PHN 1: TNG QUAN V BIODIESEL Chng I. Khi qut v BioDiesel: 1.1.

Biodiesel l g

BioDiesel manh nha t rt sm nm 1853 nh cng trnh nghin cu ca E. Dufy v J. Patrick v chuyn ha este ca du thc vt, nhng BioDiesel ch c chnh thc ghi nhn vo ngy 10/08/1893, ngy m k s ngi c Rudolf Christian Karl Diesel cho ra mt ng c Diesel chy bng du lc, sau ngy 10/08 c chn l Ngy BioDiesel quc t (International BD Day). n nm 1907 Herry Ford, ngi sng lp cng ty a quc gia Ford Motor Company, cho ra i chic xe bng Etanol. Nhng do xng du c ngun gc t nhin liu ha thch c gi r hn nn nhin liu sinh hc cha c coi trng. Nhng trong thi gian gn y, do gi xng du bin ng, nguy c cn kit nhin liu ha thch e da v yu cu bc thit v chng s bin i kh hu ton cu m nhin liu sinh hc tr thnh mt nhu cu thit thc ca nhn loi, nht l khi cc cng ngh bin i gen gip lm tng t bin sn lng mt s sn phm nng lm nghip. Tm li, c th hiu mt cch tng qut Diesel l loi nhin liu bt k dng cho ng c Diesel. Da theo ngun gc c th chia Diesel thnh 2 loi: Petro Diesel (thng c gi tt l Diesel) l 1 loi nhin liu lng thu c khi chng ct du m phn on c nhit t 175 0C n 3700C, thnh phn ch yu l hidrocacbon t C16 n C21. BioDiesel: C ngun gc t du thc vt (c, to, cy Jatropha, cy cao su) hay m ng vt. Cc loi du m ng thc vt, du m thi tuy rng c th chy iu kin thng nhng v c nht cao, mt s loi c ch s acid ln nn chng khng th dng trc tip cho cc ng c m chng cn phi c chuyn ha thnh MonoankylEste ri mi em

i s dng. Theo phng din ha hc, BD l metyl este ca nhng acid bo (trong , thnh phn to nng lng ch yu l gc hidrocacbon) Ti sao s dng Biodiesel

1.2.

Dn s th gii ngy cng tng nhanh, p lc v nng lng v mi trng cng ln. Tr lng du m ngy cng gim dn, do vn t ra l cn tm nhng ngun nng lng thay th. c th l nng lng ht nhn, nng lng mt tri, nng lng gi, sng bin, nng lng nhit trong lng t. Tt c ngun nng lng hin ang c nghin cu ng dng nhng vn an ton khi sn xut v gi thnh ca n cao nn vic p dng i tr gp nhiu tr ngi. Mt ngun nng lng mi t Biomass ang c ch v c nhiu trin vng v tnh hin thc cng nh kh nng ti sinh v ph hp vi sinh thi. Etanol i t ma ng, tinh bt cng s l mt dng nhin liu sinh hc c trin vng. Du m ng thc vt cng l mt dng nguyn liu to ra khng ch cc hp cht hu c c bn m cn to ra nhin liu cho cc ng c t trong tng t du DO hay FO ca du m. chnh l Biodiesel. D bo ngun nhin liu ny s chim 15-20% trong tng nhu cu nhin liu ca th gii trong vng 50 nm ti. Biodiesel khng n thun l nhin liu sinh hc, m km theo l trng cy c du ph xanh t trng i trc, chng xi mn t, tng lng oxy kh quyn, gim kh CO2, xa i gim ngho cho vng trung du min ni. Bn cnh cn c mt lot sn phm c gi tr khc thu c qua qu trnh sn xut Biodiesel nh glixerin,vitamin,m t b v cc cht c hot tnh sinh hc khc nh saponin, photpholipit, gluxit 1.3. u im ca Biodiesel so vi Diesel truyn thng:

