GVHD: Th.

S Nguyn Hu Sn

M U
Trong bi cnh ngun ti nguyn du m ang cn kit v nhng tc ng xu ln mi trng ca vic s dng nhin liu cng vi s pht trin trnh cao ca ngnh cng nghip, cc nhin liu ti sinh sch ang ngy cng khng nh v tr l ngun nhin liu thay th mang tnh kh thi nhm m bo ngun nng lng cn thit cng nh bo v mi trng sng trn tri t ca chng ta. Cng ngh sinh hc vi tc pht trin nhanh chng v ang to ra cuc cch mng trong nng nghip, cng nghip thc phm, dc phm, vt liu mi, nhin liu sinh hc... phm vi hp chng ta ang chng kin s pht trin nhanh ca cng nghip sn xut vi to trn th gii do nhiu u th ca c th ny so vi thc vt bc cao nh vng i ngn, nng xut cao, h s s dng nng lng nh sng cao, cng ngh sn xut khng phc tp, khng cnh tranh vi din tch t nng nghip... Cho n nay nhn loi c hng lot cc cng ngh nui trng, thu hoch, ch bin sinh khi vi to. Cc cng ngh ny ang khng ngng c hon thin nhm h gi thnh v nng cao cht lng sinh khi. Vic ng dng vi to c m rng trong cc lnh vc nh dng vi to lm thc n b dng cho ngi, thc n cho ng vt, c bit cho ngnh nui trng thy sn, ngun phn bn sinh hc, x l mi trng, ngun ha cht cho cng nghip v dc phm, ngun nng lng sch thn thin vi mi trng. hiu thm cc vn xung quanh nhin liu sinh hc c bit l biodiesel (du diesel sinh hc) nhm chng em chn ti sn xut biodiesel t vi to mt ti ang c rt nhiu nha khoa hc quan tm v mi ch xut hin trong thi gian gn y lm ti nghin cu tiu lun. V iu kin thi gian c hn nn chng em khng th nghin cu chi tit, y ton b mi vn . Nhng iu chng em trnh by ch mang tnh khi qut. Rt mong c s ng gp kin qu bu ca thy v cc bn!

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GVHD: Th.S Nguyn Hu Sn

NI DUNG
Chng 1. Tng quan v biodiesel v vi to 1.1 Biodiesel Biodiesel cn c gi Diesel sinh hc l mt loi nhin liu c tnh cht ging vi du diesel nhng khng phi c sn xut t du m m t du thc vt hay m ng vt. Biodiesel, hay nhin liu sinh hc ni chung, l mt loi nng lng sch. Mt khc chng khng c v d phn gii trong t nhin. Mt mu diesel sinh hc Bn cht ca Biodiesel l sn phm Ester ha gia methanol hoc ethanol v acid bo t do trong du thc vt hoc m ng vt. Ty thuc vo loi du v loi ru s dng m alkyl Ester c tn khc nhau. VD: Nu i t du cy u nnh (soybean) v Methanol th ta thu c SME (soy methyl Esters). y l loi Esters thng dng nht c s dng ti M. Nu i t du cy ci du (rapeseed) v Methanol th ta thu c RME (rapeseed methyl Esters). y l loi Esters thng dng nht c s dng chu u. Theo tiu chun ASTM th Biodiesel c nh ngha: l cc mono alkyl Ester ca cc acid mch di c ngun gc t cc lipit c th ti to li nh: du thc vt, m ng vt, c s dng lm nhin liu cho ng c diesel. Biodiesel c th c s dng trc tip hoc phi trn vi nhin liu diesel truyn thng. Ngi ta k hiu B100 vi nhin liu cha 100% biodiesel, nu phi trn 20% th tch biodiesel vi 80% diesel th nhin liu ny c k hin l B20. Tng t ta cng c cc loi nhin liu B5, B10

