quyn Cn chn khng
Hnh 1: Thp chng ct chn khng sn xut du nhn 1.2.2 Tch nha, asphalten S c mt ca nha, asphalten trong du gc chnh l nguyn nhn l m cho du gc c nht cao, ch s nht (VI_Viscosity Index) thp, c bn oxi ho thp, d gy n mn v l m xu m u du (do thng c cc d nguyn t trong chng), l nguyn nhn xut hin keo l m mt tnh ng nht ca du. tch nha, asphalten thng thng ngi ta dung phng php chit vi dung mi thch hp. Vic la chn dung mi ph thuc v o tnh chn lc ca n, tc l v o kh nng phn tch hai nhm cu t khc nhau v mt ho hc. Dung mi dng phi r, sn c, bn v mt ho hc trong khi s dng, khng gy n mn v d s dng. Ng y nay, ngi ta thng s dng propan l m dung mi cho qu trnh chit tch nha, asphalten. Hiu sut ca qu trnh chit ph thuc v o ba yu t c bn: bn cht ca dung mi, nhit tin h nh v t l dung mi trn nguyn liu. i vi dung mi propan, qu trnh chit thng c tin h nh 40 - 960C vi t l dung mi: nguyn liu l 5 : 8. 1.2.3 Tch aromactic Cc hydrocabon thm c ch s nht thp, nht ln, ng thi chng rt km bn, d b oxi ho l m tng khuynh hng to cc do vy trong qu trnh sn xut du gc ngi ta phi loi cc aromatic. Vic tch aromatic cng c thc hin bng phng php chit. C ba dung mi thng c s dng l furfurol, phenol v n-metyl-2pyrolydon (NMP). Nu em BM. Lc Ha du
5
Dng Vit Cng

dung mi ho trn k vi phn on du sau yn cho hn hp n y tch lng th hai pha hoc hai lp s c to th nh. Pha chit cha hu nh to n b dung mi cng vi cc cu t tan trong m ch yu l cc hydrocabon thm; pha cn li gm mt t cu t khng tan, ch yu l cc hydrocabon no v mt t dung mi. Sau khi tch dung mi, phn chit ra cn li u khng bin i g v mt ho hc.
Rafinat v dung mi
Nguyn liu phn on chng ct
Dung mi
Thp chit
Ct ct dung mi trong Rafinat
Ct ct dung mi trong phn chit
Phn chit v dung mi Rafinat

Hnh 2: S chit cc Aromatic, nha asphalten 1.2.4 Tch parafin (tch sp) Hn hp cc parafin mch thng (sp) c nhit nng chy cao v ho tan km trong du m. V th chng khng c php c mt trong du nhn th nh phn, ngoi tr khi h m lng rt thp, hoc cc loi du c s dng trong nhng iu kin c bit. Trn thc t, hu nh tt c cc loi du gc khong u phi qua qu trnh tch parafin. Tch parafin l mt trong nhng khu quan trng nht v kh khn nht trong qu trnh sn xut du gc. C hai quy trnh chnh hin ang c s dng cho mc ch n y. Quy trnh th nht l l m lnh kt tinh sp; quy trnh th hai l dng qu trnh cracking chn lc b g y phn t parafin to th nh nhng sn phm nh, phng php n y cn c gi l phng php tch parafin dng cht xc tc. 1.2.4.1 Tch sp bng phng php kt tinh Sp du m bao gm nhng hp phn d tch ring do kt tinh khi l m lnh phn on c cha chng. Nh vy bng cch kt tinh c th d d ng x l du cha sp th nh du khng cha sp. Qu trnh n y da trn nguyn l l m lnh du kt
Phn chit
BM. Lc Ha du
Dung mi
Dng Vit Cng

tinh parafin rn sau lc hoc ly tm tch ring phn rn ra khi pha lng. Tuy nhin, phng php n y khng lin tc, i hi c p sut cao nhiu khu; nht cao ca du l m cho qu trnh lc rt kh khn c bit vi cc du c nht ln; khng p dng phng php n y vi nhiu loi du c cc loi sp vi tinh th.... Chnh v th, khc phc nhng nhc im trn ngi ta kt hp l m lnh vi vic s dng dung mi. Thng thng ngi ta thng s dng hn hp cc dung mi khc nhau l m tng tnh linh hot ca qu trnh. Hn hp mytyl etyl xeton (MEK) vi metyl izo butyl xeton (MIBK) hoc MEK vi toluen hay c s dng. 1.2.4.2 Qu trnh hydro cracking chn lc Qu trnh hydrocracking chn lc dng tch parafin t du c hai loi: loi th nht ch dng mt loi cht xc tc nhm h nhit ng c; loi th hai dng hai loi cht xc tc va h nhit ng c va tng bn oxi ho ca sn phm. Cht xc tc c s dng l cc zeolit tng hp. Cc cht xc tc n y c th b g y mch hydrocacbon mch thng v hydrocacbon c mch d i mt cch chn lc. Phng php n y c nhiu u im hn so vi phng php kt tinh nh hiu sut cao, khng cn c cng on l m sch bng hydro, vn u t thp, cho php sn xut du gc c nhit ng c thp t nhng nguyn liu c h m lng parafin cao. 1.2.5 L m sch bng hydro Qu trnh tinh ch sn phm du tch parafin l qu trnh cn thit nhm loi b cc cht hot ng v mt ho hc, c nh hng n tnh cht ho l ca du gc. V d cc hp cht cha nit nh hng mnh n m u sc cng nh bn m u ca du gc v th phi loi b chng v chnh l yu cu ca qu trnh tinh ch bng hydro. RSH + H2 --- H2S + RH C5H5N + H2 -- C5H12 + NH3 ....................................... Sau tin h nh tch loi H2S, NH3.... s thu c du gc c bn ho l cao v phm cht tt ph hp hn cho qu trnh sn xut du bi trn thng phm. 1.2.6 Cch gi tn du gc Phn loi du gc - Phn loi theo th nh phn: Cn c v o th nh phn ca cc loi Hydrocacbon n o chim u th trong du gc m c th phn du gc th nh cc loi nh: du khong farafin, du gc khong naphten, du gc khong aromatic. Bng 1 cho thy s khc nhau v tnh cht vt l v ha hc ca du bi trn c cu trc khc nhau. Du gc aromat c dn ra bng n y ch so snh m khng c dng sn xut du bi trn. BM. Lc Ha du
7
Dng Vit Cng
Bng 1. c tnh vt l v ha hc ca cc loi du khong khc nhau Tnh cht/ th nh phn ha hc nht 40oC, cSt nht 100oC, cSt Ch s nht T trng 200C Nhit chp chy, oC im anilin, oC Nhit ng c, oC Phn t lng, vc Ch s khc x Phn tch qua t st % hp cht phn cc % th nh phn thm % th nh phn no Loi nguyn t cu trc nhm (phn tch cu trc nhm) % CA % CN % CP Du parafin 40 6,2 100 0,8628 229 107 -15 440 1,4755 0,2 8,5 91,3 Du naphten 40 5,0 0 0,9194 174 73 -30 330 1,5068 3,0 43 54 Du aromat 36 4,0 -185 0,9826 160 17 -24 246 1,5503 6,0 80 14
2 32 66
19 37 44
41 36 23
- Phn loi theo nht: Phn chng ct c s dng l m nguyn liu cho qu trnh sn xut du gc thng nm trong khong 11 n 150 cSt 400C. nht ca cc phn on cn khong 140 n 1200 cSt. Du gc khong c cch gi tn to s khc bit gia cc phn on u chng ct v du cn theo nht: + Cc phn on du gc trung tnh SN (Sovent Neutral) c phn loi theo nht Saybolt (SUS) 1000F: SN 70, SN 150, SN 500 Chng hn, du gc SN 150 l phn on du chng ct c nht 150 SUS 1000F (29 cSt 400C). + Cc phn on cn BS (Bright Stock) c phn loi theo nht Saybolt 0 210 F: BS 150, BS 250 Chng hn, du BS 150 l phn on du cn c nht 150 SUS 2100F (30,6 cSt 1000C). - Phn loi theo ch s nht (VI): + Du c ch s nht cao (HVI): VI > 85, c sn xut t du gc parafin qua cng on tch chit bng dung mi v tch sp. + Du c ch s nht trung bnh (MVI): 30 < VI < 85, c sn sut t c BM. Lc Ha du
8
Dng Vit Cng

hai phn ct naphten v parafin. + Du c ch s nht thp (LVI): VI < 30, c sn sut t phn on du gc naphten v c dng khi ch s nht v oxy ha khng cn thit ch trng lm. Cng ngh hydrocracking c th to du gc c ch s nht cao hn 140, l cc loi du c ch s nht rt cao (VHVI) hoc siu cao (SHVI) hay cn gi l du gc bn tng hp. Du gc bn tng hp l dng trung gian gi du gc khong tiu biu v cc hydrocacbon tng hp, chng to ra du gc c tnh cht tt hn. - Phn loi theo nhm: Ngo i cc h thng phn loi bit, ngi ta cng phn loi du gc theo nhm da v o ch tiu v h m lng lu hunh (S) v ch s nht theo tiu chun API nh bng 2. Bng 2. Phn loi du gc theo nhm HC no (%) H m lnglu hunh (%) Ch s nht (%) < 90 90 90 > 0,03 0,03 0,03 80 - 120 80 120 > 120
Du gc Nhm I Nhm II Nhm III
1.3 Ph gia 1.3.1 Tng quan Ph gia l nhng hp cht hu c, c kim v v c, thm ch l cc nguyn t, c thm v o cc cht bi trn nng cao cc tnh cht ring bit vn c hoc b sung cc tnh cht cha c ca du gc nhm thu c du bi trn c phm cht tt hn tho m n cc yu cu tnh nng i vi mt mc ch s dng n o . Thng mi loi ph gia c dng nng t 0,01 n 5%. Tuy nhin, trong nhiu trng hp mt ph gia c th c a v o khong nng dao ng t v i phn triu n trn 10%. Phn ln cc loi du bi trn cn nhiu loi ph gia khc nhau tho m n tt c cc yu cu tnh nng. Trong mt s trng hp cc ph gia ring bit c pha thng v o du gc. Trong nhng trng hp khc, hn hp cc loi ph gia c pha trn th nh ph gia ng gi, sau s c a tip v o du. C loi ph gia ch c mt chc nng nhng cng c nhiu ph gia c th m nhiu chc nng. Nh ph gia ZnDDP c chc nng chng oxi ho, gim m i mn, c ch n mn. Do vy s c ph gia n chc v ph gia a chc. Cc loi ph gia khc nhau c th h tr ln nhau, gy ra hiu ng tng h,
BM. Lc Ha du
Dng Vit Cng

hoc hiu ng i khng. Trng hp sau c th l m gim hiu lc ca ph gia, to ra nhng sn phm ph khng tan hoc nhng sn phm c hi khc. Nhng tng tc n y do hu ht cc ph gia u l cc ho cht hot ng v th chng tc dng qua li ngay trong ph gia ng gi hoc trong du to ra cc cht mi. Du gc nh hng n ph gia qua hai tnh nng chnh: tnh tng hp v tnh ho tan. Tinh ho tan c trng cho kh nng gi cc ph gia trong du, khng cho chng tch ra ca du gc. Tnh tng hp c trng cho kh nng tng thch ca du gc vi ph gia, khng l m gim hiu lc ca ph gia, c trng cho kh nng bo to n cu trc phn t v hiu qu tc dng ca ph gia. Tnh ho tan v tnh tng hp ph thuc v o bn cht ca du gc. Du gc tng hp c tnh tng hp tt song c tnh ho tan km cn du gc khong th ngc li, c tnh ho tan tt cn tnh tng hp km. Trong qu trnh s dng, du bi trn rt d b bin cht l m gim phm cht cht lng. Cc ph gia c s dng ngn chn cc qu trnh vt l, ho hc xy ra l m gim cht lng ca du bi trn. Cc chc nng chnh ca ph gia l (16): - L m tng bn oxi ho - Kh hot tnh xc tc ca kim loi - Chng n mn - Chng g - Chng s to cn bm v cn bn - Gi cc tp cht bn dng huyn ph - Tng ch s nht - Gim nhit ng c - L m du c th trn ln vi nc - Chng s to bt - Ngn chn s pht trin ca vi sinh vt - L m cho du c kh nng bm dnh tt - Tng kh nng l m kn - L m gim ma st - L m gim v ngn chn s m i mn - Chng s kt xc cac b mt kim loi 1.3.2 Gii thiu mt s loi ph gia in hnh 1.3.2.1 Ph gia chng oxi ho du Hu ht cc hp phn ca du bi trn u tc dng nhanh hoc chm vi oxi to th nh qu trnh oxi ho. Kh nng bn oxi ho ca cc hp cht hydrocabon tng dn theo th t: BM. Lc Ha du
10
Dng Vit Cng