 u im: BD l mt trong nhng ngun nhin liu thay th t gy nh hng n mi trng v sc kho con ngi; l loi nhin liu sch hn v kh thi khi t BD hu nh s khng c SOx, hm lng CO v hidrocacbon thm gim so vi khi t diesel truyn thng. L ngun nhin liu thay th cho diesel khi s dng cho ng c diesel m khng nh hng n ng c. L loi nhin liu c th c dng di dng t do hoc pha trn vi diesel nhm t c hiu qu s dng v kinh t theo yu cu ca tng quc gia. L loi nhin liu ti sinh nn BD s l th mnh ca cc nc c nn nng nghip pht trin. L loi nhin liu b vi sinh vt phn hu nn khi khi thi ra ngoi mi trng s t c hi hn rt nhiu so vi cc loi xng du t du m. Khi t cc tiu chun th BD s l nhin liu t n mn ng c hn so vi diesel. Nhc im: Trong phn t biodiesel c cha nguyn t oxy nn nhit tr thp hn diesel truyn thng. V vy, khi s dng biodiesel lm nhin liu s tiu hao hn nhiu so vi nhin liu diesel truyn thng. D b oxy ha nn vn bo qun l vn hng u khi s dng BD (Lu tr trung bnh 6 thng). Chi ph sn xut cao so vi diesel. Hin ti mun BD thng phm c ng dng rng ri vn phi cn chnh sch h tr ca Chnh Ph nhm y mnh pht trin ngun nng lng ny. Tuy nhin vi tnh trng ngun nhin liu ha thch ang cn dn, th trong tng lai, BD gn nh l gii php thay th duy nht.

Bng 1: Mt s thng s k thut c a ra so snh gia hai loi nhin liu. Kh thi NOx n v g Diesel truyn thng BD t du nnh BD t du thi 0.944 1.156 1.156

CO

0.23

0.136

0.156

Hidrocacbon g

0.0835

0.0040

0.0038

Bng 2: So snh nng kh thi gia DO v Biodisel. Nhin liu DO BDO Methanol Glyxerin Du da Du Jatropha Nng sut to nhit (MJ/Kg) 44,8 37,2 18,2 18,3 35,3 39,6

Du ht cao su

39.18

Bng 3: Bng so snh nng sut to nhit ca mt s loi nhin liu. c tnh nhin liu Nhit tr, Btu/gal nht ng hc 400C, mm2/s T trng 150C, lb/gal 7,079 Hm lng nc v cn c hc, max 7,328 1,34,1 4,06,0

Diesel

Biodiesel

129,05

118,17

0,05

0,05

Chng 2: Biodiesel v thc trng biodiesel ti VN. 2.1. Hin trng sn xut biodiesel: Nhm gim s ph thuc vo nhin liu ha thch v n nh ngun cung ng, cc quc gia thuc khi EU t ra mc tiu l nhin liu sinh hc chim 5,75% trong lnh vc giao thng vo nm 2010, v t con s 10% vo nm 2020. Trong cc loi nhin liu sinh hc EU th biodiesel l nhin liu c sn xut nhiu nht, chim 82% tng s nhin liu sinh hc. Hin nay, cc th trng dn u v biodiesel l EU v Hoa K t c nng sut cc ln trong nhng nm qua. Trong , EU ng u vi tng sn lng biodiesel ca nm 2008 l 7,8 triu tn (trong c sn xut nhiu nht, chim 2,8 triu tn), tng 35.7% so vi nm 2007 l 5,7 triu tn.

Hnh 1: th sn lng v tr lng biodiesel ca EU. Hoa K ng th hai, sn lng tng t 946 triu lt nm 2006 ln 1,7 t lt nm 2007, v khong 2,46 t lt trong nm 2008, vi 1 gallon tng ng 3,78 lt.

Hnh 2: th sn lng v tr lng biodiesel ca Hoa K.

Hnh 3: th sn lng v tr lng biodiesel trn ton th gii. Tnh hnh sn xut biodiesel ti Vit Nam:

2.2.