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GVHD: Th.S Nguyn Hu Sn 1.1.1 Lch s pht trin ca biodiesel Biodiesel bt u c sn xut khong gia nm 1800, trong thi im ngi ta chuyn ha du thc vt thu Glycerol ng dng lm x phng v thu c cc ph phm l methyl hoc ethyl Ester gi chung l biodiessel. Ln u tin (10/08/1893) Rudolf Diesel s dng Biodiesel do ng sng ch chy my. Nm 1912, ng d bo: Hin nay, vic dng du thc vt cho nhin liu ng c c th khng quan trng, nhng trong tng lai, nhng loi du nh th chc chn s c gi tr khng thua g cc sn phm nhin liu t du m v than . tng nh ngui c cng u tin on c gi tr to ln ca Biodiesel, Nation Board Biodiesel quyt nh ly ngy 10 thng 8 hng nm bt u t nm 2002 lm ngy Diesel sinh hc Quc t (International Biodiesel Day). Ti Hi ch th gii t chc ti Pari (1900), Diesel biu din ng c dng du Biodiesel ch bin t du phng (lc). Trong nhng nm ca thp k 90, Php trin khai sn xut Biodiesel t du ht ci. V c dng dng B5 (5% Biodiesel vi 95% Diesel) v B30 (30% Biodiesel trn vi 70% Diesel). Cho ti nay, trn th gii sn xut c biodiesel t nhiu ngun nguyn liu khc na nh m ng vt (m c tra, c ba sa), cy jatropha,..v mi nht l vi to. Biodiesel c th c s dng trc tip hay phi trn vi diesel truyn thng. Hin c nhng loi biodiesel sau y: - B5 gm 5% biodiesel pha vi 95% du diesel. - B10 gm 10% biodiesel pha vi 90% du diesel. - V B20 gm 20% biodiesel pha vi 80% du diesel 1.1.2. Cc tnh cht ca biodiesel Biodiesel l mt cht lng, c mu gia vng hay nu ti ph thuc vo nguyn liu ch bin. Methyl ester in hnh c im bc chy khong ~150 0C (3000 F), t trng thp hn nc (d= ~0,88g/cm3), c nht tng t diesel t du m.

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GVHD: Th.S Nguyn Hu Sn - Mt s u im ca nhin liu biodiesel Ph gia tng kh nng bi trn: ch cn phi trn t 0,4% n 5% biodiesel vi nhin liu diesel s lm tng kh nng bi trn ca nhin liu. tng kh nng ny ca nhin liu diesel ngi ta cho thm lu hunh. Tuy nhin khi nhin liu cha lu hunh b t cht s to lu hunh dioxit, mt thnh phn ca ma acid, gy nhim mi trng. Nhin liu biodiesel c u im l c hm lng lu hunh rt t (khong 0,001%) v vy khi ch n s hn ch c nhc im to ra kh SO2 ca nhin liu truyn thng. Tr s cetan cao: tr s cetan l mt trong nhng yu cu rt quan trng cho nhin liu ca ng c diesel. N c trng cho kh nng bt chy ca nhin liu cng nh tin1nh n nh ca ng c. Nhin liu diesel thng thng c tr s cetan t 50 n 54, trong khi biodiesel c tr s cetan t 56 n 58. S d biodiesel c tr s cetan cao nh vy v biodiesel c cc alkyl ester mch thng c kh nng t bt chy cao. l u im rt ln ca nhin liu biodiesel, khng nh vai tr thay th ca nhin liu ny cho nhin liu truyn thng i vi ng c diesel. Kh nng phn hy sinh hc: biodiesel c kh nng phn hy sinh hc v khng c hi, so vi nhin liu diesel du khong th biodiesel c kh nng phn hy sinh hc nhanh gp bn ln. Do tnh cht thn thin vi mi trng nh vy m biodiesel rt thch hp lm nhin liu cho cc my mc lm vic nhng khu vc nhy cm nh cc khu vc ng dn c, hay khu vc song h An ton trong vn chuyn v tn tr: trong iu kin thng biodiesel khng c kh nng t bt chy hay n do n c nhit chp chy cao khong 130oC, trong khi nhin liu diesel khong c nhit chp chy ch trn 50oC. V l do ny m vic tn cha v vn chuyn biodiesel an ton hn nhiu. Gim ng k lng kh thi gy c hi vi con ngi v gy nhim mi trng: so vi nhin liu diesel truyn thng th biodiesel c lng kh thi thp hn nhiu. Biodiesel khng thi kh lu hunh dioxide, carbon dioxide v gim n 20% kh carbon monoxide v c nhiu oxy t do: Khng thi kh SO2 Quy trnh sn xut Biodiesel t Vi to Trang 4