Hydrocabon khng no < hp cht d nguyn t < hydrocacbon thm < naphten < parafin. Tc ca qu trnh oxi ho chu nh hng ca nhiu yu t nh bn cht ca du gc, nhit , hiu ng xc tc ca kim loi, s khuy trn, nng oxi trong du. C ch ca phn ng oxi ho l c ch gc xy ra theo 3 giai on: giai on khi m o, giai on pht trin mch v giai on tt mch. Giai on khi m o: 2RH + O2 ---> 2R* + H2O2 Giai on pht trin mch: R* + O2 ---> ROO* ROO* + RH ---> ROOH + R* ROOH --->RO* + O*H RO* + RH ---> ROH + R* OH* + RH ---> H2O + R* 2ROOH ---> ROO* + ROO* + H2O RRHCO* ---> RCHO + R* RRRCO* ---> RRCO + R* ----------Giai on tt mch: cc gc t do kt hp vi nhau to ra cc sn phm bn khc nhau: R* + R* ---> R-R R* + R* ---> R- CH=CH2 + RH 2RO* ---> ROOR 2ROO* ---> ROOR + O2 Mt khc, trong qu trnh s dng trong du bi trn lun c mt cc ion kim loi, y cng l xc tc y nhanh qu trnh oxy ha du. S c mt ca chng ng vai tr nh tc nhn cho qu trnh khi m o v qu trnh pht trin mch: Giai on khi m o: M(n+1)+ + RH ----> Mn+ + H+ + R* Mn+ + O2 ---> M(n+1)+ + O2*Giai on pht trin mch: M(n+1)+ + ROOH ----> Mn+ + H+ + ROO* Mn+ + ROOH ---> M(n+1)+ + OH* + RO* Song song vi qu trnh oxi ho lun xy ra qu trnh polime ho cc hp cht trung gian cha cc lin kt bi to ra nha, asphalten, cn bn... Qu trnh bin tnh ca du lun xy ra c nhit thp v nhit cao. nhit thp l s hnh th nh cc sn phm nh peoxit, ru, andehyt, xeton v nc. Di iu BM. Lc Ha du
11
Dng Vit Cng

kin nhit cao cc dng axit c hnh th nh sau cng ca qu trnh bin tnh du. Du b oxi ha s l m tng nht v kh nng bay hi, to cn bn v du vecni. Mt khc axit cng c hnh th nh t phn ng ca gc t do ankyl peoxit vi andehyt hoc xeton, y chnh l tin ca qu trnh hnh th nh cn bn ca du nhn. - Phn ng to cc axit t xeton v andehyt nhit >1200C.
- Phn ng to cc ngng t aldol t xeton v andehyt nhit >1200C.
Da v o c ch ca phn ng oxi ho, ngi ta chia cc ph gia chng oxi ho theo c ch tc dng ca chng. l ph gia c ch theo c ch gc v ph gia phn hy. - Ph gia c chng oxy ha theo c ch gc l cc cht c kh nng tc dng vi cc gc t do to sn phm bn ngn chn qu trnh oxi ho tip tc xy ra, cc cht c kh nng chng to cn cacbon ph gia loi n y cn c xem nh cc cht chng oxi ha s cp. C ch hot ng ca chng l nhng mt nguyn t H qua cc phn ng vi gc ankyl v /hoc vi cc gc ankyl peoxit l m gin on c ch pht trin mch ca qu trnh oxi ha du. Sn phm to th nh l cc gc bn nh: gc ankyl s th nh HC, gc ankyl peoxit tr th nh hydropeoxit. Cht chng oxi ha s cp c dng pha ch v o trong du nhn l cc dn xut ca phenol v amin thm. Tuy nhin, s chuyn ha ca nguyn t H t nguyn t oxi hoc nguyn t nit n gc c cc dng quinon hoc quinon amin khng th bo v c ht cc gc t do ca chui phn ng. C ch chung ca cc cht chng oxy ha s cp c th c biu din nh sau: R* + InhH ---> RH + Inh* BM. Lc Ha du
12
Dng Vit Cng

Inh* + R* ---> InhR (bn) * C ch hot ng ca ph gia chng oxy ha gc phenol Mt cht in hnh ca ph gia chng oxy ha gc phenol l 3,5-di-t-butyl-4hydroxytoluene (2,6-di-t-butyl-4-methylphenol), gi tt l BHT.
Da v o cc phn ng trn th hng s tc phn ng ca gc ankyl vi oxy to th nh ankyl peoxit ln hn nhiu so vi hng s tc ca gc ankyl vi BHT. iu c ngha trong s c mt ca oxy th phn ng ca gc ankyl vi BHT rt t xy ra. Thay v o BHT v cc dn xut ca phenol khc nhng mt nguyn t H cho gc ankyl peoxit v by chng.
Cn ch rng cc gc dn xut ca phenol l bn bi cc hiu ng khng gian v cu trc cng hng. Cu trc cng hng ca gc Cyclohexadien c th kt hp vi mt gc ankyl peoxit th hai to th nh cyclohexadien ankyl peoxit, cht n y bn nhit nh hn 1200C. Phn ng di y ch ra rng nhit cao hn cyclohexadien ankyl peoxit c th b phn hy th nh gc alkoxy, gc ankyl v 2,6di-t-butyl-1,4-benzoquinon.
BM. Lc Ha du
13
Dng Vit Cng
Hai gc phenol cu trc cng hng c th b thay i giai on tt mch ca phn ng theo c ch gc. Mt gc phenol c th nhng mt nguyn t H cho gc phanol khc to th nh mt phn t BHT v mt phn t metylen cyclohexadien.
* C ch hot ng ca ph gia chng oxy ha gc amin thm. Cht ph gia chng oxy ha gc amin thm thng c s dng l alkylat diphenylamin. C ch phn ng ca cht c ch oxy ha bng alkylat diphenylamin c bt u tht k l vi mt nguyn t H c tch ra bi s c mt ca cc gc ankyl, ankyl peoxit v alkoxyl nh di y.
BM. Lc Ha du
14
Dng Vit Cng

Do s tp trung phn ln ca cc gc ankyl peoxit nn chng c th phn ng c alkylat diphenylamin to th nh mt phn gc amin v phn ln cc ankyl hydropeoxit. Di y l 5 bc xy ra theo c ch c ch oxi ha ca cc amin thm nhit thp (< 1200C).
bc th 2 gc amin phn ng vi mt gc ankyl peroxy th hai to th nh gc nitroxyl v mt gc ankoxy. Gc nitroxyl lun bn qua ba dng cu trc cng hng theo c ch di y:
cc bc 3,4 v 5 cc gc nitroxyl tip tc phn ng vi cc gc ankyl peoxit to th nh hn hp nitroxyl peoxit (bc 3), nitroxyl cyclohexadien (bc 4) v bc 5 nitroxyl cyclohexadien phn hy th nh 1,4 benzoquinon v ankylat nitrosobenzen. nhit thp (<1200C) gc nitroxyl cng c th phn ng vi mt gc ankyl to th nh N-sec-alkoxy diphenylamin trung gian. Cht trung gian n y di tc dng nhit s sp xp li th nh mt xeton v ho n nguyn alkylat diphenylamin.
BM. Lc Ha du
15
Dng Vit Cng
Tuy nhin nhit cao (>1200C) , gc nitroxyl c th phn ng vi mt nguyn t H c tch ra t gc ankyl to th nh N- hydroxyl dephenylamin v anken. N- hydroxyl dephenylamin sau c th phn ng vi gc ankyl peoxit ho n nguyn gc nitroxyl v mt ankyl hydropeoxit
* Tnh tng h gia cht c ch oxi ha gc amin thm v gc cc dn xut ca phenol. Trong nhiu trng hp khc nhau, gia cc ph gia lun c s nh hng ln nhau th hin qua tnh tng h v tnh i khng. Trong trng hp n y, tnh tng h gia ph gia gc amin thm v ph gia gc dn xut ca phenol c th hin phn ng di y:
- Ph gia chng oxi ho bng cch phn hu cc hydropeoxit (hydropeoxit l mt trong nhng cht sinh ra gc t do thc y qu trnh oxi ho) to sn phm bn
BM. Lc Ha du
16
Dng Vit Cng

c xem nh l cht chng oxy ha th cp hay cn gi l cc ph gia phn hu. Hp cht ca lu hunh v /hoc hp cht ca pht pho thng c s dng nhm gim bt cc hydropeoxit trong phn ng chui gc to th nh cc ancol. Cc cht chng oxi ha th cp thng c s dng l Zinc dialkyldithiophosphate, phosphites, v cc thio khc Km dialkyldithiophosphate (ZDDP) l ph gia c s dng s dng t rt lu v c iu ch bi Herbert C. Freuner thuc hip hi du m California thuc Los Angeles. Theo th ZDDP c tng hp nh sau:
bc u ca phn ng c ch n mn, ZDDP phn ng nhanh vi hydropeoxit to th nh mui baz ZDDP nh di y:
Gc diankyldithiophotphoryl tip tc phn ng vi hydropeoxit to axit diankyl dithiophotphoric, axit n y li tip tc phn ng nhanh vi ROOH to ra cc sn phm l cc cht khng hot ng trong chui phn ng c ch oxi ha. H thng cc phn ng mt chiu s l m gim s c mt ca cc gc hydropeoxit mt cch ng k.
Sn phm ca cc phn ng c ch oxy ha bao gm: disulfide, cc ng ng ca mono v trisulfide v cc hp cht c dng nh: (RO)n(RS)3-nP=S v (RO)n(RS)3-nP=O. Cc sn phm n y cho thy chng rt t hot ng ging nh cc BM. Lc Ha du
17
Dng Vit Cng

cht c ch oxy ha hoc cc cht chng mn khc. Cc nh khoa hc cng pht hin ra s c mt ca cc ion hot ng, nhng ion n y s l tc nhn l m cc axit diakyl dithiophotphoric.
nhng ni c s tp trung ca ZDDP thp, c th s xy ra phn ng thy phn ZDDP th nh mui km trung tnh v axit diakyl dithiophotphoric. nhit cao hn 1250C diakyl dithiophotphoryl disulfide s b phn hy to th nh gc diakyl dithiophotphoryl, nhng gc m sau s phn ng c vi ROOH to ra nhiu axit diakyl dithiophotphoric. V vy, c rt nhiu cch khc nhau c th dng to th nh cc axit diakyl dithiophotphoric. ZDDP trung tnh cng c th phn ng c vi ROOH theo c ch chuyn dch electron, khi s ko theo s n nh (gim kh nng hot ng) ca cc gc hydropeoxit trung gian, kt qu l to ra cc sn phm diakyl dithiophotphoryl disulfide khng hot ng.
BM. Lc Ha du
18
Dng Vit Cng

Loi ph gia Bng 3: Mt s loi ph gia chng Oxy ho Tn ph gia Cng thc ho hc 2,6 diter butyl paracresol
Cc dn xut ca Phenol 4,6 diankyl phenol
Diankylphenylamin Diankylphenyl_ Alphanaptylamin Amin thm Phenyl_ Alphanaptylamin
Diamin thm
Cc Phenol c cha N hoc S
Dn xut ca Ur R = C8 C12 Phenol Sunfua R = C8 C12 v x = 1 hoc 2
Km iankyldithiphotphat (ZnDDP)
ZnDDP
BM. Lc Ha du
19
Dng Vit Cng

1.3.2.2 Ph gia th ng ho kim loi Cc b mt kim loi (Cu, Fe..) l cc cht xc tc l tng cho qu trnh oxi ho, l qu trnh khng mong mun xy ra trong qu trnh s dng du bi trn. Do vy phi v hiu ho hot tnh xc tc ca chng. Cc ph gia th ng ho kim loi bm ln trn b mt kim loi da trn s hnh th nh phc cht (phc Chelat) ngn cn s tip xc trc tip gia b mt kim loi vi du bi trn do vy th ng ho c kim loi. i vi cc ht kim loi trong khi du th cc ph gia n y tc dng vi n hnh th nh phc cht ri lng xung. i vi cc b mt kim loi cc ph gia n y hp ph ln b mt n to th nh mt m ng bo v ngn cn hot tnh xc tc ca kim loi. Cc ph gia in hnh l N-salixilidenetylamin hoc N,N disalixilidenetylamin, EDTA (etylendiamin tetra axetic), benzotriazon.... - N-salixilidenetylamin: - N,N disalixilidenetylamin:
1.3.2.3 Ph gia c ch n mn Trong qu trnh l m vic, cc b mt kim loi tip xc vi du bi trn rt d b n mn bi cc tc nhn c tnh axit nh cc axit hu c hoc v c, cc hp cht hot ng cha S, cc peoxit.... do vy du bi trn phi c ph gia c ch n mn. Cc ph gia n y hp ph ln b mt kim loi to th nh mt m ng bo v (m ng n y cn c tc dng th ng ho kim loi). M ng bo v n y s phi dnh cht ln b mt kim loi trnh b trc ra bi cc cht phn tn hoc ty ra. Cc ph gia in hnh l ZnDDP, limonen sunfua, pinen photphosunfua, benzothiazol..... - Limonen sunfua: - Pinen photphosunfua:
- Benzothiazol:
BM. Lc Ha du
20
Dng Vit Cng