Vit Nam quan tm n Diesel sinh hc (Biodiesel) cch y 20 nm. n pht trin ngun Nhin liu sinh hc(NLSH) n nm 2015, tm nhn n nm 2025 c Th Tng Chnh Ph ph duyt ngy 20/11/2007. V tim nng c nhiu ngun nguyn liu sn xut biodessel nh: Du m thi qua s dng: Gm cc ph phm du m i t cc nh my ch bin du m, du m qua s dng, c thu hi sau qu trnh rn, nu t cc c s ch bin thc n. Vi to l gii php duy nht c th gii quyt vn din tch t trng v n c chu k pht trin rt ngn, sng c khp ni c nh nng mt tri, nc v CO2. R ng, ng cc, vng, lc, da, m c basa... Cy Jatropha, c ngun gc t Trung M, di thc sang Chu Phi,n v Nam M, cy chu hn, trng t kh cn, c nhiu loi. Nc ta c th tn dng 9 triu ha t hoang ha, dc ven cc ng quc l, trng cy Jatropha ly du. Vit Nam chng ta ang gp nhng kh khn v nhin liu. Gi du v kh t tng lin tc. Ngoi cc sn phm du m th cha c mt nghin cu

no v biodiesel. So vi cc nc, by gi chng ta mi ni n nhin liu sinh hc th qu mun. Trong sn xut biodiesel, Vit Nam c nhiu thun li, v chng ta c nhiu loi cy c du. Loi cy m c th gii tn nhim nh thu du ( ging Jatropha) th Vit Nam khng thiu, bn cnh cn c cc cy c du nh: gai du, s, tru, cy en, vng, lc, da... nhng ci kh l chng ta cha c mt ch trng ng n, r rng. Cng c tc gi xut dng cy du m, dng m c ba sa sn xut nhin liu sinh hc, hin c mt s cng ty ca Php, Singapore ang c d nh hp tc vi Vit Nam trng cy du m, nhng cn c nhng iu tra nghin cu thm, bi chi du m c ti 175 loi m Vit Nam cha c mt s liu no v loi c u th v hm lng, cht lng du. Ngh An cng c nhiu loi cy ly du. Ring cy thu du mc hoang ri rc nhiu ni, cng c ni trng b ro nhng chng my ngi quan tm. Trong giai on khan him nhin liu nh hin nay, tnh cn c k hoch cho iu tra, tm kim loi c hm lng du cao trng, bi n d trng v t hoang ho c th ph xanh bng cy ny va thu du cho sn xut biodesel va gp phn lm sch mi trng khng kh nh kh nng quang hp mnh ca chng. S dng nguyn liu cung cp cho ch bin biodiesel chnh l li dng kh nng quang hp ca thc vt bin i nng lng nh sng thnh nng lng ho hc - mt dng nng lng sch. S tch lu nng lng trong cc lin kt ho hc l kt qu ca vic ng ho carbon dioxide to ra hydrat carbon ri t to ra cht bo nh xc tc ca cc enzim c hiu. Bn cnh , cng nh cc loi cy xanh khc, khi trng nhiu nhng cy ly du, n cn gp phn quan trng trong vic lm gim kh nh knh. Chng 3. Nguyn liu sn xut Biodiesel 3.1. Khi qut Du thc vt l nhin liu ti to. Gn dy loi nguyn liu ny ang rt c quan tm v nhng thun li v mt mi trng v trong thc t chng

c sn xut t nhng ngun nguyn liu ti to. Du thc vt l mt ngun nng lng khng c nguy c cn kit nh du m, vi gi tr nng lng gn vi nhin liu diesel. Sn lng du thc vt ton cu tng t 56 triu tn nm 1990 ln 88 triu tn nm 2000. Rt nhiu cc loi du thc vt c th tng hp biodiesel: du u tng, du ht ci, du c, du hng dng, si gai du, M ngi ta s dng rng ri u tng cho cc sn phm v vy du u tng l ngun nguyn liu u tin sn xut biodiesel. Malaysia v Indonesia, du c li c dng nhiu hn c sn xut biodiesel. Du ht c l hng i ca rt nhiu nc Chu u. Ti n v ng Nam , cy Jatropha c tm thy nh l mt nguyn liu thch hp a v sn xut nhin liu sinh hc. M ng vt c to thnh t nhng m m. T gia th k 29, m ng vt v b tr thanh ngun cht bo quan trng bc nht ti Chu u. Ngoi vic ng dng trong thc phm, xa xa m cn c dng trong m phm v lm cht t cho n. M ng vt cng c thnh phn nh du ng vt. iu kin thng, m tn ti dng rn trong khi du dng lng, thnh phn ca m cng nh ca du u ph thuc vo ngun thu ca chng. Sn lng m ng vt ti cc nc pht trin cng nh cc nc ang pht trin lun chim phn trm a s v th m ng vt l ngun glixerit quan trng sn xut biodiesel. Thnh phn ha hc ca du m ng thc vt

3.2.