GVHD: Th.S Nguyn Hu Sn Khng thi kh CO2 Gim lng khi mui t 40% n 60% Gim lng kh CO t 10% n 15% Gim lng hydrocarbon t 10% n 15% Gim ng k lng hydrocarbon thm a vng: Gim 97% phenanthren, 56% benzofloanthen, 71% benzapyren. Gim hoc tng lng kh NOx t 5% n 10% ty thuc vo tui th ca ng c. D dng sn xut: do ngun nguyn liu sn xut biodiesel l ngun du thc vt v m ng vt l nhng ngun nguyn liu c kh nng ti sinh v khng lm nh hng n ngun nng lng t nhin. V vy ngun nguyn liu sn xut biodiesel c th c cung cp ch ng v d dng. - Mt s nhc im ca nhin liu biodiesel Bn cnh rt nhiu u im k trn ca biodiesel th nhin liu ny cng c mt s nhc im sau: Gi thnh cao: biodiesel thu c t du thc vt tinh khit c gi thnh t hn so vi nhin liu diesel thng thng. Tuy nhin nhc im ny c th khc phc c bng cch i t nhng ngun nguyn liu r tin hn nh du s ch hoc du thu hi. ng thi qu trnh sn xut biodiesel c sn phm ph l glycerin, ha cht c nhiu ng dng trong cng nghip nh sn xut mc vit, kem nh rng, thuc l v cc loi mui dng ch bin phn bn, nn c th b li gi thnh ca qu trnh sn xut biodiesel. Thi nhiu kh NOx: khi d dng biodiesel vi nhng ng c c th lng kh NOx thi ra s tng ln. Tuy nhin cng c th gim lng kh thi ny bng hai cch l gim nhit t chy v lp hp xc tc ng x ca ng c. Lm hng cc b phn bng cao su trong ng c: nhin liu biodiesel c xu hng lm hng cc b phn bng cao su bn trong ng c v ru c trong biodiesel lm hng cao su. Nu mt ng c s dng 100% nhin liu biodiesel trong vng 160.000km th cc phn cao su trong ng c s phi thay th. hn ch nhc im ny cc nh sn xut ng c thay th cc b Quy trnh sn xut Biodiesel t Vi to Trang 5

GVHD: Th.S Nguyn Hu Sn phn ny bng cc vt liu tng hp, v d fluroelastomer. Ngoi ra nhng vt liu tng hp bn vi nhin liu oxy ha, methanol v ethanol u ph hp khi s dng vi biodiesel. Nhit ng c ca biodiesel ph thuc vo nguyn liu sn xut nhng ni chung l cao hn nhiu so vi du diesel thnh phm. iu ny nh hng rt ln n vic s dng biodiesel nhng vng c thi tit lnh. Ngoi ra, biodiesel rt ho nc nn cn nhng bin php bo qun c bit trnh tip xc vi nc. Biodiesel khng bn rt d b oxy ha nn gy nhiu kh khn trong vic bo qun. 1.1.3 Tnh hnh nghin cu, sn xut v s dng nhin liu biodiesel Vit Nam v trn th gii 1.1.3.1 Tnh hnh th gii T u nhng nm 80 trn th gii biodiesel c nghin cu pht trin v s dng. n nay biodiesel l mt nhin liu thay th c s dng trn nhiu nc. Trn th gii c t nht 28 quc gia nghin cu sn xut biodiesel. Cc nh my sn xut ch yu nm chu u v M. Ti M hu ht nhin liu biodiesel c lm t du u nnh hoc du thu hi t du n u nnh, c phi trn vi diesel t l 20% v dng lm nhin liu cho cc xe bus a n hc sinh ca rt nhiu thnh ph. Ti Php tt c cc nhin liu diesel c pha trn vi 5% biodiesel. Nm 1991 c bt u a ra chng trnh pht trin biodiesel, n nm 1995 bt u trin khai d n v nm 2000 ti nc c c 13 nh my sn xut biodiesel vi tng cng sut l 1 triu tn/nm. V thng 1 nm 2005 Nh nc c ban hnh sc lnh buc phi pha nhin liu biodiesel vo xng, du theo t l 5%. Khng ch cc nc chu u hay M l nhng nc i u trong vic nghin cu nhin liu ny m chu , chnh ph nhiu nc cng c nhng quan tm ng k n vic pht trin ngun nhin liu sinh hc thay th nhin liu truyn thng.