1.3.2.4 Ph gia c ch g Trong qu trnh s dng di iu kin l m vic du c th b ln (hoc trc tip l m vic vi mi trng nc) hoc di s c mt ca cc tp cht du cc b mt kim loi c th b g. Vi st, g l s hnh th nh st hydroxyt, g l mt dng c bit quan trng ca n mn b mt. Cc cht c ch g ngn nc thm qua m ng hu c bo v. iu n y t c bng cch s dng cc hp cht phn cc c hp ph chn lc trn b mt kim loi v tc dng nh m ng ngn chng m. Ni chung, cc cht c ch g tc dng bng cch ph ln b mt kim loi mt m ng y nc. Cc ph gia in hnh c th k tn l axit ankyl suxinic, amin photphat, sunfonat, ankylthioaxetic..... - Axit ankyl suxinic: - Amin Photphat - Sunfonat:
Cc amin hu c v axit ankyl suxinic c dng trong trng hp h m lng trong du nh cn sunfonat kim loi v amin photphat c s dng khi h m lng nc trong du ln. Do khi h m lng nc ln th phn cc ca axit tng l m tng tnh axit s d gy ra hin tng n mn. 1.3.2.5 Ph gia ty ra Du bi trn l m vic di iu kin khc nghit c th xut hin s chy ca nhin liu hay s oxi ho du bi trn. y chnh l nguyn nhn gy ra cc sn phm axit v mt lng ln cn bn... chng c th l m tng nht ca du, gy n mn, l m du mt tnh ng nht, lng ng ln b mt kim loi l m tn hao cng sut.... Chnh v vy, cn phi c ph gia ngn khng cho cc cn bn bm trn b mt kim loi hoc li ko cc cn bn ra khi b mt kim loi v phn tn chng trong du di dng huyn ph. Vi ph gia ty ra, cc ph gia n y s hp ph ln cc cn bn v li ko chng ra khi b mt m chng bm dnh, gi chng trng thi l lng trong khi du. Cn ph gia phn tn hp ph ln cn bn l m cn bn khng t c vi nhau, gim kh nng sa lng, trnh to cn bn. Cc ph gia ty ra thng hay c s dng l canxi sunfonat trung tnh, canxi sunfonat kim v canxi sunfonat kim cao ngo i ra cn c phenolat, salixylat, photphonat.... Cc cht c s dng l m ph gia phn tn c cng thc ha hc
BM. Lc Ha du
21
Dng Vit Cng

chung theo cc dng di y:
a = c = 1 v b = 2 nu M l kim loi kim ha tr 1 a = c = 2 v b= 1 nu M l kim loi kim ha tr 2 Cc ph gia ty ra rt d b thu phn to ra hydroxit khng tan v axit l m gim tr s kim tng ca du: Me2+ + 2HOH ---> Me(OH)2 + 2H+ iu ch mt s ph gia phn tn: - Sunfonat ca kim loi Ca hoc Mg v cu trc Mixen ca ph gia ty ra kim cao:
Trong :
iu ch cc sunfonat ta thng bt u t Benzen hoc cc naphtalen c sunfonic ha bi tc nhn SO3 hoc Oleum
BM. Lc Ha du
22
Dng Vit Cng

T cc axitankyl benzensunfonic ta c th d d ng iu ch c cc sunfonat kim loi trung tnh, kim v kim cao:
Sunfonat trung tnh Cc loi sunfonat kim c cng thc nh:
V cc loi Sunfonat kim cao c iu ch nh di y:
BM. Lc Ha du
23
Dng Vit Cng

- Ankyl phenolat: bao gm cc phenolnat bnh thng, phenolat c cu metylen v phenolat c cu sunfua (sunfua ankylphenolat kim loi). iu ch cc Akylphenolat thng c bt u t phenol nh di y:
T ta c th iu ch c cc phenolat trung tnh, kim v kim cao: Cc dng Phenolat kim c cng thc ha hc nh sau:
V cch iu ch cc phenolat kim cao:
BM. Lc Ha du
24
Dng Vit Cng

Hoc nh:
- Ankylsalixylat: c dng nhiu cho du ng c nh cht ty ra v cht chng oxy ha. Chng cho php tha m n phn ln chc nng ty ra. c bit l tnh nng ngn cn cn bm trn pittng ng c diezen. C th iu ch cc Ankylsalixylat nh di y:
Ankylsalixylat trung tnh:
BM. Lc Ha du
25
Dng Vit Cng

Ankylsalixylat kim:
Ankylsalixylat kim cao:
- Photphonat:
BM. Lc Ha du
26
Dng Vit Cng

Cc dng Photphonat:
1.3.2.6 Ph gia phn tn Cc cht phn tn l cc cht c kh nng ngn nga hoc l m chm qu trnh to cn v lng ng trong iu kin hot ng nhit thp. Nh vy chc nng c bn ca cht phn tn l l m yu lc cu kt gia cc tiu phn ring bit vi nhau, to iu kin l m tan r cc kt ta xp v cc khi kt t, do cho php tng tiu phn c th tn ti nh mt thc th ring bit. Ni cch khc, cc cht phn tn c mt i lc mnh vi cc tiu phn gy bn du v chng bao quanh mi tiu phn bng cc phn t tan trong du, nh gi c cc cn ca du khng b kt t v ng cn li trong ng c. Vi ph gia phn tn l ankenyl polyamin suxinimit, ankylhydroxybenzyl polyamin.....Cc ph gia phn tn c cu to gm ba phn c bn: nhm a du v nhm phn cc. Hai phn c ni vi nhau bng nhm ni. BM. Lc Ha du
27
Dng Vit Cng

Nhm a du thng l cc hydrocabon mch d i gip cho ph gia c th tan tt trong du gc c s dng. Nhm phn cc thng cha c nguyn t N, O, hoc P Cu trc chung ca cc cht phn tn c m t nh trn hnh 3:
Phn a du
Nhm Phn phn cc ni Hnh 3. Cu trc chung ca cc cht phn tn 1. Cc ph gia ankenyl polyamin suxinimit c iu ch nh sau: - Tng hp cc isobutylen:
- Tng hp gia ankenylsuxinic anhydrit theo c ch chung di y:
C ch n y c gii thch qua hai phn ng ca Diels-Alder v Ene:
BM. Lc Ha du
28
Dng Vit Cng
- Tng hp cc Polyamin theo s di y:
- T cc hp cht iu ch trn ta s tng hp c cc ankenyl polyamin suxinimit di cc dng nh amit, este..
BM. Lc Ha du
29
Dng Vit Cng
Trong : R Ankenyl t polyizobutenyl c trng lng phn t t 500 n 2000 v x = 1 4. Nhng cht phn tn n y c s dng rng r i trong cc du cacte ng c. Chng cng c xem nh nhng ph gia c chc nng c ch g. 2. Cc ph gia ankylhydroxybenzyl polyamin c tng hp nh sau:
BM. Lc Ha du
30
Dng Vit Cng

Trong R nhm polyizobutenyl (PIB) trng lng t 500 2000 v x = 2 5. 3. Cc Este photphonat: Cc cht n y cng c s dng l m cc cht ph gia c ch g, chng c iu ch nh sau:
4. Cc Polyacrylat: Cc cht n y cng cho kh nng phn tn, ngo i ra chng cn c tnh nht nhit tt (cht ci thin ch s nht) nn chng c s dng nh l ph gia phn tn nhiu tc dng, in hnh nh: DOCP, polymetarylat, copolyme
BM. Lc Ha du
31
Dng Vit Cng

C ch hot ng ca polymetarylat nh sau:
Copolyme:
1.3.2.7 Ph gia ci thin ch s nht Trong qu trnh s dng, du bi trn c th b oxi ho, chu nhng tc ng khc nhau l m cho tnh nht nhit ca du bi trn b gim i. ng thi, nhit l m vic ca du c th thay i trong khong rng t nhit rt thp ti nhit rt cao do vy vy trong mt s loi du bi trn cn phi c ph gia ci thin ch s nht. Ph gia ci thin ch s nht l m tng nht ca du nhit cao v hu nh khng l m tng nht ca du nhit thp. Chnh v vy, cc ph gia ci thin ch s nht thng l cc polime tan c trong du v c cu trc dng xon nhit thp (khi du gc l dung mi ho tan km). Khi nhit cao (du gc l dung mi ho tan tt) th cc polime n y dui d i ra, tri rng ra v do vy l m tng nht ca du. Cc ph gia n y c trng lng phn t nm trong
BM. Lc Ha du
32
Dng Vit Cng

khong t 10000 n 50000 vC nhng tt nht nm trong khong t 50000 n 150000 do nu trng lng phn t thp qu th khng c cn trng lng phn t ln qu th km bn nhit, km bn c hc. Cc ph gia ci thin ch s nht chia th nh hai dng c bn. Dng hydrocacbon l cc copolyme etylen propylen, polyizobutylen, copolime styren butadien hydro ho....... Cc polime metacrylat, polyacrylat v cc copolime ca este styrenmaleic l cc v d minh ho cho cc ph gia ci thin ch s nht dng este.
Vic la chn ph gia ci thin ch s nht ph thuc v o c tnh ca du gc c dng pha ch cng nh v o loi du th nh phm cn pha ch. Cn phi lu rng: - Vic thm ph gia ci thin ch s nht s l m thay i tnh chy ca du gc, nht ng hc ca du pha ch s thay i vi tc trt. - Trng lng phn t ca ph gia ci thin ch s nht c ng tng th chng c ng nhy cm vi s thay i ng sut c hc. - ng sut dch chuyn c sinh ra, chng hn gia pittng v th nh xi lanh trong ng c, s dn n qu trnh t g y khng thun nghch ca cc phn t polime th nh cc mch nh hn, qu trnh n y l m cho nht gim i. 1.3.2.8 Ph gia gim nhit ng c Du gc khong c th cha sp. Khi du bi trn c s dng hay bo qun trong mi trng nhit thp sp s kt tinh th nh cc tinh th c cu trc kiu BM. Lc Ha du
33
Dng Vit Cng

li mt co v ngn cn s chy ca du. Chnh v vy trong nhiu loi du bi trn cn c ph gia gim nhit ng c. Cc ph gia l m gim nhit ng c ca du do l m chm qu trnh to th nh cc tinh th sp ho n ho bng cch bao bc xung quanh hoc cng kt tinh vi sp. iu n y s thc y qu trnh to th nh cc tinh th nh hn thay cho cc m sp vn xp hnh th nh khi khng c cc ph gia. Cc ph gia gim nhit ng c khng gy nh hng ti nhit kt ta, lng v mng tinh th sp tch ra. Ch hnh dng bn ngo i v kch thc ca tinh th b thay i. Cc tinh th hnh cu c hnh th nh thay cho cc tinh th hnh kim v hnh phin. S bin i nh vy l m gim kh nng ni chng v an c i v o nhau ca cc tinh th to nn nhng khi kt ln ca sp gy cn tr i vi s chy ca du. Hu ht cc ph gia gim nhit ng c l cc polime, trong c mt s ph gia cng c tc dng ci thin ch s nht. Di trng lng phn t ca cc ph gia n y thp hn so vi ph gia ci thin ch s nht thng t 5000 100000 vC. in hnh c th k tn l cc polime ankylmetacrylat, cc polime alphaolefin v cc copolime, naphtalen c ankyl ho, ankylphenol mch d i..... Naphten c ankyl ho:
1.3.2.9 Ph gia chng to bt Trong thc t s to bt ca du l mt vn nan gii. Khi xy ra hin tng to bt l m cho du b tht thot nhiu, l m kh khn khi vn h nh h bi trn tribology, ngn cn s lu thng tun ho n ca du gy nn bi trn khng y , l m tng thi gian phn hi ca h thu lc. ng thi, s to bt mnh l m tng s BM. Lc Ha du
34
Dng Vit Cng

oxi ho du do khng kh c trn nhiu v o trong du. Kh nng chng li s to bt ca du bi trn khc nhau ng k v ph thuc v o bn cht ca du th, phng php, mc ch bin, v nht ca du. Kh nng n y c th c ci thin bng cch cho thm mt lng nh cc ph gia chng to bt. Cc ph gia to bt hp ph ln bt l m gim sc cng b mt ca bt khin cho cc bt t li vi nhau th nh bt ln ni ln b mt v v ra l m thot khng kh ra ngo i. Cc ph gia chng to bt thng c s dng l cc silicon lng, c bit l polymetylsiloxan: -((CH3)2 Si- O)-n l cht chng to bt hiu qu rt tt. Thng thng cc silicon c pha vi nng t 1 n 20 phn triu. Nu pha vi nng cao hn th c th l m cho du b to bt nhiu hn c mc cha cho ph gia chng to bt nn khng kh li xm nhp v o du nhiu hn. Mt iu cn lu l ph gia phn tn l cht to bt rt tt nn i vi cc du bi trn c pha ph gia phn tn th bt buc phi pha ph gia chng to bt. 1.3.2.10 Ph gia tribology Trong thc t, khi iu kin l m vic tr nn khc nghit hn (ti trng cao, tc thp, rp b mt ln..) th m ng lng (du bi trn) se khng th ho n to n gnh chu ti trng ln. Cc im nh trn b mt rn s cng gnh chu ti trng vi m ng cht lng. Ch bi trn chuyn t m ng lng sang ch bi trn m ng mng hn hp ri sau chuyn sang ch bi trn gii hn. S tip xc gia cc b mt rn sinh ra m i mn, tng ma st v hin tng h n dnh cc im mp m. Chnh v th m cc ph gia tribology c cp ti l m gim ma st, m i mn v ngn cn s h hi ca b mt tip xc. Ph gia tribology pht huy tc dng hai ch bi trn: bi trn m ng mng hn hp v bi trn gii hn. Ph gia tribology l mt nhm cht cc k quan trng c pha v o hu ht cc du bi trn, c bit l du bnh rng v du ng c. Chng c chc nng l m bin tnh ma st (ph gia bin tnh ma st FM), gim m i mn (ph gia chng m i mn AW) v chu ti trng cao (ph gia cc cp EP). a. Ph gia chng m i mn, AW (Anti-Wears) Trong thc t c ba dng m i mn chnh: m i mn dnh (s tip xc trc tip kim loi vi kim loi), m i mn ht (m i mn do s c mt ca cc ht) v m i mn ho hc (do s tn cng ca cc cht gy n mn, cc cht c tnh axit). - S m i mn dnh trong h thng bi trn xy ra khi cc iu kin ti trng, tc v nhit cao, m ng du bi trn tr nn mng n mc cc ch mp m trn b mt tip xc vi nhau. Do vy l m i mn do vt liu chuyn t b mt n y sang b mt kia trong khi hai b mt chuyn ng tng i vi nhau dn ti
BM. Lc Ha du
35
Dng Vit Cng