Lipit Hm lng lipit dao ng t 1/4 n 1/3 khi lng ht. Trong cc ht c du, lipit thng lin kt vi cc chatts khc nh protein, saccarit v dn xut ca chng to thnh cc kiu hp cht khc nhau v bn vng. Triglyxerit

Triglyxerit l thnh phn chim ch yu (95-98%) ca lipit qu v ht du. V cu to ha hc, chng l cc este ca ru ba chc glyxerit vi axit bo. Photpho Lipit L lipit phc tp, thng c photpho v nito. Hm lng dao ng t 0,25 n 2% so vi lng du trong ht. V cu to ha hc, photpho lipit l dn xut ca glyxerin. Sp Theo cu to, so thuc loi lipit n gin, Chng l cc este ca axit bo mch cacbon di (c t 20-26 nguyn t C) v rc 1 hoc 2 chc. Hp cht cha Nit Hp cht to thnh nito trong ht du chim 20 -25% khi k]ngj ht. Trn 90% cc hp cht c nito l protein Saccarit v cc dn xut ca chng Trong ht c du, lng saccarit t nhin m ch yu l xenlulozo v hemixenlulozo to nn nhng t bo ca nhng m thc vt. Tecpenoit Tecpenoit cng l thnh phn khng x phng ha trong cht bo, nhm ny gm c cc tecpen v ancol tecpen. Tritecpen xut hin trong cht bo vi nng cao (trn 0,5%). Nguyn t khong cht (cht tr) Cc nguyn t khong cht phn ln tp trung trong nhn ht. Hm lng tro ch yu ca ht gm photpho oxit, kali oxit chim 90% lng tro. Cc thnh phn khc Mt s loi du cha cc cht c bit, chng hn nh du vng cha 0,3-0,5 sesamolin mt glycozit ca phenol sesamol v 0,5-2% sesamin, chng gay ra cc phn ng mu v chng oxy ha. Ngoi ra, ty loi du m c cc thnh phn khc nhau.

Thnh phn khc nhau ca du thc vt l cc axit bo. Cc axit bo c trong du thc vt phn ln dng kt hp trong glyxerit v mt lng nh trng thi t do. Cc glyxerit c th thy phn cc axit bo. Mt thnh phn khc trong du thc vt l glyxerin, n tn ti dng kt hp trong glyxerit. Ngoi cc hp cht ch yu trn, trong du thc vt cn cha mt lng nh cc hp cht khc nh cc photphatit, cc cht sp, cht nha, cht nhn, cc cht mu, cc cht gy mi, cc tin t v sinh t 3.3. Mt s loi du, m ng thc vt in hnh tng hp biodiesel Du u nnh: du u nnh tinh khit c mu vng sng, thnh phn axit bo ch yu ca n l linoleic (50-57%), oleic (23-29%). Du da: Da l cy sinh trng lu nm, thch hp vi kh hu nng m, c th trng c cc ni nc mn, l, chua Trong du da c cha cc axit bo lauric (44-52%), myristic (13-19%), panmitic (7,510,5%). Hm lng cc cht bo khng no rt t. Du c: C l cy nhit i c trng nhiu Chile, Ghana, T y Phi, mt s nc chu u v chu . T cy c c th sn xut 2 loi du: du nhn c v du ci c. C 2 loi ny u l nguyn liu tt sn xut biodiesel. Du ht cao su: c p t ht cao su. Hm lng axit bo trong du ht cao su cao hn cc loi du khc. Du s: Cy s c trng nhiu vng nhit i. Thnh phn axit bo ca du s bao gm axit oleic (>60%), axit linoleic (15 -24%) v axit panmitic (15-26%). Du bng: Bng l cy trng mt nm. Trong du bng c sc t carotenoit v c bit l gossipol (l mt c t) lm cho du bng c mu c bit: en hoc sm.