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GVHD: Th.S Nguyn Hu Sn Malayxia v Indonesia, hai th trng xut khu du c ln nht th gii cng nhau xy dng mt chin lc nhm m rng th trng sn xut. Ngoi mc ch m rng th trng du n th vic cung cp ngun nguyn liu sn xut nhin liu sinh hc biodiesel cng c tnh n v u t. Cng ty in lc quc gia Tenaga Nasional Bhd, ln nht Malayxia s dng du nhin liu trn ln du c cch y khong 4 5 nm. Mc d d tr du c hin nay ca Malayxia t mc l lc nhng gi du c th ca nc ny d kin vn tng cho n nm 2007 do nhu cu du biodiesel trn ton cu ngy cng tng. Trung Quc nc nhp khu nhin liu hng u chu c th s khuyn khch nhu cu s dng nhin liu sinh hc. Ti Thi Lan, B nng lng sn sang h tr s dng du c trn phm vi ton quc. Hin nay B ang hon tt th tc h tr pht trin biodiesel nhm xy dng ngun nng lng phc v cho lnh vc nng nghip v duy tr cc v ma du c trn c nc. B ny cng a ra mc tiu s dng du diesel pha 5% biodiesel (B5) trn ton quc vo nm 2011 v pha 10% biodiesel vo nm 2012. 1.1.3.2 Tnh hnh trong nc Trc hnh hnh pht trin mnh m nhin liu sinh hc trong c diesel sinh hc hay biodiesl trn th gii, cc nh khoa hc, cc nh nghin cu Vit Nam bc u bt tay vo nghin cu v sn xut nhin liu biodiesel quy m phng th nghim v quy m sn xut nh. Vic sn xut biodiesel Vit Nam c thun li v nc ta l mt nc nng nghip, thi tit li u i cho vic pht trin cc loi thc vt ph hp sn xut biodiesel nh cy vng, lc, jatropha, vi to Bn cnh ngun m ng vt cng l mt nguyn liu qu gi sn xut biodiesel. Mt doanh nghip c phn xut nhp khu thy sn An Giang sn xut thnh cng v a ra th trng sn phm du diesel sinh hc sn xut t m c basa. Theo cng ty 1kg m c th sn xut c 1,13 lt biodiesel vi gi bn 7.000/lt. Cng ty ang chun b xy dng nh my sn xut Basa biodiesel vi cng sut 10 nghn tn/nm v d kin a vo sn xut i tr vo u nm 2007. Quy trnh sn xut Biodiesel t Vi to Trang 7

GVHD: Th.S Nguyn Hu Sn Ngoi ra mt s cc Vin nghin cu ca nc ta cng c nhng nghin cu thnh cng cho vic sn xut biodiesel t du thc vt. Khng ch c cc nh khoa hc quan tm n nhin liu sinh hc m cc nh qun l cng bc u c quan tm. n Pht trin nhin liu sinh hc cho n nm 2015, tm nhn 2020 do B Cng nghip ch tr s sm c chnh ph ph duyt i vo hot ng. 1.1.4 Khi qut v qu trnh tng hp Biodiesel 1.1.4.1 Gii thiu mt s loi cy lm nguyn liu sn xut biodiesel 1- Cy c du Cy c l loi cy nhit i sinh trng ch yu vng kh hu nng. Loi c c bit n nhiu nht l loi c Chu phi sinh trng vng Ty Chu Phi, c tn khoa hc l Elaeis guineensis. C Chu Phi l mt trong nhng cy cho du ln nht trn th gii. Mt hecta cy c c th cung cp n 5 tn du mt nm. C l loi cy lng tnh. T cy c ta c th thu c hai loi du l du nhn c v du ci c. Du ci c thu c bng cch chit sut t phn ci ca qu c. Du nhn c c tnh cht tng t du da, nhit phng n tn ti th rn. Du ny thng dng lm mayonaise, du n, kem v cc sn phm bnh ko. C hai loi du nhn c v du ci c u c th s dng san xut biodisel. 2- Cy da Cy da l mt trong nhng loi cy c nhiu gi tr s dng nht trn th gii. Da c ngun gc t vng Nam M, v hin nay c tt c cc vng kh hu nhit i trn th gii. Ta c th sn xut rt nhiu sn phm t cc phn khc nhau ca cy da. Trong du da, c cc axit bo: loric(44 52%), milistic(13 19%), panmitic(7,5 10,5%). Hm lng cc axit bo khng no rt t. 3- Cy lc Vit Nam, cy lc c trng nhiu trn cc lu vc sng.

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GVHD: Th.S Nguyn Hu Sn Trong du lc, axit bo ch yu l oleic (50% -63%), linoic (13% -33%), panmitic (6% -11%). Hm lng cc axit bo khc khng nhiu lm. 4- Cy u tng Ngun gc cy u tng l ng bi v nhng nc ny c nhiu ging du mc di. Cc axit bo ch yu trong du u tng l linolic chim (51% -57%), oleic(23% -29%), plinolenic(3% -6%), panmitic (2,5% -6%), stearic(4,7% -57,5%). 5- Cy s y l loi cy c trng nhiu cc vng nhit i Chu . Nc ta cy s c trng nhiu cc tnh trung du v min ni (Vnh Phc, Lng Sn...). Thnh phn axit bo ch yu cu du s l axit oleic (>60%), axit linoleic(155 -24%), axit panmitic (15% -26%). 6- Cy ng Cy ng l ng cc c trng nhiu trn th gii. nc ta hu ht cc a phng u trng ng, nht l nhng ni c t ph sa. Hm lng du trong ht ng rt thp khong 10% -12%. Du tp trung ch yu phi 30% 50%. Ngoi ra trong phi cn cha nhiu protein c ga tr sinh hc cao. Cc axit bo ch yu trong du ng l axit linolic (43,4% -49%), axit oleic(37,7% -40%), axit bo no ch yu l panmitic v stearic (xp x 14%). 7- Cy vng Cy vng l loi cy c t rt lu,c trng nhiu cc nc Chu . nc ta cy vng c trng nhiu cc a phng v c dng lm thc n trc tip. Cc axit bo ch yu c trong du vng: axit oleic (33% -48%), axit linolic(37% -48%), axit panmitic07% -8%), axit stearic94% -6%). 8- Cy bng y l loi cy c trng nhiu cc tnh trung du nc ta. Gi tr kinh t ch yu ca cy bng l ly si bng. Cc axit bo ch yu c trong du bng l axit linolic (40% -48%), axit oleic(30% -35%), axit panmitic(29% -22%), hm lng axit bo khc xp x 1%. Quy trnh sn xut Biodiesel t Vi to Trang 9