qu trnh h n dnh pha rn. S tip xc kim loi vi nhau c th ngn cn c khi cho hp cht to m ng v o du bi trn v nh c s hp ph vt l hoc phn ng ho hc m thng b bin dng do chy do dn ti s phn b ti trng khc i m n bo v c b mt kim loi. ZnDDP (Km iankydithiophotphat), cc hp cht c photpho nh tricresyl photphat v cc hp cht ca lu hunh nh sunfua, disunfua, molipden dithiocacbonat.... l cc ph gia chng m i mn dnh rt tt. - S m i mn ht l do cc ht m i, cc tp cht t bn ngo i a v o hoc do cc phn t t m i mn dnh gy ra. C ch ch yu ca s m i mn vt liu l s ct vi m ca cc vt cng. M i mn ht c th ngn cn c bng cch lc tch cc ht rn, cng ra khi du. - M i mn ho hc do c cc phn ng ho hc xy ra trn b mt kim loi kt hp vi tc ng c xt l m cho ch kim loi b n mn b ct tch ra. Cc axit mnh c to th nh trong qu trnh s dng du bi trn c th tn cng v o b mt kim loi to ra cc hp cht m chng d b bc ra khi c s ch xt. Dng m i mn n y c th hn ch c bng vic s dng cc cht ty ra dng kim cao do c tc dng trung ho cc sn phm mang tnh axit tn ti trong du. b. Ph gia cc p EP (Extreme pressure) Ph gia cc p ngn nga hin tng kt xc, h n dnh gia cc b mt kim loi khi ang hot ng di p sut cc ln (chu ti trng rt nng). Cc ph gia cc p tc dng vi cc b mt kim loi ma st to ra cc hp cht mi c ng sut ct thp hn kim loi gc nn lp ph mi hnh th nh chu trt ct trc tin v nhiu hn so vi kim loi. Trong thc t, ph gia cc p thng ch c tc dng tt khi xy ra phn ng ho hc. iu n y cng ng ngha vi vic gia tng kh nng m i mn ho hc. Cc ph gia cc p c s dng rng r i l cc loi du bo c sunfua ho, cc este, cc hydrocacbon nh polybuten, dibenzyl disunfua, dibutyl disunfua...... - Hydrosunfua:
- Sunfua olefin:
BM. Lc Ha du
36
Dng Vit Cng
- Este cha lu hunh:
- Tricesyl photphat: OPO3(R-CH3)3 c. Ph gia bin tnh ma st FM (Friction Modifiers) Ph gia bin tnh ma st c m t nh l cht l m gim h s ma st v t c s trt phng nhn hoc l m tng h s ma st t c s dng trt. Thng thng ph gia n y l m tng bn ca m ng du v nh gi cho b mt kim loi tch ri nhau v ngn khng cho lp du b ph hu. Ph gia FM m l m gim h s ma st s bo tn c nng lng. Chng c s dng ch yu trong du ng c v du bnh rng truyn ng ng c. Ni chung chng c s dng khi cn to ra chuyn ng trt m khng c rung ng v khi cn c h s ma st nh nht. Ph gia thuc loi n y bao gm cc hp cht cha O, N, S, Mo, Cu v mt s nguyn t khc. Cc ph gia n y l m tng bn ca m ng du ch yu do hin tng hp ph vt l nh l m gim ma st. bn ca m ng du do tc dng ca ph gia lin quan ti d i ca mch ankyl trong phn t ph gia FM. Do cc hp cht ph gia FM mch d i nh axit bo, este bo hoc amin, amit bo c s dng. d y v hiu qu ca m ng du
BM. Lc Ha du
37
Dng Vit Cng

bo v ph thuc v o d i ca mch cacbon (mch c ng d i th d y c ng ln), phn cc ca nhm chc, cu trc, du gc, kim loi hc v nhit . Cc cht ph gia loi n y thng c s dng l :
1.3.2.11 Ph gia to nh, kh nh Khi du bi trn phi l m vic trong mi trng bt buc c s c mt ca nc th ph gia to nh hoc kh nh s phi c s dng. Cht to nh l nhng cht hot ng b mt phn tn nc trong du hoc du trong nc. T h nc trong du ta thu c h thu lc chng chy, cht bi trn dng trong khoan v mt v i loi mi trng dng trong ko si kim loi. Cc cht to nh thng dng l cc ankenyl suxinimit, cc mui sunfonat, cc axit bo v mui ca axit bo, polyankylen glycol, etanol amin...... C ba nhm cht to nh: cht to nh anion, cht to nh cation v cht to nh khng ion. Cc cht kh nh bao gm triankyl photphat, polyetylen glycol, ankyl amin, axit cacboxylic. Ngo i cc ph gia nu trn, trong du bi trn thng phm cn c th c ph gia dit khun, c cc tc nhn bm dnh, tc nhn l m kn......
BM. Lc Ha du
38
Dng Vit Cng

1.4 Mt s tnh cht ha l in hnh ca du nhn v cch xc nh
Trong thi gian s dng, du phi m nhim cc chc nng nh c cp v phi chu tc ng ca cc yu t nh: - Nhit cc b phn khc nhau. - nh hng ca ti trng. - Tip xc vi oxy khng kh. - nh hng xc tc ca cc b mt kim loi. - Nhim bn do nhin liu, cc sn phm chy, bi bn, nc V vy trong qu trnh s dng, du ng c thng c phn tch nh gi theo cc tnh cht ha - l sau: + nht ng hc + Ch s nht + Tr s kim tng + Nhit chp chy + H m lng nc + H m lng cn + H m lng kim loi + H m lng tro sunfat + Khi lng ring 1.4.1 nht - ASTM D 445 nht l mt ch tiu quan trng v c bn ca du bi trn, n l mt tnh cht quyt nh d y m ng du, n l m gim ma st v m i mn gia hai b mt tip xc. N c nh hng n kht, tn hao cng ma st, kh nng chng m i mn, kh nng chng to cn, kh nng l m mt cc chi tit l m vic Trong ng c, nht ng vai tr quyt nh lng tiu hao nhin liu, kh nng tit kim du v hot ng ca ng c. i vi mt s loi ng c, c bit l ng c t cng nh hng ti khi ng v tc trc khuu. nht qu cao s l m gim tc ca trc v do l m tng lng nhin liu tiu hao (k c sau khi ng c khi ng). nht qu thp s dn ti chng m i mn v tng lng tiu hao du. V vy cn phi chn nht ph hp vi tng ng c v iu kin hot ng ca chng. V vy nht c ly l m c s cho h thng phn loi du nhn (Theo cp nht SAE). nht l s o kh nng chng li s chy ca du nhn, c xc nh bng t s gia ng sut trt v tc trt. ng sut trt l lc trt trn mt n v din tch vung gc vi phng thng ng. Tc trt l s chnh lch tc trn mt n v khong cch theo phng thng ng. Ni chung cc phng tin ti trng nng, tc thp th s dng cc du bi trn c nht cao. Ngc li nhng phng tin ti trng nh, tc cao th dng du c nht thp. BM. Lc Ha du
39
Dng Vit Cng

Cc nguyn nhn l m thay i nht du ng c trong khi ng c hot ng ht sc a dng. C hai dng thay i nht lin quan n s mt nht ca cc loi du cha ph gia polyme. Dng th nht l s mt nht tm thi do tnh cht ca dng chy khng Newton. Dng th hai l s mt nht vnh vin do cc phn t polyme trong ph gia ci thin ch s nht b b gy th nh cc phn t nh hn. Cng c hai qu trnh b gy polyme: b gy do oxy ha v b gy do nhit. Cc qu trnh n y cng dn n s thay i nht vnh vin v chng khng c tnh thun nghch. Bng 4: Nhng thay i nht c kh nng xy ra i vi du ng c trong qu trnh hot ng: Nguyn nhn ca s thay i nht nh hng ti nht ng sut trt ca cc loi du khng Newton Gim nht Phn hy cc ph gia polyme Gim nht Du b bay hi Tng nht Du b ln nhin liu Gim nht Qu trnh oxy ha cc th nh phn du gc Tng nht Du b ln nc Tng nht Du cha b hng Tng nht * Quy trnh xc nh nht khi dng nht k mao qun: - Chn nht kt ph hp vi nht ca du sao cho tc chy khong 200 giy. - Np v o dng c o (nht k) mt lng du thch hp. - n nh nhit ti mt nhit nht nh trong khong thi gian (30 pht), dng ng h bm giy o thi gian chy ca lng du trn t vch n y n vch kia ca dng c o, ph thuc v o hng s nht k (k) ta tnh c nht ng hc ca du theo cng thc sau y: = k.t (7) Trong : : nht ng hc (cSt); k: hng s nht k (cSt/s); t: thi gian chy (s).
Hnh 3: B xc nh nht
BM. Lc Ha du
40
Dng Vit Cng

1.4.2 Ch s nht ASTM D 2270 Ch s nht (VI) l mt ch s chuyn dng nh gi s thay i nht ca du bi trn theo nhit . Thng thng khi nhit tng nht s gim. Du nhn c coi l du bi trn tt khi nht ca n t b thay i theo nhit , y l loi du c nht cao (cc loi du naphten). Ngc li nu nht thay i nhiu theo nhit , c ngha l du c ch s nht thp (cc loi du parafin). Ch s VI l mt gi tr bng s nh gi s thay i nht theo nhit da trn c s so snh khong thay i tng i v nht ca hai loi du chn lc chuyn dng, hai loi du n y khc bit nhau rt ln v ch s nht VI.
nht ng hc
L (VI = 0) U
H (VI =100) 40 Nhit , oC 100
Hnh 4. S thay i nht ca du bi trn theo nhit . Trong : L - nht ca du c VI = 0 (du c VI thp du naphten) H - nht ca du c VI = 100 (du c VI cao du parafin) U - nht ca du cn phi tnh ch s nht Da v o nht ng hc 400C v 1000C ca tng loi du tnh ch s nht (VI) tng ng ca chng theo tiu chun ASTM D 2270. Tiu chun n y a ra hai cch xc nh: cch th nht p dng cho cc sn phm du m c gi tr VI < 100; cch th hai p dng cho cc sn phm du m c VI > 100.
BM. Lc Ha du
41
Dng Vit Cng

+ Cch th nht: Ch s nht VI c tnh theo cng thc sau:
VI =
(L U ) 100 (L H )
(2)
Trong : L nht ng hc 400C ca mt loi du c VI = 0 v c cng nht ng hc 1000C vi du m ta cn tnh VI, cSt; U nht ng hc 400C ca du ta cn phi tnh ch s nht, mm2/s; H- nht ng hc hc 400C ca mt loi du c VI = 100 v c cng nht ng hc 100oC vi du m ta cn tnh VI, cSt; Nu nht ng hc ca du 1000C nh hn hay bng 70 cSt th cc gi tr tng ng ca L v H cn phi tra bng trong ASTM D 2270. Nu nht ng hc 1000C li nh hn 70 cSt, th gi tr L v H c tnh nh sau: L = 0,8353 Y2 + 14,67 Y 216 (3) H = 0,1684 Y2 + 11,85 Y 97 (4) Vi Y l nht ng hc 1000C ca du tnh ch s nht, cSt. + Cch tnh th hai: Ch s nht c tnh theo cng thc sau: VI = [ (antilogN 1)/0,00715] + 100 (5) Trong N = (logH logU)/logY (6) Gi tr H c tnh nh cch tnh th nht. Ngo i ra, cc bng trong tiu chun ASTM DS 39B cho php c trc tip ch s nht ca cc loi du m. Da v o ch s nht ngi ta c th la chn loi du thch hp vi iu kin l m vic ca my. Trong nhiu trng hp, nu nhit ca my t thay i th ngi ta cng t quan tm n ch s nht. Cn trong trng hp nhit chy my thay i trong mt khong rng, nh ng c t, th cng vi tnh nng khc, ch s nht cng rt c coi trng. nng cao ch s nht ca du trong iu kin nht nh, ngi ta hoc pha thm v o du khong ph gia ci thin ch s nht, hoc s dng nhng loi du gc tng hp hoc bn tng hp. Trong qu trnh s dng du c biu hin thay i ch s nht th l do du b nhim bn bi c ln sn phm khc. i khi, qu trnh oxy ha l nguyn nhn l m tng ch s nht trong qu trnh s dng. Vic gim ch s VI cng c th do c nhng lc ph v cu trc phn t ca cc ph gia polyme c mt trong du bi trn.
BM. Lc Ha du
42
Dng Vit Cng

1.4.3 im chp la - ASTM D 92 im chp la ca du c nh ngha l nhit thp nht m ti du c nung nng bc ln to vi khng kh mt hn hp kh le chy mt lt khi ngn la a v o. Nhit thp nht m hi du nung nng bc ln to vi khng kh chy lin tc trong 5 giy khi c ngn la i v o trong iu kin ca phng php th tiu chun c gi l im bt chy. im chp la v im bt chy ca du mi thay i theo nht. Du c nht cao s c im chp la v bt chy cao hn. Thng thng th im chp la v im bt chy ca du ph thuc v o loi du th. Du naphten thng c im chp la v im bt chy thp hn du parafin c cng nht. Quy lut chung l i vi cc hp cht tng t nhau th im chp la v im bt chy s tng khi trng lng phn t tng. Thng im bt chy cao hn im chp la khong 30oC. Du nhn thng c xc nh im chp la cc h theo ASTM D 29 v cc kn theo ASTM D 93. Du mi c im chp la thp hn gi tr m n cn phi c, th l du hiu ca s c mt loi du c nht thp, c phn on nh, dung mi d bay hi hay xy ra qu trnh cracking du, do l m vic nhit cao. im chp la c gi tr cao hn trung bnh bo hiu s pha trn du c nht cao hn. * Quy trnh xc nh: mt lng du theo mc cho php, t v o my o chp chy, ni my vi bnh ga, sau chnh ngn la c ng knh 3,2 n 4,8 mm v iu chnh nhit ca mu sao cho t 14oC n 170C /pht. Khi nhit ca mu thp hn im chp la d on 560C gim tc xung cn 5-60C /pht, cho n khi nhit d on xung cn 28oC th gim xung 20C chm la 1 ln. C th cho n khi pht hin v kt thc nhit chp chp chy. 1.4.4 im ng c - ASTM D 97 im ng c l nhit thp nht m du bi trn gia c tnh linh ng iu kin cho. y l ch tiu cho bit tnh cht chy nhit thp, xc nh tnh linh ng ca du nhn. Khi nhit gim xung th nht ca du tng ln t ngt l m cho tnh linh ng gim. Khi t ti nhit ng c n s ng c li hoc khng chy c lu di tc dng ca trng lc. BM. Lc Ha du
43
Dng Vit Cng