 Du hng dng: Hng dng l loi cy hoa mt nm v hin ti c trng nhiu x lnh nh chu u, chu M, chu v c bit Lin X c. y l loi cy c sn lng du cao v nng sut ln. Du hng dng c th sn xut biodiesel rt tt nhng c s dng nhiu cho ngnh thc phm v trong n cha nhiu protein. Du thu du: c ly t ht ca cy thu du c trng nhiu vng kh hu nhit i. Du thu du l loi khng kh, c ch s iot t 80-90, t trng ln. Du lc: Du lc cha ch yu axit oleic (50-63%), linoleic (13-33%), panmitic (6-11%). Hm lng cc axit bo khc khng nhiu. Du lc ch yu dng vo cc mc ch thc phm. Tuy nhin du lc cng c s dng sn xut biodiesel. Du vng: Cy vng c trng nhiu chu . Cc axit bo trong du vng ch yu l axit oleic (33-48%), linoleic (37-48%), stearic (4-6%). Du vng dng lm thc phm, cng s dng sn xut biodiesel. Du ng: Cy ng c trng trn khp th gii. Cc axit bo trong du ng thng l: axit linoleic (43-49%), oleic (37-40%), axit panmitic v atearic gn bng 14%. Du Jatropha: Du ht Jatropha c coi l ngun nguyn liu c gi tr nht sn xut ra biodiesel do n c hm lng du cao, li d trng nhng ni t kh cn, bc mu, ni t ct, nhim mn M ng vt trn cn: cha nhiu axit bo no, ch yu l palmaitic v axit stearic (m heo, m b). M ng vt trn cn cha nhiu axit bo thuc nhm omga-6 hn, hu nh khng c omga-3 nn thng trng thi rn trong iu kin nhit thng. Cc axit bo thuc nhm omga 6 c tc dng lm co mch, tng huyt p. M ng vt di nc: cha hm lng axit bo khng no thuc nhm omga-3 tng i ln, th lng trong iu kin nhit thng.

Nc ta thuc vng nhit i, c nhiu sng nc nn ngh nui v ch bin thy sn pht trin mnh v c cht v lng, khng ch phc v nhu cu trong nc m cn hng n xut khu. Trong phi k n ngh nui v ch bin c da trn khu vc ng bng sng Cu Long. Hot ng ch bin cc sn phm t c da trn thi ra ngoi mt lng ln cc ph phm, nh hng n mi trng. Do , nu s dng cc ph phm ny nh ngun nguyn liu cho nhin liu mi l mt phng n c hiu qu v mt kinh t ln cho mi trng. Vic la chn loi du thc vt hoc m ng vt no ph thuc vo ngun ti nguyn sn c v iu kin kh hu c th ca tngvng. Chng hn nh Chu u s dng ch yu l ci du v du hng dng; Chu M du u nnh, hng dng v thu du; min Nam Chu Phi - du u nnh, du m; ng Nam - du c, du da v du m; Chu c - ci du, du lanh v du c nhp t ng Nam . S dng ngun ti nguyn sn c, cc nguyn liu ph thi s gip phn lm gim gi BD, a BD vo s dng rng ri hn.

Chng 4. Cc phng php sn xut Biodiesel

4.1. Pha long du thc vt: nht ca du thc vt c th c lm thp xung bng vic trn ln vi etanol tinh khit, hoc pha trn vi du khong. Chng hn hn hp 25% du hng dng v 75% du khong c tnh cht tng t nh nhin liu diesel. S pha long nh vy gip lm gim nht ca du thc vt t c gi tr gn tng ng du diesel trong ng c. 4.2. Nhit phn du thc vt: Nhit phn l phn hy cc phn t du thc vt bng nhit khng c mt ca oxy, kt qu to ra cc alkan, alkadien, cc axit cacboxylic, hp cht thm v lng nh cc sn phm kh. Qu trnh nhit phn cc hp cht bo c