GVHD: Th.S Nguyn Hu Sn Do trong du bng c nhiu axit bo no panmitic nn nhit phng n c th th rn. Bng cch lm lnh du, ngi ta c th tch c panmitic dng sn xut macgarin v x phng. Trong du bng cn c sc t carotenoit v c bit l gossipol v cc dn xut ca chng, lm cho du bng c mu sm hoc en. Gossipol l mt c t mnh hin nay dng phng php tinh ch bng kim hoc axit antranilic c th tch c gossipol. Kh du bng cha nhiu protein (30%), c hot ng sinh hc mnh nh acghinin(7,4%), hitechin(2,65%), izo loxin(5%), loxin(3,3%). 9- Cy hng dng Cy hng dng c trng nhiu cc vng ni cao: Cao Bng, Lng Sn, Lai Chu... Axit bo ch yu trong du hng dng l linolic (46% -62%), oleic (24% -40%), panmitic (3,5 -6,4%), stearic(1,6% - 4,6%). 10- Bn cnh ngun du thc vt l ngun nguyn liu chnh sn xut biodiesel th cn c cc ngun khc nh du thu hi t du n s dng, m ng vt v to. Trn th gii ngi ta nghin cu thnh cng qu trnh sn xut nguyn liu biodiesel t m ng vt nh m b, m ln, m g v c m c. Hng nm cc nh hng M cung cp hn 11 triu lt du thu hi, y l ngun nguyn liu r tin sn xut biodiesel. Hin nay mt ngun nguyn liu sinh hc rt c gi tr khc ang c nghin cu l to. So vi du thc vt th to cho hiu sut thu hi biodiesel ln hn v mt u im na l n hp th cacbon ioxit nhiu hn so vi cc loi thc vt khc. 1.1.4.2 Nguyn liu cho qu trnh sn xut biodiesel 1- Du m ng thc vt Nguyn liu dng sn xut biodiesel l cc loi du thc vt, m ng vt v du m qua s dng. Cc hp cht ny c cha triglyxerit, axit bo t do v cc tp cht khc ty thuc vo mc x l trc khi a vo lm nguyn liu sn xut biodiesel. V biodiesel l este ca mono akyl ca axit

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GVHD: Th.S Nguyn Hu Sn bo nn nguyn liu u ca qu trnh sn xut biodiesel ngoi du m cn c ru. 2- Ru Ru n gin hay c s dng cho qu trnh sn xut biodiesel l metanol mc d cc ru khc nh etanol,isopropanol,v butanol u c th s dng lm nguyn liu cho qu trnh ny. Mt ch tiu quan trng i vi ru l hm lng nc. Nc dn n gim hiu sut phn ng, to nhiu x phng. Mt l do khc ngi sn xut la chn s dng ru no l ga c ca loi ru v ru phi s dng d so vi du m thu c hiu sut chuyn ha cao. Chnh v vy vn gi thnh cng phi c quan tm v tnh ton n. 3- Xc tc Xc tc s dng cho qu trnh c th l xc tc baz, xc tc axit hoc enzym. Xc tc hay c s dng l xc tc baz (NaOH hoc KOH), v cho hiu sut chuyn ha cao. Tuy nhin khi s dng xc tc ny th cn lu cc yu cu cho nguyn liu vo nh l hm lng axit bo t do cu du m v hm lng nc. Nu cc hm lng ny khng c khng ch ph hp th s gim hiu sut phn ng v cht lng ca sn phm. Xc tc axit cng c th s dng cho qu trnh chuyn ha triglyxerit thnh biodiesel nhng so vi qu trnh s dng xc tc baz th thng chm hn. S dng xc tc ny c u im l gii quyt c vn nguyn liu u vo c hm lng axit bo t do cao. 1.1.4.3 Cc phng php sn xut biodiesel Vic s dng trc tip du thc vt v m lm nhin liu cho ng c Diesel gp nhng kh khn nh qu trnh ha hi nhin liu nhit thp km gy tr ngi cho qu trnh khi ng, qu trnh chy khng hon ton dn n gim cng sut ca ng c, nht cao lm nghn filter, gy kh khn cho h thng phun nhin liu. Du thc vt v c bit l m ng vt c nht cao gp khong 11 17 ln so vi nhin liu Diesel. gim nht ca du v m th ngi ta s dng mt trong s cc phng php sau sn xut chng thnh biodiesel: Quy trnh sn xut Biodiesel t Vi to Trang 11