Hu ht du nhn u cha mt s sp khng tan v khi du c l m lnh, nhng sp n y bt u tch ra dng tinh th an c i vi nhau to th nh mt cu trc cng, gi du trong cc ti nh ca cc cu trc . Khi cu trc tinh th ca sp n y to th nh y th du khng lun chuyn c na. gim nhit ng c ngi ta dng ph gia h nhit ng c. i vi mt s loi du khng cha sp, nht ca chng tng ln khi nhit gim i v n mt nhit n o th du mt tnh linh ng. Ngi ta khng th dng ph gia h im ng c h thp nhit ng c ca cc loi du n y v cc ph gia ch c tc dng ngn cn s ln ln v bao bc ca cu trc tinh th sp. Chnh v vy mt s loi du khng cha sp th c im ng c gii hn. im ng c cho bit gii hn thp nht m du c th s dng c. * Quy trnh xc nh: Trc tin ngi ta phi un nng mu ln m bo cho cc cu t trong du tan ho n to n, sau l m lnh theo tc quy nh, c sau 3 pht li kim tra tnh linh ng ca du mt ln. Kt qu nhit ng c ca du c xc nh l ly nhit m ti du khng linh ng na khi ta nghing bnh ng n trong 5 giy, sau cng thm 30C. 1.4.5 Tr s kim tng TBN - ASTM D 2896 kim trong du nhn c biu th bng tr s kim tng (TBN) , cho bit lng axit clohydric hay percloric, c quy chuyn sang KOH tng ng cn thit trung ha ht cc hp cht mang tnh kim c mt trong 1g mu. Hin nay, nhiu loi ph gia s dng nhm nng cao phm cht du bi trn. Cc hp cht c coi l c tnh kim bao gm: cc cht kim v c v hu c, cc mui ca cc kim loi nng, cc ph gia, c bit l cc ph gia c dng trong iu kin khc nghit, nh ph gia ty ra Rt nhiu loi ph gia hin nay s dng cho du ng c c cha cc hp cht kim, nhm trung ha cc sn phm axit ca qu trnh chy, lng tiu tn cc th nh phn kim n y l mt ch s v tui th s dng ca du. Du c kim cao th kh nng chng n mn tt. Khi TBN gim n mt gi tr gii hn n o th du ng c cn phi c thay mi. Khi kim qu thp hay khng cn th du khng c kh nng bo v cc chi tit ng c khi n mn. Phng php ASTM D 2896 thng c dng xc nh cc hp cht kim trong cc sn phm du m. * Quy trnh xc nh: Phng php ca tiu chun ASTM D 2896 l phng php chun in th. Cc tin h nh nh sau:
BM. Lc Ha du
44
Dng Vit Cng

- Cn mt lng mu theo quy nh ph thuc v o lng TBN d on: Lng mu m(g) = 10/TBN d on. - Ln lt cho 40 ml Cloruabenzen v 20 ml axit acetic v o mu - a mu ln my np s liu sn v ch my chy n kt thc quy trnh chun , my s t ng cho kt qu.
Hnh 6: My o tr s kim tng 1.4.6 H m lng tro sunfat - ASTM D 847 Tro sunfat l phn cn cn li sau khi than ha mu, sau phn cn c x l bng H2SO4 v nung nng n khi lng khng i. H m lng tro sunfat dng ch nng ph gia cha kim loi trong du mi. Phng php n y ch xc nh h m lng tro sunfat thp ti 0,005% i vi du cha ph gia v khng p dng cho du ng c ph thi, du cha ch, du khng c ph gia. Thng h m lng tro sunfat lin quan n tr s kim ca du ng c. Ni chung h m lng tro sunfat ln th gi tr tr s kim ln v ngc li. H m lng tro sunfat l gm c tro ca cc ph gia a v o l m tng tnh nng ca du, cn khi ta thy lng tro tng qu mc th l do s c mt ca cc tp cht nh cc cht bn, cn do m i mn v cc loi tp khc. Lng ph gia cho v o du nhn c khi ln ti 20% khi lng v cc ph gia thng l sunfunat, phenolat, salisilat ca cc kim loi kim (Ba, Ca, Na). iu n y gii thch v sao h m lng tro sunfat ca du ng c cao. * Quy trnh xc nh: Nung chn s nhit 700 - 8000C trong khong 3045 pht, ngui trong bnh ht m n nhit phng (khong 45 pht) v cn vi chnh xc ti 0,1 mg. Cn chnh xc lng mu th (khong 5 - 10g) v o chn nung c giy lc bng xanh khng tro l m lt chn, sau dng ng giy lc l m phu trn lp du, phu thm ht du ta cho chn mu ln bp ri chm ngn la t t t n khi ch li tro v cn cacbon khi chy ht. chn mu sau khi cho ho v nhit phng th dng axit sunfuaric c nh tng git l m m to n b cn, ri nung tip tc trn bp n khi c khi trng bc ln th cho v o l nung 775250C khong 45 - 60 pht, ly chn ra l m ngui cng thi gian ban u ca chn khng ri cn n trng lng khng i.
BM. Lc Ha du
45
Dng Vit Cng

1.4.7 T trng ASTM D 1298 T trng l t s gia khi lng ring ca mt cht cho nhit quy nh so vi khi lng ca nc nguyn cht nhit quy nh . T trng c xc nh theo ASTM D 1298 bng phng php t trng k. Ch tiu t trng c th thy s ln sn phm khc v o du khi thy mt gi tr bt thng ca khi lng ring. Vic xc nh n y cng cn thit chuyn i gia trng lng v th tch, hn th n cng c ch trong vic nhn bit loi sn phm du, nu bit thm khong nhit chng ct hay nht. * Quy trnh xc nh: Rt mu nh nh ng v o ng ong loi 500 ml sao cho trnh to bt v trnh bay hi mt phn nh, t trng k ni v c c s . Sau t ng cha mu thng ng, th t t t trng k thch hp v o mu th sao cho khng chm th nh ng v yn. Sau khi ch cho mu v t trng k n nh th tin h nh c kt qu. 1.4.8 Cn khng tan ASTM D 893 Trong qu trnh ng c l m vic du lun b bn do nhiu sn phm khc nhau tch li trong du nh: nc, m hng, nhin liu, cc ht mui than, bi, cc ht do m i mn, cc sn phm oxy ha, x phng kim loi S pha trn ca du b bn ni trn trong iu kin nht nh s dn ti to th nh mt cht dnh sn st tch t du ra v lng xung y cacte du, hp supap, trong ng ng dn du, trong h thng bi trn v cc bu lc. Hin tng tch cn trong ng c c th l m ng c hot ng mt bnh thng v l m hng ng c nh: - Cn c th l m tc r nh du, ng du v cc bu lc, do c th xy ra nng chy bc lt , kt c trc khuu v c th gy ra s c. - Cn c th l m cho du mi gim phm cht ngay sau khi mi cho v o ng c Th nh phn ca cn thng ph thuc v o iu kin sinh ra n. Thng cn gm 50 n 70% du v 5 n 15% nc, cn li c nhin liu, sn phm oxy ha v cc ht rn. nht ca du tng ln th kh nng to cn gim i. Cc loi du khng n nh i vi hin tng oxy ha s to cn nhanh hn v khi lng cn nhiu hn. Cc loi du c ph gia chuyn dng s t c khuynh hng to cn v chng gip cho du gi c cc tp cht khng ha tan v kh nng chng oxy ha mnh hn. Nh vy, s to cn trong qu trnh hot ng ca ng c l mt trong BM. Lc Ha du
46
Dng Vit Cng

nhng yu t chnh lin quan ti cht lng du nhn. Cc cn n y bao gm: - Lp vecni mng vng chc, khng tan c, ng trn cc chi tit chuyn ng trong ng c xng. - Cn lc ng trn cc chi tit chuyn ng trong ng c diesel. - Cn bn l loi cn mm, tch t trn b mt cc chi tit khng chuyn ng trong ng c. Vecni, cn lc l loi cn nhit cao, cn cn bn l loi cn nhit thp. C th phn bit v xc nh: - Cn khng tan trong dung mi khng cc (pentan): l cn c hc v lng nha ng thc t. - Cn khng tan trong dung mi c cc (toluen): l cn c hc Do phn tn ca du trng ti nng dng cho ng c diesel ph thuc v o cc tnh nng ca sn phm, nn cn phi da v o kinh nghim nh ra gii hn cn khng tan, m ti du phi thay. Thng ngi ta cng quan tm n ngun gc ca du bi trn v tnh nng ca ng c. Vi du ng c c phn tn cao, th lng cn khng tan c t n 3 - 4% vn chp nhn c. * Quy trnh xc nh: Cn khong 10 gam mu gia nhit khong 600C cho u mu, cho v o ng ly tm ra sch sy kh 10050C n trng lng khng , cho tip khong 100 ml dung mi pentan (ln 1) v toluen (ln 2), nt ng ly tm li v cho v o my ly tm theo ch t trc. C th lc li 2 n3 ln cho cn sch du, ri cho v o sy 1050C n trng lng khng i. Nu du trong pentan v toluen kho tch c, ngi ta phi dng ch ng t v lp li nh trn. 1.4.9 H m lng kim loi ASTM D4628 Kim loi c trong du nhn di cc dng sau: - Dng phn tn trong du s dng di cc ht m i mn v cc ht g, ht n mn. - Dng ha tan c trong du nhn l kim loi trong cc hp cht c kim ca ph gia. Nhiu loi du bi trn c pha ch vi cc ph gia c cha kim loi, cc ph gia n y c tc dng nh l cc cht ty ra, cc tc nhn chng m i mn, cc cht c ch oxy ha, cc cht chng g Mt v i loi ph gia ng gi c cha khng ch mt m nhiu kim loi nh: canxi, magi, km. Vic phn tch cc nguyn t trong du mi v du s dng thng c tin h nh bng cc phng php phn tch cng c nh quang ph hp th nguyn t, quang ph pht x v quang ph hunh quang tia X. Php phn tch nguyn t l
BM. Lc Ha du
47
Dng Vit Cng

rt cn thit gip cho vic khng nh h m lng ph gia, nhn ra cc h thng b m i mn v xc nh nhim bn. * Quy trnh xc nh: Theo Phng php ASTM D4628 Dng cht chun c nng chun dng ng chun. Mu chun c pha lo ng bng du ho tinh khit, ta thit lp mt ng chun bng ba mu chun trong gii hn pht hin ca my. Mu du cn phn tch cng c ch ha bng cch pha lo ng nh ng chun v phi nm trong ng chun. Sau nhng dung dch n y c em phn tch bng cch t chng trong ngn la axetylen/oxy khng kh ca my quang ph hp th nguyn t. T ta xc nh h m lng kim loi c trong mu du.
Hnh 7: My hp th nguyn t xc nh h m lng kim loi 1.4.10 H m lng nc ASTM D 95 H m lng nc ca du l lng nc c tnh bng phn trm theo trng lng th tch hay theo ppm (phn triu). H m lng nc trong du bi trn l mt c trng quan trng i vi mt s loi du nh du thy lc, du t, du bnh rng cng nghip c bit l n cc k quan trng i vi du bin th. S c mt ca nc trong du bi trn y nhanh qu trnh gy n mn, g chi tit my, tng qu trnh oxy ha du v cn gy to nh l m mt tc dng ca ph gia cha trong du. Trong mt v i trng hp, nc cn l m thy phn cc ph gia, to nn nhng bn mm xp. V vy, h m lng nc trong du mi cng nh du ang s dng phi c khng ch rt nghim ngt. Vi nhng loi du c bit nh du bin th chng hn, khng c php c mt ca nc. khng ch lng nc trong du iu kin my ang l m vic ngi ta phi cho v o du nhng ph gia c tnh kh nh tch nc nhanh ra khi h thng.
BM. Lc Ha du
48
Dng Vit Cng