thc hin cch y 100 nm, c bit nhiu ni trn th gii c t hoc khng c du m. 4.3. Cracking xc tc du thc vt: Bng phng php cracking c th to ra cc alkan, xycloalkan, alkylbenzen Tuy nhin vic u t cho mt dy chuyn cracking xc tc rt tn km nn phng php ny t s dng. Phng php transeste ha. Qu trnh ny to ra cc alkyl este axit bo (biodiesel l tn gi cc alkyl este axit bo ny khi chng c dng lm nhin liu) c nht thp hn nhiu so vi cc phn t du thc vt ban u. Cc este ny c trng lng phn t bng 1/3 so vi phn t du thc vt v c nht xp x bng diesel khong. V vy, biodiesel thu c c tnh cht ph hp nh mt nhin liu s dng cho ng c diesel. y l phng php c s dng nhiu nht. Transester ha bao gm nhiu phn ng thun nghch ni tip nhau. Trong , phn t triglyceride c chuyn ha tng bc thnh diglyceride, monoglyceride v cui cng l thnh glycerol (Hnh 4). S hnh thnh cc alkyl ester t monoglyceride c cho l bc quyt nh tc phn ng, bi v monoglyceride l hp cht trung gian kh bn. Tc nhn phn ng trao i este: Metanol: Tc nhn phn ng trao i este l cc alcol khc nhau, nhng thng thng hay s dng l metanol. Metanol c cng thc CH 3OH, l ru u tin ca dy no, phn cc. V gc CH3- c khi lng nh nn metyleste to ra c t trng nh hn nhiu so vi pha glyxerin, l cho sn phn d phn lp v tch biodiesel d dng. Phn ng trao i este l phn ng thun nghch nn mun tng hiu sut biodiesel phi dng lng d metanol (to iu kin phn ng theo chiu thun), tuy nhin phi dng lng d metanol theo mt t l thch hp v nu lng metanol d nhiu lm qu trnh phn lp sn phm s kh khn v tn

4.4.

nhiu nng lng cho qu trnh thu hi metanol. Thng thng t l metanol/du thch hp l t 6/1 n 9/1. Metanol r tin, d kim, tuy nhin rt c. Etanol: Etanol l mt loi alcol c ng dng nhiu nht trong ngnh tng hp hu c ha du v etanol khng c hi, hn na etanol c th sn xut t ngun nguyn liu sinh hc nh t go, sn bng qu trnh ln men. Chnh v nhng l do trn m hin nay ngi ta ang quan tm n s dng etanol lm nguyn liu cho qu trnh tng hp biodiesel t du thc vt. Tuy nhin hiu sut to thnh biodiesel thp do kh nng tn cng ca C2H5O- km hn so vi gc CH3O-. Cc loi ru no khc: V nguyn tc, c th s dng cc ru c s cacbon bng 3 hoc 4. Tuy nhin, mch ca ru cng ln, tc trao i este cng nh, s phn tch pha cng km, do vy chng t c ng dng.

Hnh 4: Phn ng transester ha ca triglyceride vi ru. C ch phn ng: Xc tc baz: Phn ng trao i este c thc hin trn nhiu loi xc tc khc nhau, tuy nhin cho n nay c ch mi c nghin cu k trn xc tc baz kim. u tin l phn ng khi mo, ru s phn ng vi xc tc baz to ra anion alkoxide RO- v proton H+. Tc nhn alkoxide tn cng vo nguyn t carbon ca nhm carbonyl hnh thnh nn mt hp cht trung gian c cu trc t din, t cu trc ny ti sp xp li hnh thnh nn alkylester v anion diglyceride tng ng. Anion diglyceride ny tc dng vi proton BH+ to ra phn t diglyceride v gii phng ra baz B tip tc tham gia xc tc phn ng khc. Cc diglyceride v monoglyceride cng c c ch phn ng tng t hnh thnh nn hn hp alkylester v glycerol.

u im ca phn ng transester ha vi xc tc kim tnh l tc phn ng nhanh, cao hn khong 4000 ln khi so snh vi phn ng xc tc axit. Nhc im ca xc tc kim l ch dng c cho cc loi du tng i sch, hm lng axit bo t do nh hn 1%. Khi hm lng axit bo t do ln hn 1%, th hiu sut ca phn ng b gim bi v axit bo t do phn ng vi cht xc tc kim (KOH, NaOH) hnh thnh nn x phng. X ph ng hnh thnh trong phn ng gy kh khn cho qu trnh thu hi glycerol, v lm gim ng k hiu sut phn ng. Hm lng nc trong du m cng c nh hng n hiu sut hnh thnh alkylester bi v n lm cho phn ng x phng ha din ra.