GVHD: Th.S Nguyn Hu Sn 1- Phng php sy nng. nht s gim khi nhit tng. Tuy nhin phng php ny khng hiu qu v du thc vt v m t c nht cn thit cho nhin liu Diesel th i hi nhit kh cao (v d nh i vi du Canola nhit mi trng th nht ca n gp 12 ln so vi nhin liu Diesel, nhit 80oC th nht vn cn gp 6 ln so vi nhin liu Diesel), hn na h thng gia nhit cho du khng th duy tr mi khi ng c khng hot ng iu lm cho du s b ng li c bit l vo ma ng, trc khi khi ng du cn phi c t nng iu gy ra nhng bt tin cho ngi li xe. 2- Phng php pha long. Pha long du hoc m vi nhin liu diesel theo t l no ta thu c hn hp nhin liu mi, hn hp ny ng nht v bn vng. Cc t l du : diesel 1 :10 v 2 : 10 em li hiu qu tt nht v nht v cc tnh cht nhit thp ca hn hp. 3- Phng php nh tng ha. Nh ha l s phn tn keo ca cc cht lng c cu trc rt nh vi ng knh nm trong khong 1nm 150nm. Phng php nh tng ha c th khc phc nhc im nht cao ca du v m bng dung mi l cc ru n gin nh etanol, metanol. H nh tng du ru c nhng tnh cht tng t vi nhin liu diesel nhng nhc im l kh duy tr v n nh h nh tng ny. 4- Phng php cracking. y l qu trnh s dng nhit cracking du thc vt to ra cc alkan, cycloalkan, alkylbenzen...Du v m sau khi b nhit phn s to thnh cc hp cht c mch ngn hn do nht s gim i. Xc tc tiu biu s dng trong qu trnh nhit phn l SiO2 v Al2O3. Nhc im ca phng php l thit b s dng trong qu trnh rt t. Biodiesel cng c th c sn xut bng hydrocracking. Nhng qu trnh cng ngh mi ang c pht trin m khng to ra Glycerol. Qu trnh ny bao gm cc cng on: hydrocracking, lm sch bng hydro v hydro ho. Quy trnh sn xut Biodiesel t Vi to Trang 12

GVHD: Th.S Nguyn Hu Sn Hiu sut thu sn phm khong 7580% vi ch s cetane cao (~100). Thnh phn sulfur thp hn 10 ppm. N phn r 95% sau 28 ngy, trong khi du diesel phn r 40% trong cng mt khong thi gian. Li ch chnh hn nhng Biodiesel khc l n lm gim lng NOx. Qu trnh ny s dng xc tc hydro ho v hydro tinh khit thng mi thng thng. Qu trnh hydrocracking c th l mt la chn thch hp cho nhng nh my lc du. Phng php ny c th d dng thch hp vi nh my lc du nh vo ngun hydro c to ra trong nh my. Tuy nhin, qu trnh ny vn cha c p dng vo thc t. 5-Phng php chuyn ha Ester. Chuyn ha este l phn ng gia lipit vi ru to thnh alkyl este v glyxerol:

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GVHD: Th.S Nguyn Hu Sn Cc alkyl este to ra c nht v trng lng phn t nh hn nhiu so vi phn t du m ban u. V vy n c c tnh cht tng t nh diesel khong. y l phng php hay c s dng nht v qu trnh tng i n gin, sn phm thu c li t hiu qu tt, ph hp l nhin liu cho ng c

diesel v sn phm ph glycerol c gi tr s dng cao trong cng nghip m phm v dc phm. Cc cng on chnh sn xut biodiesel t du, m ng thc vt bng phng php ester ha 1.2 Vi to 1.2.1 Khi nim To (Algae) l nhng thc vt bc thp gm mt hay nhiu t bo c cu to n gin, c mu khc nhau, lun lun c cht dip lc nhng cha c r, thn, l. Hu ht to sng trong nc. y l nhng thc vt m vch thn cha xenluloz, l nhng sinh vt t dng v cha dip lc a, quang tng hp