1.5 Cc php th tnh nng p ng yu cu bi trn nhiu loi my mc khc nhau, cc cht bi trn cn phi khng nhng c mt ph rng v thuc tnh vt l v ho hc, m cn phi tri qua cc php th tnh nng. Php th tnh nng ng vai tr quan trng, gip sn xut ra nhng sn phm ng nht. Vic th nghim tin h nh trong iu kin thc t l bin php tt nht nh gi tnh nng ca du bi trn v l vic nh gi cui cng i vi mt loi du mi hay mt n pha ch mi c a v o th trng. Mt khc, vic th tnh nng trn hin trng ngay bc u ca vic nghin cu du bi trn l khng kh thi v n i hi thi gian d i v khng kinh t. Chnh v vy, cc phng php th nghim trong phng th nghim di cc iu kin th nghim tng t nh iu kin l m vic thc t ca du bi trn c la chn. 1.5.1 Php th chng m i mn v chu p cao Thuc tnh chng m i mn ca du bi trn thng c tin h nh bng my bn bi theo tiu chun ASTM D4172 (c tnh chng m i mn ca cc cht lng bi trn). Phng php th n y c th xc nh tnh chng m i mn ca du bi trn trong tip xc trt nhng iu kin nh trc. ng knh bn vin bi l 12,7 mm Lc tc dng ln vin bi trn cng l 147N hoc 392 N Nhit ca qu trnh th nghim c duy tr 750C Vin bi trn cng c cho quay vi tc 1200 vng/pht. Thi gian th nghim l 60 pht. Du bi trn c rt v o cc c cha cc vin bi c nh. iu quan trng l phi m bo du ngp cc phn tip xc ca cc vin bi th nghim. Cc loi du bi trn c so snh vi nhau bng cch cn c v o kch thc trung bnh ca ng knh vt m i trn ba vin bi c nh. - Thuc tnh chu p cao Thuc tnh chu p cao cng c xc nh bng my bn bi theo tiu chun ASTM D2783 (xc nh chu p ca cc cht lng bi trn). Phng php n y xc nh tnh chu ti ca cc loi du bi trn, k c t s ti trng m i mn v ti trng gy h n dnh. V c bn phng php n y tng t i vi phng php xc nh thuc tnh chng m i mn ca du bi trn, ch khc ch trong phng php n y ti trng F c tng dn t thp ti cao cho ti khi xut hin hin tng h n dnh th dng li. Ch s ti trng m i mn lin quan ti kh nng gim m i mn ti mc nh BM. Lc Ha du
49
Dng Vit Cng

nht mt ti trng nht nh ca mt cht lng bi trn. im h n dnh l ti trng nh nht l m vin bi quay h n dnh v o ba vin bi c nh th hin mc p sut ti a m cht lng bi trn chu c.
E B A
Bin dng n hi Hnh 8: th biu din s ph thuc ca ng knh vt xc v o ti trng ABE: ng b chnh; B ti trng cc i m cha kt my, BC: vng gy ra kt my; CD: vng kt my tc thi; D: ti trng h n dnh Ngo i cc phng php nu trn cn c cc phng php xc nh m i mn cho tng loi du bi trn nht nh nh phng php ASTM D2882 l phng php o m i mn dng bm Vicker xc nh tnh m i mn ca cc cht bi trn thu lc..... 1.5.2 Php th n mn tm ng Du th c th cha cc hp cht cha lu hunh, phn ln cc hp cht n y c loi ra khi du trong qu trnh ch bin. Tuy nhin, cc hp cht lu hunh cn li trong du bi trn th nh phm se gy n mn nhiu kim loi khc nhau, Theo phng php n y tm ng c nh bng v ngm ngp trong mu du cn th nghim. Ngi ta gia nhit n mt nhit nht nh v gi trong mt thi gian nht nh, tu thuc v o tng loi du. Khi php th kt thc, tm ng c ly ra, ra sch v em so vi bng tiu chun ASTM v n mn tm ng.
BM. Lc Ha du
50
Dng Vit Cng

Bng 4: nh gi mc n mn tm ng Phn loi 1 Ch nh Hi m M t a. Da cam nht hu nh ging vi tm ng mi nh bng. b. Da cam ti a. ru vang b. M u xanh nht pha hi (m u Lavender) c. Nhiu m u vi m u xanh nht pha hi hoc c hai b che ph bi m u ru vang d. Bc e. ng thau hoc v ng a. M u ti c ph trn tm ng b. Nhiu m u v xanh nhng khng c m u xm a. en chuyn tip xm en hoc m u nu vi m u xanh hi bic r rt b. M u n than ch d. M u en bng
M trung bnh
M ti
n mn
Mc n mn 1a l thp nht (n mn t nht) v mc n mn 4c l cao nht (n mn nhiu nht). 1.5.3 Php th c tnh to bt Vic nh gi kh nng to bt ca du ht sc quan trng. Bt c th l m thc y qu trnh oxi ho du, l m mt tnh ng nht ca du, gim hiu sut bi trn ca du, gy hng hc cc h thng c hc, gy ra cc hin tng n mn.... Bn cht ca bt l mt lng khng kh nh c bao quanh bi mt m ng du bi trn cc mng, bt c hnh th nh trong iu kin du b khuy trn (mnh) khi tip xc trc tip vi khng kh (nu khng tip xc vi khng kh th d khuy trn mnh th n o cng khng to bt). Tiu chun ASTM D892 (c tnh to bt ca du bi trn) a ra nhng c trng to bt ca du mi, t l du cha b bn. Kt qu thu c s l khng tng ng nu du b ln cc cht khc nh hi nc m, cc cn g rt mn... v nhng cht n y l m tng kh nng to bt ca du. Nguyn tc ca phng php th n y l ngi ta sc khng kh v o mu du nhit , thi gian nht nh sau o to bt V2, 10 pht cho bt xp bt o bn ca bt V2 v th tch ban u ca mu du l V1. Thng thng ngi ta xc nh c tnh to bt ca du bi trn theo ba giai BM. Lc Ha du
51
Dng Vit Cng

on: giai on 1 xc nh to bt 240C, giai on 2 xc nh to bt 940C v giai on 3 xc nh to bt 240C. * Quy trnh xc nh: Cho 180 ml du mi v o ng ong loi mt lt, sau ngm ng ong c du v o b gia nhit theo mt nhit cho php, trong khong thi gian nht nh. Sau dng khuych tn ngm trong 5 pht, ri ni khuych tn vi ng dn kh v o v iu chnh tc kh n 945ml, buc khng kh kh sch i qua khuych tn trong 5 pht 3 giy, thi gian tnh t bong bng u tin ri khi vin . Khi ngng 5 pht thi kh l ta phi ghi ngay th tch bt t mc du cho ti nh ca bt v theo di sau 5 pht tip theo (hoc 10 pht k t lc thi kh) th tch bt cn li bao nhiu.
V2 V2
Khng kh
V1
Hnh 9. Xc nh c tnh to bt ca du 1.5.4 Php th c tnh to nh ca du Trong rt nhiu trng hp cc loi du bi trn thng ln nc. S d c nc ln v o du nh vy l do nc c trong khng kh ngng t hay do du tip xc vi hi nc nh trong trng hp du tuabin hi nc. Nu lng nc khng nhiu v khng ho n to n tch ra, th nh s c to th nh v nc c gi trong du dng nh tng, phn nc n y tip xc vi cc b phn bng st ca thit b c bi trn v l m han g cc b phn n y. Nh cng l m tng qu trnh oxi ho du bi trn v gim kh nng bi trn ca du. Phng php ASTM D 1410 v D2714 cho php o khuynh hng to nh vi nc ca du. Phng php ASTM D1410 (kh nng tch nc ca cc cht lng du m v tng hp) l php o kh nng tch nc ca du bi trn. Mc d ngi ta xy dng phng php n y l cho ring cc loi du tuabin hi nhng n cng c th dng cho cc loi du bi trn khc vi nhng nht khc nhau. Php o n y c tin h nh nh sau: v o mt ng ong hnh tr 40ml mu du v 40 ml nc ct , ri khuy mnh trong 5 pht 540C, mc tch nh c ghi li theo tng thi gian. i vi hu ht cc loi du i hi sau 30 pht, lp nh ch c cn li t hn 3 cm3. Nu sau 1h vic tch ho n to n nh khng xy ra, th phi ghi li th tch du, th tch nc v th tch nh. BM. Lc Ha du
52
Dng Vit Cng

1.5.5 Php th bn oxi ho Oxi ho l qu trnh khng mong mun xy ra i vi du bi trn. bn oxi ho ca du bi trn l mt c trng quan trng ca du. c bit nhng my tuabin v bin th i hi nhng loi du dng lu m khng bi hng. S oxi ho du bi trn ph thuc v o nhit , lng oxi cha trong du v hiu ng xc tc ca nhng kim loi. Phng php xc nh bn oxi ho hay c s dng l ASTM D943 (c tnh oxi ho ca cc loi du khong c cha cc cht c ch), phng php n y c th p dng cho hu ht cc loi du bi trn, c bit l cc loi du cha ph gia chng oxi ho. Tuy nhin, phng php n y c xy dng ch yu cho du tuabin hi nc nn n c bit coi trng vic xc nh bn oxi ho i vi du bi trn c ln nc. Quy trnh th nghim ca phng php n y nh sau: du cn th c ng trong mt ng nghim c cha nc ct v mt cun dy ng st l m cht xc tc. Ti u ng nghim c b phn l m lnh bng nc gi li cc th nh phn hi. Mt dng oxi c tc quy nh c sc v o hn hp du nc k trn nhit 950C cho n ch s trung ho bng 2,0; theo tiu chun quy nh th thi gian th nghim c gi l thi gian sng ca qu trnh oxi ho Ngo i ra ngi ta cn c th dng phng php ASTM D2893 ( bn oxi ho ca du bi trn chu p): mu du c gi 950C vi s c mt ca khng kh kh trong vng 312h. Sau du c em xc nh ch s kt qu v s tng ca nht ng hc. 1.5.6 Php th kh nng chng g Trong nhiu trng hp du bi trn c th b ln nc do vy trong qu trnh s dng n c th gy ra hin tng g. Phng php ASTM D665 (nhng c tnh chng g ca du c cht c ch khi c mt nc) c dng rng r i nh gi kh nng chng g ca du bi trn. Phng php n y gm hai phn: mt quy trnh (A) s dng nc ct v mt quy trnh (B) s dng nc bin nhn to. Mt mu thp th c ngm trong hn hp du vi nc ct hay nc bin nhn to. Hn hp n y c khuy lin tc trong qu trnh th, thng qu trnh n y ko d i trong 24h. Cn lu rng rt kh nh gi thuc tnh chng g ca du bi trn. Qu trnh g st l qu trnh phn ng ho hc nn khi n xy ra rt kh ngn chn chng, bi vy khi ta chun b mu cho php th n y cn trnh ti a s tip xc ca mu vi khng kh hay hi m t trnh mu vt b g trc khi th nghim. Ngay c khi tin h nh th nghim ht sc cn thn, php th n y thng t khi cho kt qu c tnh lp li cao. BM. Lc Ha du
53
Dng Vit Cng

1.6 Pha ch du nhn Mi loi du bi trn c cp nht cng nh cp phm cht API khc nhau th n pha ch ca mi loi du l khc nhau. c mt loi du bi trn mi, ngi ta tin h nh qu trnh pha ch du da trn cc n pha ch. n pha ch c hnh th nh da trn cc kt qu ca qu trnh nghin cu v th nghim. Cc nh ch to thit b da v o cu to v tnh nng hot ng ca thit b m a ra cc yu cu v cht bi trn. Da v o cc yu cu n y, cc nh nghin cu v sn xut du bi trn la chn nguyn liu cho qu trnh pha ch. Bao gm du gc v cc loi ph gia tng hp tt vi nhau theo mt t l n o p ng yu cu bi trn cho thit b cn c bi trn. Trc ht, ngi ta pha th trong phng th nghim mt du bi trn nh d nh trn v tin h nh o cc thng s ha l, cc thng s ca cc php th tnh nng; Tip theo l tin h nh th trn cc thit b trong phng th nghim, m cc thit b n y c ch hot ng tng t nh cc thit b cn bi trn bn ngo i. Nu kt qu th nghim tt, th du c a ra th hin trng. Sau khi th nghim hin trng cng cho kt qu tt th mt n pha ch cho loi du bi trn c lp ra. Vy mun nh gi pha ch mt mu du nhn ta phi tin h nh kho st v la chn hai yu t cn bn, quyt nh l : du gc v cc loi ph gia. 1.6.1 La chn du gc Du gc l hp phn ch yu ca du nhn, bn thn du gc m nhim c cc chc nng theo cc yu cu bi trn. La chn du gc chnh xc s gip cho ng c hot ng mt cch trn chu khi ng c hot ng cc iu kin khc nhau, chng loi khc nhau. Bng 5, 6, 7 a ra mt s ch tiu c bn ca mt s loi du gc thng c s dng pha ch du nhn Vit Nam. Du bi trn thng c kt hp t nhiu th nh phn khc nhau. Do to ra mt loi du c nht nh mong mun ta phi xc nh nht ng hc nhit n o ca tng th nh phn to nn hn hp . Tiu chun ASTM 341 a ra phng php xc nh th nh phn phn trm th tch ca tng loi du gc. S dng theo biu hnh 10 v 11. Trc ho nh biu din nhit (0C), trc tung biu din nht ng hc (cSt). Cn c v o nht du cn pha ch (v d y l 15 cSt), loi du gc, k ng thng song song vi trc ho nh c tung l nht ng hc, tm cc im tng ng cho du SN 150, SN 500 v BS 150. Trong Du SN 150 ng 1, du BS 150 ng 2 v du SN 500 ng 3. Ni hai im ca mi loi du li ta c ng thng nhit nht ca loi du . ng thng nm ngang n y ct ng 1 ti N, ct ng 2 ti M, ct ng 3 ti K v ct ng thng ng i qua im 1000C ti I. BM. Lc Ha du
54
Dng Vit Cng