Ch thch:

B: xc tc kim tnh R: gc alkyl ca ru R1, R2, R3: mch hydrocarbon ca cc axit bo Hnh 5: C ch ca phn ng xc tc kim tnh. Xc tc axit: C ch ca phn ng transester ha triglyceride s dng xc tc axit: u tin, din ra qu trnh proton ha nhm carbonyl ca ester thnh carbocation nh ion H+. Sau phn t ru s gn vo, to ra hp cht trung gian c cu trc t din. Hp cht trung gian ny s tch phn t diglyceride ra hnh thnh nn ester, gii phng ra ion H+ tip tc qu trnh xc tc.

Ch thch: R1, R2, R3: mch hydrocarbon ca cc axit bo R4: gc alkyl ca ru Hnh 6: C ch ca phn ng transester ha vi xc tc axit.

 Kt hp xc tc axit v xc tc kim: i vi nhng nguyn liu u c hm lng axit bo t do cao th axit bo s phn ng vi xc tc to thnh x phng nu phn ng s dng xc tc kim. Lng axit bo t do ti a i vi phn ng xc tc kim l 2% nhng tt nht l 1%. Tuy nhin nhiu nguyn liu u vo c hm lng axit bo t do cao hn nhiu v chng phi c tinh ch t n yu cu. Qu trnh tinh ch thng c tin hnh trn phn ng hai giai on: chuyn ha este trn xc tc axit lm gim hm lng axit bo t do xung di 1% , sau tin hnh phn ng trao i este bng xc tc kim. Giai on mt: Tin hnh phn ng este ha trn xc tc axit nhm chuyn lng axit bo thnh este a hm lng axit bo t do trong du xung di 1%. Ru c dng l metanol vi t l mol metanol/du l 25/1. Lng metanol cho d rt nhiu so vi lng du do phn ng este ha to ra nc s lm gim hiu sut ca phn ng khi s dng xc tc axit (H 2SO4 c), metanol d s hp th nc c to ra. Phn ng c tin hnh trong 1,5 gi, hm lng xc tc l 1% theo th tch hn hp phn ng, nhit phn ng l 60 0C. Sau khi kt thc th hn hp phn ng s lng tch thnh hai lp. Lp trn ch yu l metanol d, axit sunfuric, nc s c tch ra. Sn phm thu c lp di c ra v chng loi nc s c hm lng axit bo m bo (<1%) c dng lm nguyn liu tng hp biodiesel s dng xc tc kim. Giai on hai: Tng hp biodiesel t du x l trn xc tc kim (NaOH). Sn phm ca giai on mt sau khi tch axit, metanol, nc c dng lm nguyn liu cho giai on hai. Phn ng c tin hnh trong iu kin: nhit phn ng 600C, thi gian phn ng l 2h, hm lng xc tc (theo khi lng du) 0,8%, t l mol metanol/du l 4/1. Sau khi phn ng kt thc th hn hp phn ng s lng tch thnh hai lp. Lp trn ch yu l biodiesel c ra nc, chng loi nc thu c biodiesel t ch tiu cht lng. Lp