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GVHD: Th.S Nguyn Hu Sn nh nh sng v CO2. To c nhiu dng: n bo, si xin, si phn nhnh, hnh ng, hnh phin. Vi to (Microalgae) l tt c cc to c kch thc hin vi. Mun quan st chng phi s dng ti knh hin vi. Trong s khong 50 000 loi to trn th gii th vi to chim n khong 2/3. V tr ca to trong gii sinh vt nhn tht: Theo P.H. Raven v G.B. Johnson (2002) h thng phn loi chia lnh gii sinh vt nhn tht ra thnh 6 gii: -Gii Archezoa: gm cc Nguyn sinh cha c ty th, bao gm Pelomyxa, Giardia. -Gii Protozoa (ng vt nguyn sinh): bao gm 14 ngnh Nguyn sinh- trong c Hypermastigotes, Euglenoides, Slime molds (Nm nhy), Choanoflagellates, Dinoglagellates, Ciliates, Apicomplexans, Rhizopods, Heliozoans, Foraminiferans, v Radiolarians. -Gii Chromista: gm 10 ngnh Nguyn sinh, trong c To nu (Phaeophyta) v To silic (Diatoms ) -Gii Fungi (Nm): Bao gm nm v 1 ngnh Nguyn sinh sng hoi sinh l ngnh Chytridiomycota. -Gii Plantae (Thc vt) : bao gm Thc vt v 5 ngnh Nguyn sinh (nhiu To lc nh Volvox, Ulva, Spirogyra v To (Rhodophyta). -Gii Animalia (ng vt) . 1.2.2 Phn loi Vi to ch yu thuc v cc chi trong cc ngnh sau y: 1-Ngnh To lc (Chlorophyta): Cc chi Closterium, Coelastrum, Dyctyosphaerium, Scenedesmus, Pediastrum, Staurastrum, Dunaliella, Chlamydomonas, Haematococcus, Tetraselmis, Chlorella,... 2- Ngnh To lng roi lch (Heterokontophyta) Cc chi Melosira, Asterionella, Cymatopleurra, Somphonema, Fragilaria, Stephanodiscus, Navicula, Malomonas, Dinobryon, Peridinium, Isochrysis, Chaetoceros, Phaeodactylum, Skeletonema, Nitzschia...... Quy trnh sn xut Biodiesel t Vi to Trang 15

GVHD: Th.S Nguyn Hu Sn 3- Ngnh To mt (Euglenophyta): Cc chi Phacus, Trachelomonas, Ceratium... 4- Ngnh To (Rhodophyta): Cc chi Porphyridium, Rhodella... 1.2.3 Vai tr ca vi to trong t nhin v trong i sng nhn loi: To ni chung v vi to ni ring c vai tr rt quang trng trong t nhin v trong i sng nhn loi. Chng ta bit rng i dng chim 71% din tch b mt Tri t. Mt s tc gi Hoa K cho rng hng nm to c th tng hp ra trong i dng 70-280 t tn cht hu c. Trong cc thy vc nc ngt to cung cp xy v hu ht thc n s cp cho c v cc ng vt thy sinh khc. To gp phn bo v mi trng nui thy sn bng cch tiu th bt lng mui khong d tha. Canh tc bin l nhm trng v thu hoch cc to sinh khi ln v c hm lng dinh dng cao. Nhiu to bin cn khai thc sn xut thch (agar), alginate, sn phm giu iod... Nhiu to n bo c nui trng cng nghip to ra nhng ngun thc n cho ngnh nui tm hay thuc b tr giu protein, vitamin v vi khong dng cho ngi. Mt s vi to c dng sn xut carotenoid, astaxanthin, cc acid bo khng bo ha... To silic to ra cc m diatomid, l loi nguyn liu xp, nh, mn c dng trong nhiu ngnh cng nghip. To phn b ht sc rng ri khp mi ni, t nh ni cao n y bin su. Nhng to sng lp nc pha trn c gi l To ph du (Phytoplankton) cn nhng to sng bm di y thy vc, bm trn cc vt sng hay thnh tu thuyn c gi l To y (Phytobentos). Dng to cng sinh vi nm thnh a y cng l dng phn b rt rng ri v nhiu loi c khai thc dng lm dc phm, nc hoa, phm nhum v cc mc ch kinh t khc. Hin nay, vi to cn c dng sn xut ra nhin liu diesel sinh hc, m ra trin vng mi cho ngnh cng ngh sinh hc bi kh nng c th thay th hon ton cho nhin liu ha thch ang cn kit.