V d 1: Hn hp du gc trong mu s 1 (gm BS 150 v SN 500): Phn th tch ca du c nht ng hc cao (BS 150) cn pha v o hn hp l : VBS 150% = (KI/KM).100 = (1,12/3,48).100 = 32,18% Vy phn th tch ca du c nht ng hc thp (SN 500) l : VSN 500% = 100 32,18 = 67,82%
30 500 400 300 200 40 50 60 70 80 90 100 110 120 130 500 400 300 200 150
kinematic viscosity, centistokes
150 100 75 50 40 30
(2) (3)
100 75 50 40 30
20 15
20
i k
15
10 9.0 8.0 7.0 6.0 5.0 30 40 50 60 70 80 90 100 110 120 130
10 9.0 8.0 7.0 6.0 5.0
temprature, degrees, celcius
Hnh 10: Biu xc nh th nh phn ca hn hp BS 150 v SN 500 ( 100C tng ng vi 1 n v d i) V d 2: Hn hp du gc trong mu s 2 (gm BS 150 v SN 150): Phn th tch ca du c nht ng hc cao (BS 150) cn pha v o hn hp l : VBS 150% = (NI/NM).100 = (4,15/6,51).100 = 63,75% Vy phn th tch ca du c nht ng hc thp (SN 150) l : VSN 150% = 100 63,75 = 36,25%
BM. Lc Ha du
55
Dng Vit Cng

30 500 400 300 200 40 50 60 70 80 90 100 110 120 130 500 400 300 200 150
kinematic viscosity, centistokes
150 100 75 50 40 30
(2)
100 75 50 40 30
20 15
(1) m N I
20 15
10 9.0 8.0 7.0 6.0 5.0 30 40 50 60 70 80 90 100 110 120 130
10 9.0 8.0 7.0 6.0 5.0
temprature, degrees, celcius
Hnh 11: Biu xc nh th nh phn ca hn hp BS 150 v SN 150 ( 100C tng ng vi 1 n v d i)
BM. Lc Ha du
56
Dng Vit Cng

Bng 5: Kt qu cc ch tiu ha l ca du gc SN150 TT 1 2 3 4 5 6 7 8 9 10 11 12 13 14 Tn ch tiu Cm quan nht ng hc 400C nht ng hc 1000C Ch s nht (VI) Khi lng ring 150C Khi lng ring 300C H m lng nc kh nh to bt 93,50C Nhit chp chy mu n mn tm ng H m lng cn cacbon Kh nng OXH: - nht ng hc 1000C sau khi oxh - Axit tan trong nc - Axit tan trong du - Tng h m lng cn Phng php Nhn mt thng ASTM D 445 ASTM D 445 ASTM D 2270 ASTM D 1298 ASTM D 1298 ASTM D 95 ASTM D 1401 ASTM D 892 ASTM D 92 ASTM D 1500 ASTM D 130 ASTM D 524 GOST 981-75 n v cSt cSt kg/l kg/l %V ml/ml/ml/ph ml/m 0 C % Kt qu Trong 29,13 5,01 95 0,8738 0,8648 Vt 40/40/3/12 30/0 230 1,0 1a 0,14 5,36 0,36 1,12 0,112
cSt mg KOH/g mg KOH/g %
BM. Lc Ha du
57
Dng Vit Cng

Bng 6: Kt qu cc ch tiu ha l ca du gc SN500 TT 1 2 3 4 5 6 7 8 9 10 11 12 13 14 Tn ch tiu Cm quan nht ng hc 400C nht ng hc 1000C Ch s nht (VI) Khi lng ring 150C Khi lng ring 300C H m lng nc kh nh to bt 93,50C Nhit chp chy mu n mn tm ng H m lng cn cacbon Kh nng OXH: - nht ng hc 1000C sau khi oxh - Axit tan trong nc - Axit tan trong du - Tng h m lng cn Phng php Nhn mt thng ASTM D 445 ASTM D 445 ASTM D 2270 ASTM D 1298 ASTM D 1298 ASTM D 95 ASTM D 1401 ASTM D 892 ASTM D 92 ASTM D 1500 ASTM D 130 ASTM D 524 GOST 981-75 n v cSt cSt kg/l kg/l %V ml/ml/ml/ph ml/m 00C % cSt mg KOH/g mg KOH/g % Kt qu Trong 98,50 10,93 95 0,8844 0,8755 Vt 40/40/0/6 40/0 260 1,0 1a 0,12 11,59 0,54 1.45 0,1226
BM. Lc Ha du
58
Dng Vit Cng

Bng 7: Kt qu cc ch tiu ha l ca du gc BS150 TT 1 2 3 4 5 6 7 8 9 10 11 12 13 14 Tn ch tiu Cm quan nht ng hc 400C nht ng hc 1000C Ch s nht (VI) Khi lng ring 150C Khi lng ring 300C H m lng nc kh nh to bt 93,50C Nhit chp chy mu n mn tm ng H m lng cn cacbon Kh nng OXH: - nht ng hc 1000C sau khi oxh - Axit tan trong nc - Axit tan trong du - Tng h m lng cn Phng php Nhn mt thng ASTM D 445 ASTM D 445 ASTM D 2270 ASTM D 1298 ASTM D 1298 ASTM D 95 ASTM D 1401 ASTM D 892 ASTM D 92 ASTM D 1500 ASTM D 130 ASTM D 524 GOST 981-75 n v cSt cSt kg/l kg/l %V ml/ml/ml/ph ml/m 0 C % cSt mg KOH/g mg KOH/g % Kt qu Trong 467,60 30,94 96 0,9002 0,8909 Vt 40/40/3/17 35/0 305 4,5 1a 0,45 32,23 0,16 0,91 0,0091
1.6.2 La chn ph gia Ph gia dng pha ch du bi trn phi c c cc tnh cht chung nht c th c a mt cch hiu qu v o du gc, nhng tnh chung l : - Tan ho n to n trong du gc - n nh ha hc. - Khng c hi - C tnh tng hp - bay hi thp - Hot tnh c th khng ch c - Tnh linh hot Du ng c thng cha h ph gia a th nh phn, bao gm: Ph gia ci thin ch s nht, ty ra phn tn, tribology, c ch oxy ha, chng to bt
BM. Lc Ha du
59
Dng Vit Cng

Cc ph gia n y c th tng tc vi nhau trn b mt, l m nh hng xu ti chc nng ca du. V d: Ph gia phn tn, ty ra tng tc vi c ZDDP ln ph gia cc p l m xu i kh nng chng oxy ha v tnh gim m i mn ca du. Mt khc, cn lu l chc nng ca ph gia thng ph thuc v o kh nng tan c chng trong cht bi trn. do m ZDDP c kh nng tch khi khi cht bi trn v bm v o b mt chi tit my c bi trn lmf gim m i mn. Trong ph gia ng gi c cha ph gia phn tn th n c th ko gi ZDDP li trong dung dch v v th m ngn cn tc ng ca ZDDP. Mt khc, cc ph gia hot ng b mt c th cnh tranh ln nhau. V d c ZDDP v mt s ph gia chng g, th ng ha kim loi u hp ph ln b mt kim loi v chng cnh tranh nhau trn cng b mt. Hu qu l ph gia chng g c th thay th ph gia chng m i mn trn b mt v c hi cho s c ch m i mn. Tng t nh vy phuj gia chng m i mn c th th ch ph gia chng g. Thng thng ph gia to kh nng phng nga cn thit cho du khi s dng nhit cao, p sut cao v tc cao. Trong khi bn cht ca ph gia c th nh nhau i vi cc loi cht bi trn khc nhau th loi ph gia c th c la chn ph thuc v o mc ch s dng ca du bi trn v c tnh ca du gc. iu n y lin quan n kh nng tan ca ph gia v s phn ng li ty theo th nh phn ca du gc. Bng 8 a ra cc loi ph gia c dng pha ch cc loi du bi trn khc nhau. 1.6.3 iu chnh h m lng kim loi, tr s kim tng trong qu trnh pha ch du nhn. Khi iu chnh nht, nu s iu chnh y l m cho nng cc ph gia trong du tng ln hoc gim i, iu c th dn n h m lng kim loi, tr s kim tng nm ngo i vng quy nh. Lc phi phi hp iu chnh sao cho c nht, TBN cng nh h m lng kim loi u phi nm trong vng quy nh. C nhng m pha ch tuy khng phi iu chnh nht nhng khi phn tch cc ch tiu trn cng cho kt qu nm ngo i vng cho php th cn phi iu chnh sao cho cc ch s n y tr v trong khong gii hn quy nh. Song cng nh trn vic iu chnh lun lun phi phi hp sao cho c nht, TBN v h m lng kim loi u phi nm trong vng cho php. i vi nhng loi ph gia mang tnh kim, nh ph gia ty ra l cc hp cht cha Ca, Mg th kt qu xc nh TBN v kt qu phn tch hai kim loi trn bng quang ph hp th nguyn t c th h tr kim tra ln nhau. V vy vic iu chnh s tnh ton nh sau: Nu TBN v h m lng kim loi Ca, Mg thp hn vng BM. Lc Ha du
60
Dng Vit Cng

quy nh th phi tnh ton thm mt lng ph gia ty ra. Nu TBN v h m lng kim loi cao th ta phi thm mt lng du gc thch hp v o sao cho nht ca du gc thm v o tng ng vi nht ca du cn iu chnh. Bng 8: Cc loi ph gia c dng pha ch cc loi du bi trn khc nhau Loi du bi trn Ph gia Du ng c Cht ci thin ch s nht Cht c ch oxi ha Cht phn tn - ty ra Cht c ch n mn Cht c ch g Cht Chng m i mn Cht chng to bt Ph gia Tribology Cht ci thin ch s nht Cht c ch oxi ha Cht chng to bt Ph gia Tribology Cht c ch g Cht c ch oxi ha Cht chng to bt Ph gia Tribology Cht c ch g Cht c ch n mn Cht c ch g Ph gia Tribology Cht c ch oxi ha Cht c ch n mn Cht c ch g Cht to nh, kh nh
Du thy lc
Du bnh rng
Du cng c
Du tuabin hi nc
i vi nhng ph gia khng mang tnh kim, nh cc ph gia chng m i mn Diankydithiophotphat km th tr s kim tng v h m lng kim loi khng lin quan g vi nhau. Do kt qu phn tch kim loi khng tham kho cho kt qu ca TBN. Trong trng hp n y khi iu chnh phi ph thuc v o tng th nh phn m c s iu chnh khc nhau tt c kt qu u t nh mong mun.
BM. Lc Ha du
61
Dng Vit Cng

1.7 Mt s loi du bi trn
Trong thc t, du bi trn c chia th nh hai loi c bn: du ng c v du cng nghip. Trong tng loi du, gip cho vic s dng du mt cch thch hp, ngi ta tip tc chia th nh cc loi du khc nhau da v o cc ch tiu k thut hoc da v o mc ch s dng. 1.7.1 Du ng c Du ng c l du bi trn c s dng bi trn cc ng c. Du ng c l nhm du quan trng nht trong cc loi du bi trn. Tnh trong bnh, chng chim khong 40% tng cc loi du bi trn trn th gii. Ti Vit Nam hin nay du ng c chim khong 70% lng du bi trn. Ti cc nc ang pht trin khc tnh hnh cng tng t. Mi loi ng c yu cu mt loi du bi trn thch hp tng ng. Tuy nhin, d cho l ng c nh th n o th du bi trn vn phi m bo thc hin c cc chc nng: bi trn, l m mt, l m kn v l m sch. Mc t c cc chc nng n y ti u ph thuc v o loi du c la chn ph hp vi c tnh thit k ban u ca ng c, nhin liu c s dng, iu kin vn h nh. Cht lng bo dng ng c cng rt quan trng, n lin quan ti c tui th ng c ln chu k thay du. Vic phn loi du ng c hin nay c kh nhiu phng php, trong ph bin nht l phn loi du ng c da trn cp nht v phn loi theo tiu chun cht lng. 1.7.1.1 Phn loi du ng c theo cp nht SAE (Society of Automotive Engineers) i vi phng php n y ngi ta chia du ng c th nh ba loi c bn: du ma ng, du ma h v du bn ma. Du ma ng c k hiu l SAE SW: l loi du c nht c xc nh ti 180C. Du ma h c k hiu l SAE n (n l s hiu v d 50, 60.... s c trnh b y c th trong phn tip theo): l loi du ng c c nht c xc nh ti 1000C. Du bn ma c k hiu l SAE SW/n: l loi du c cp nht tng ng vi du SAE SW khi xc nh nht 180C v tng ng vi du SAE n khi xc nh nht 1000C. V d: Du bn ma c k hiu l SAE 50W/60 ngha l du n y c cp nht l 60 khi vn h nh iu kin ma h v cp nht l 50W khi vn h nh trong ma ng. BM. Lc Ha du
62
Dng Vit Cng

Bng 9: Cp nht SAE ca du ng c Cp nht nhit (0C), mPa.S, max nht 1000C, mm2/s nht SAE Khi ng Kh nng bm Min Max OW 3250 30 30.000 35 3,8 5W 3500 -25 30.000 -30 3,8 10W 3500 -20 30.000 -25 4.1 15W 3500 -15 30.000 -15 5.6 20W 4500 -10 30.000 -15 5.6 25W 6000 -5 30.000 -10 9.3 20 5.6 <9.3 30 9.3 <12.5 40 15.5 <16.3 50 16.3 <21.9 60 21.9 <26.1 Tuy nhin cch phn loi trn ch tp trung phn loi du bi trn trong phm vi nht, m khng cp hoc bao h m cc tnh cht khc ca du. 1.7.1.2 Phn loi theo tiu chun API (American Petroleum Institute) Theo phng php n y du ng c c chia th nh bahm chnh: - Nhm S: du ng c c s dng cho ng c xng - Nhm C: du ng c dng cho ng c diesel - Nhm S/C: du ng c dng cho c ng c diesel v ng c xng i vi nhm S v nhm C ngi ta s dng cc ch ci biu hin mc cht lng ca du ng c. SA, SB, SC, SD, SE, SF, SJ theo th t n y mc cht lng ca du ng c xng tng dn. Tng t, CA, CB, CC, CD, CE, CF theo th t n y cht lng ca du ng c diesel tng dn. Du c s dng cho c ng c xng v ng c diesel tng ng vi tng mc cht lng khi s dng cho ng c xng v ng c diesel c k hiu l SD/CF.
BM. Lc Ha du
63
Dng Vit Cng