di ch yu l glyxerin c ra nc, chng loi nc thu c glyxerin tinh ch c gi tr kinh t cao. Xc tc ca phn ng: Xc tc axit: Xc tc axit ch yu l axit Bronsted nh H2SO4, HCl xc tc ng th trong pha lng. Phng php xc tc ng th ny i hi nhiu nng lng cho qu trnh tinh ch sn phm. Cc xc tc axit cho chuyn ha thnh este cao, nhng phn ng ch t chuyn ha cao khi nhit cao trn 100 0C v thi gian phn ng lu hn, t nht trn 6 gi mi t chuyn ha hon ton. Xc tc baz: Xc tc baz c s dng trong qu trnh chuyn ha este du thc vt c th l xc tc ng th trong pha lng nh: KOH, NaOH, K2CO3, CH3ONa Xc tc ng th CH3ONa cho chuyn ha cao nht, thi gian phn ng ngn nht, nhng yu cu khng c c mt ca nc v vy gy kh khn cho cc qu trnh cng nghip. Xc tc d th: - Xc tc MgO: y cng l loi xc tc baz, nhng s dng dng rn. Hiu sut biodiesel thu c trn xc tc ny thp hn khong 10 ln so vi NaOH hay KOH. nng cao hot tnh ca xc tc d th nh MgO, c th hot ha bng NaOH. Vic d th ha xc tc s dn n d lc ra sn phm, mt khc xc tc ny c th ti s dng v ti sinh c, s nng cao hiu qu kinh t v gim thiu s ln cn phi x l mi trng. - Xc tc nha trao i cation Amberlyst 15, titanium silicat TIS: Xc tc dng ny ang c nghin cu, hot tnh ca xc tc cn thp. - Xc tc Na/NaOH/ -Al2O3: thay th xc tc NaOH ng th, ngi ta nghin cu iu ch c xc tc d th dng Na/NaOH/ -Al2O3. Vic a Na v NaOH ln -Al2O3 c thc hin bng cch trn Na v NaOH vi -Al2O3 ri thi dng N2 3200C vo hn hp . Sau mt

thi gian s to thnh cc tm hot tnh, c nhn bit bng ph XRD, XPS v phn tch nhit TPD. Nu xc tc c 20% Na, 20% NaOH th s c hot tnh cao nht. Vi h xc tc ny, hiu sut biodiesel c th t trn 80%. Ngoi dng xc tc trn, cn c th hot ha xc tc -Al2O3 bng Na2CO3. Sau khi iu ch -Al2O3, tin hnh ngm tm dung dch Na2CO3 trn cht mang ny, sy kh v gia nhit hot ha. C th thu c n 94% biodiesel trn h xc tc ny. - Xc tc HZSM-5: c im ca xc tc ny l c t l Si/Al = 18, b mt ring 393 m2/g. C th s dng hn hp trn c hc gia HZSM-5 v zirconi sunfat (ZrSO4) vi t l 0,1/0,9 n 0,8/0,2. Xc tc loi ny thng c s dng trong phn ng iu ch biodiesel theo phng php hydrocracking. - Xc tc Rh-Al2O3: Xc tc ny c s dng trong phn ng hydrocracking du nnh. Sn phm thu c ngoi biodiesel cn c xng v cc sn phm khc. - Xc tc enzym: Hai loi lipaza extracellular v intracellular u c th l xc tc cho phn ng tng hp biodiesel. Tuy nhin cc nghin cu ch yu u tp trung vo cc extracellular c nh c thng mi l Novozym 435 t C. antarctica (c nh trn nha acrylic xp), Lipozym RM IM t R. miehei (c nh trn nha anion), Lipozym TL IM t T. lanuginosus (c nh trn ht silicagel). Hiu sut biodiesel ph thuc vo loi lipaza v hm lng s dng, ancol v t l ancol/du, nhit v dung mi. Mi loi lipaza c nh hng khc nhau i vi cc ancol bc nht v bc hai. Mc d c tc dng lm gim hot tnh ca xc tc enzym, methanol v ethanol vn c dng ph bin do gi r. Ngoi cc cht mang nha hu c t tin, lipaza cn c nghin cu c nh trn cht mang r tin khc nh cao lanh, si cotton, hydrotaxit, sili cagel. So vi xc tc ha hc, lipaza c iu kin phn ng nh nhng hn (nhit 35 400C), t l ancol/du thp hn, khng c sn phm ph, vic

tch pha v thu hi glyxerin d dng, xc tc c th ti s dng nhiu ln, hiu sut phn ng cao. Lipaza khng b nh hng bi hm lng FFAs v nc c trong du m v n xc tc cho c phn ng este ha v trao i este do thun li cho vic sn xut bng ngun nguyn liu du thi. S dng xc tc enzym c u im l cho chuyn ha cao nht, thi gian phn ng ngn nht, qu trnh tinh ch sn phm n gin. Tuy nhin gi thnh ca xc tc enzym t hn nhiu so vi xc tc kim chnh v th loi xc tc ny cha c ng dng rng ri.