Bng 10: Phn loi du ng c theo tiu chun API i vi ng c xng Cp SA SB Phm vi s dng ng c kiu c, hot ng trong cc iu kin nh nh ng v khng cn thm bt c ph gia n o. Dng cho cc ng c ti trng cc nh, ch cn mt lng ph gia bo v ti thiu chng oxy ha, g, mn , chng kt xc. Cp du n y dng cho cc loi xe sn xut trong thi gian 1964-1976. Du c kh nng hn ch cn, n mn, chng g v m i mn nhit cao hoc thp. Cp du n y dng cho cc loi xe sn xut trong thi gian 1968-1970. Du c kh nng chng to cn trong ng c nhit cao cng nh nhit thp; chng m i mn, chng g v chng n mn. Du ti trng nng, dng cho cc ng c i 1972. Du c kh nng cao hn chng li s oxy ha du, s to cn nhit cao, chng g v n mn. Du ti trng nng, dng cho cc i ng c i 1980-1988. Du c pha ch t n nh oxy ha v tnh chng m i mn cao hn. Du ti trng nng, c tng cng kh nng chng oxy ha, chng to cn v chng n mn ng c. Du cp SG cn bao gm c cp CC, CD. Du ti trng nng, c tng cng kh nng chng oxy ha, chng to cn v chng n mn ng c. Dng cho ng c i 1994. Du ti trng nng, dng xng khng ch, dng cho ng c i 1996.
SC
SD
SE
SF
SG
SH
SJ
BM. Lc Ha du
64
Dng Vit Cng

Bng 11: Phn loi du ng c theo tiu chun API i vi ng c diesel Cp Phm vi s dng CA Dng cho ng c ti nh n trung bnh, s dng nhin liu c cht lng cao, t lu hunh. CB Dng cho ng c ti trung bnh, khng c tng p, s dng nhin liu c cht lng thp hn. Du c kh nng chng m i mn v chng to cn. CC Dng cho c ng c xng v diesel ti trng nng c tng p va. CD Du ti trng nng s dng cho ng c tng p, l m vic trong nhng iu kin khc nghit, s dng nhin liu c khong cht lng rng c h m lng lu hunh cao. Do , cn khng ch cht ch s m i mn v to cn. CE Du dng cho ng c c tng p ti trng rt nng, sn xut t 1983 tr li, hot ng trong iu kin: tc thp, ti nng v tc cao, ti nng. CF Du dng cho ng c diesel kiu bm nhin liu gin tip, c hoc khng c tng p, s dng nhin liu c h m lng lu hunh cao. CF4 Dng cho i ng c 1990, gim tiu th du v tng cng kh nng chng ng cn. CG4 Du dng cho nhng ng c ti nng, tc cao cng nh tc thp, du c kh nng kim sot tt kh nng ng cn pittng nhit cao. Du dng cho nhng ng c ti trng nng, du c kh nng CH4 kim sot tt kh nng ng cn pittng nhit cao. 1.7.1.3 Phn loi theo c chng du ng c Phn loi du nhn theo c chng ng c thng c p dng cho qun i khi NATO nh: M, Anh, Php, c Bng 12. Phn loi theo c chng du ng c: Du Chc nng ca du nhn nht 100oC c chng hoc tng ng SAE Mi1-1Du nhn cho ng c xng v 2104A diesel trong iu kin l m vi khc 10 W nhau. Mi1-1Dng bo qun ng c xng BM. Lc Ha du
65
Dng Vit Cng

21260B Mi19000F Mi1-146152A (loi 1) v ng c diesel (loi 2). Dng cho ng c diesel t u thy v t u ngm. Dng cho ng c diesel t u thy ln 30 W Min 5,4 cSt 11,9 n 14,5 cSt
Ngo i ra cn c cc cch phn loi du nhn ng c khc nh: phn loi theo tiu chun Nga; phn loi theo tnh nng (cp phm cht) 1.7.2 Du bi trn cng nghip Du bi trn cng nghip bao gm mt s rt ln cc sn phm chuyn dng trong s cc cht bi trn. Do vy, tr mt s nhm nh cht lng thu lc, ngi ta kh c th phn loi du bi trn cng nghip mt cch r r ng nh i vi du ng c. Phn ln cc du bi trn cng nghip c phn loi da theo cp nht ISO 3448, v i vi chng, nht l tiu chun quan trng trong vic la chn du s dng. Tuy nhin, phng php n y kh phc tp v kh nh. V th ngi ta thng t tn du bi trn cng nghip theo mc ch s dng. Theo phng php n y, du bi trn cng nghip c cc loi c bn nh sau: - Du bi trn trc - Du bnh rng (du bi trn bnh rng) - Du my nn - Du (cht lng) thu lc - Du tuabin - Du bi trn my cng c - Du bi trn ct gt kim loi ..v.v.......
BM. Lc Ha du
66
Dng Vit Cng

Chng 2 M bi trn
2.1 Tng quan Nh trong phn trc cp, du bi trn (cht bi trn dng lng) c s dng nhiu nht trong cc loi cht bi trn. Tuy nhin, c nhng trng hp khng th s dng c du bi trn m phi s dng cc cht bi trn dng c hoc dng rn. M bi trn trong nhiu trng hp th hin c u im so vi du bi trn. Chng hn bi trn cc cm ma st kh c iu kin xem xt, ni thi hn s dng cht bi trn cn ko d i; bi trn cc v tr nm nghing thm ch l thng ng, bi trn bi ln c np che kn ti ni sn xut, s dng nhng ni c s tip xc vi nc.v.v... 2.2 Thnh phn ho hc M bi trn l loi sn phm c nhiu dng t rn cho ti bn lng do s phn b ca cc cht l m c, cht bi trn v cc tc nhn khc c a v o to nn cc c tnh ca m. Th nh phn cu to ca m bi trn gm 3 hp phn c bn. Du bi trn, thng l du khong hoc du tng hp, c nhim v bi trn. Cht l m c c nhim v gi du v chng chy du, cht l m c c th l bt c vt liu n o m khi phi hp vi loi du c la chn s to ra mt cu trc rn hoc bn rn. Thng cht l m c l cc x phng kim loi. Cht l m c c pha trn v o du vi t l thch hp thng t 6 - 25% khi lng. Hp phn th ba ca m bi trn l cc ph gia. Cc ph gia c s dng ci thin cc c tnh vn c ca m hoc l m cho m c thm cc c tnh mi cn thit. V c bn, ph gia cho m bi trn ging vi ph gia c s dng cho du bi trn. 2.3 Tnh cht ho l c trng 2.3.1 Nhit nh git Nhit nh git l nhit m ti git m u tin t chn th nghim ri khi l trong iu kin th nghim c quy nh bi tiu chun ASTM D566 hoc TCVN 2697-78. Nhit nh git th hin c tnh chu nhit ca m bi trn. Vic xc nh c nhit nh git s gip ngi s dng s dng hp l v hiu qu m bi
BM. Lc Ha du
67
Dng Vit Cng

trn. Nu nhit l m vic ln hn nhit nh git th tnh nng ho n ho ca m bi trn b gim, m s chuyn sang th lng. ng thi, nhit nh git cng c ngha trong qu trnh bo qun m cng nh trong qu trnh nng cao phm cht ca m. Dng c xc nh nhit nh git bao gm: - Nhit k nh git thng l mt b gm 2 khong o t 0 - 1500C v t 00 2500C. - Chn nh l m bng kim loi hoc thu tinh c kch thc v cu to tun theo tiu chun. - B phn gia nhit 2.3.2 xuyn cn ( ln m) xuyn cn l ln su ca mt thit b hnh cn (chp) kim loi c khi lng v kch thc quy nh theo tiu chun v o khi m th nghim 250C trong thi gian 5 giy. Tu iu kin th nghim m ngi ta chia th nh ba loi xuyn cn: xuyn cn nguyn bn, xuyn cn khng hot ng v xuyn cn hot ng. xuyn cn nguyn bn l xuyn cn c o ngay trong hp ng m, m cha c ly ra s dng. xuyn cn nguyn bn c ngha trong qu trnh bo qun m bi trn. xuyn cn khng hot ng: xuyn cn biu hin cng, mm ca m bi trn. xuyn cn c ng ln chng t m c ng mm v ngc li. ng thi, xuyn cn cn c s dng l m tiu chun phn loi m bi trn. Dng c xc nh xuyn cn bao gm: a. Dng c o xuyn - B phn thng bng dng c - Thit b hnh cn bng kim loi v tr gi c trng lng chnh xc theo tiu chun. - C cu h m m cho thit b hnh cn chuyn ng - ng h ch xuyn cn - Mm nng h cc mu a mt m chm v o mi thit b hnh cn. - Cc ng mu bng kim loi hoc thu tinh. b. Chu nc v nhit k iu chnh nhit m trong cc o v 250C. c. ng h bm giy. d. Ci gi m
BM. Lc Ha du
68
Dng Vit Cng

2.3.3 kim t do Do trong m bi trn khng c ph gia ty ra phn tn nn m bi trn phi c kim t do nht nh c th trung ho cc hp cht c tnh axit sinh ra trong qu trnh s dng m. xc nh kim t do ngi ta s dng phng php chun th tch vi cht ch th m u hoc chun in th. Cht chun l HCl 0,1N, cht ch th m u l phenolphtalein v dung mi l hn hp xng v cn. kim t do c quy i v lng NaOH cn thit trung ho ht lng axit dng trong phng php chun nu trn. 2.4 Phn loi m bi trn Hin nay, ngi ta thng s dng 3 phng php sau phn loi m bi trn: phn loi theo chng loi cht l m c, phn loi theo NGLI (national lubricating grease institute) v phn loi theo chc nng 2.4.1 Phn loi theo chng loi cht l m c Da v o cht l m c ngi ta phn loi m th nh: M x phng l loi m c cht l m c l cc loi x phng; Trong m x phng c th c chia nh hn th nh m x phng ca kim loi kim, m x phng ca kim loi kim th, m x phng ca cc kim loi khc M bi trn gc sp (gc hydrocabon rn). Nhm m n y c cht l m c l cc hydrocabon rn c nhit nng chy cao nh cc parafin, sereizin, cc loi sp t nhin hoc sp tng hp khc nhau..... M gc sp c tnh n nh tt nn thng c dng l m m bo qun (phn loi theo chc nng). M bi trn gc v c: cht l m c l cc cht v c c phn tn cao. Ph thuc v o loi cht l m c ngi ta cn phn ra cc loi m nh m silicagen, m nhn t st, m nhn bentonit, m graphit.... Loi m n y c n nh kh cao thng c dng l m m chuyn dng. M bi trn gc hu c: nhm m n y c cht l m c l cc cht hu c rn c b mt ring kh ln, chu nhit cao v chu nc kh tt.
BM. Lc Ha du
69
Dng Vit Cng

2.4.2 Phn loi theo NLGI (national lubricating grease institute) Phng php phn loi n y da v o xuyn cn. xuyn cn Dng ngo i STT Cp NGLI 250C/0,1 mm 445 475* Na lng 400 430* Cc mm 355 385 Rt mm 310 340 Mm 265 295 Mm va 220 250 Rn va 175 205 Rn 130 160 Rt rn 85 115 Cc rn Bng 13: Phn loi m bi trn theo NGLI 2.4.3 Phn loi theo chc nng (TCVN 5688 - 1992) C cc loi chnh: - M chng ma st - M l m kn - M bo qun - M chuyn dng Bng 14. Gii thiu mt s loi m ti Vit Nam c tnh v cng dng STT Nh n hiu (1) (2) (3) Cng ty PVPDC I. - L m a dng gc x phng liti, c kh nng chu nhit v chu 1. Grease MU 2
nc tt. M c dng rng r i cho c m bm v m lp. Loi m n y do cng ty thng t sn xut nc ngo i theo cng thc v tiu chun ca m Agip MU-2 - L m gc Liti vn nng do cng ty thng nhp t nc ngo i. C tnh chu nc, chu nhit v n nh ho hc. Thch hp cho cc thit b cng nghip v vn ti. - M Cana1 13 l m gc x phng hn hp canxi v natri. Dng bi trn trc ln, trc ca ng c in, may t v cc b phn chu ma st tng t - M phn ch s 4 l m tng hp gc canxi, chu m cao, c cha 9 11% graphit. Dng bi trn nhp t, t u ho , my ko, cc hp bnh rng c ti trng ln; hu m i mn v va p mnh
1 2 3 4 5 6 7 8 9
000 00 0 1 2 3 4 5 6
2.
Lithium EP 2
3.
Cana 1 13
M phn ch s 4
BM. Lc Ha du
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Dng Vit Cng
BM. Lc Ha du
71

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bc u ca phn ng c ch n mn, ZDDP phn ng nhanh vi hydropeoxit to th nh mui baz ZDDP nh di y:

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Diankylphenylamin Diankylphenyl_ Alphanaptylamin Amin thm Phenyl_ Alphanaptylamin

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Dn xut ca Ur R = C8 C12 Phenol Sunfua R = C8 C12 v x = 1 hoc 2

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Sunfonat trung tnh Cc loi sunfonat kim c cng thc nh:

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