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GVHD: Th.S Nguyn Hu Sn 1.2.4 Sinh khi Vi to l vi sinh vt quang hp chuyn i nh sng mt tri, nc v cacbon dioxit to sinh khi. Nhiu loi vi to c cha rt nhiu du, v hin nay n c th chuyn ha thnh biodiesel bng cc cng ngh k thut. Tim nng ca vi to c th sn xut biodiesel tng i bn thay th cho nhin liu t du m nh gasoil, jet fuel, v diesel. Hm lng du ca 1 s loi vi to c th chim ti 80% hm lng kh ca sinh khi to. Cn du thc vt, nh u tng v du c cng c s dng rng ri sn xut biodiesel; tuy nhin, lng du sinh ra rt nh so vi vi to (nh hn 5% tng khi lng sinh khi). Du thc vt c sn xut ra biodiesel c cht lng rt thp v c phi trn vi diesel t du m mc vi phn trm thi, v th chng khng c kh nng to ra c biodiesel c cht lng cao c th thay th cho ngun nhin liu t du m truyn thng. Vd nh du c, 1 sn phm quan trng ca du thc vt, ch t c nng sut khong 5950l/ha. Nng sut chuyn ha biodiesel t ngun gc du thc vt l khong 80% sn lng du /ha. Nu nhin liu t du m b thay th hon ton bng biodiesel, th 1 nc nh nc M th yu cu v tc tiu th l 0.53bm3/nm. sn xut biodiesel t du c vi cht lng nh th ny th cn n 111mha trng du c, chim khong 60% din tch t nng nghip trn nc M. Vic trng du c vi quy m nh th s thiu thc t, v s khng t t sn xut ra lng thc - thc phm, v cc sn phm nng nghip khc. Da trn nhng tnh ton , r rng l ta khng th sn xut biodiesel t du thc vt thay th cho nhin liu truyn thng trong tng lai c. Cn i vi vi to: Sn lng sinh khi trung bnh hng nm cc khu vc nhit i vi h thng tt c th t khong 1.535 kg.m-3.d-1. Vi mc sinh khi v hm lng du trung bnh khong 30% hm lng kh, th ta c th d on nng sut du thu c khong 123m3/ha, t khong 90%/nm. (Khong 10% trong nm khng sn xut, v cn phi ngng dy chuyn sn xut li bo tr v lm sch h thng). Vi s lng ny th nng sut chuyn ha biodiesel t vi to t 98.4m3/ha. V th chuyn ha to c 0.53bm3 Quy trnh sn xut Biodiesel t Vi to Trang 17

GVHD: Th.S Nguyn Hu Sn biodiesel cn 5.4Mha ch chim khong 3% din tch t nng nghip ca M trng vi to. Theo l thuyt kh thi ny, nu sinh khi ca to ch cn cha 15% lng du trong khi lng kh, th khng c 1 ngun no c tim nng to biodiesel nh vi to c. Mt khm ph quan trng khc na ca vi to, khng nh cc ngun du thc vt khc, ngi ta c th trng t tc trng nhanh chng v ch cn sau 24h c th tng sinh khi gp i. Thc t, thi gian tng theo s m sinh khi l sut khong thi gian pht trin, l khong rt ngn khong 3.5h Cacbon chim khi lng kh ca sinh khi vi to l loi xut pht t cacbon dioxit. Do , sn xut ra 100 tn sinh khi to, cn gn 183 tn cacbon dioxit, cung cp lin tc trong sut c ngy. Ta c th s dng cacbon dioxit t cc nh my in t nhin liu bng ha thch. Lng cacbon dioxit s dng ny thng c sn vi chi ph thp hoc khng tn chi ph no c.

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GVHD: Th.S Nguyn Hu Sn Chng 2. Cng ngh nui trng vi to v sn xut biodiesel t vi to 2.1 Quy trnh nui trng vi to v sn xut biodiesel Biodiesel t vi to dng nh xut pht t vic ti to li nhin liu sinh hc c kh nng thay th hon ton cho nhin liu t du kh. Hu ht cc du thc vt, nh l du c th khng c kh nng cung cp c nhng thnh phn cn thit tr thnh nhin liu Biodiesel nh vi to. Qui trnh tng qut sn xut du sinh hc t vi to c a ra hnh sau:

Qui trnh tng qut v sn xut biodiesel t du vi to T s ta c th tm tt quy trnh tng th nh sau: to sau khi thu hoch c chit tch ly du, phn du ny s c dng sn xut biodiesel, cn phn b s s dng lm thc n cho ng vt hoc phn hy k kh tao ra kh sinh hc pht in cho nh my hoc in li: Bc sn xut ra sinh khi ca vi to: Cn p ng yu cu v nh sng, cacbon dioxit, nc v cc cht dinh dng cn thit. nui trng vi to, ngi ta thng s dng nc bin c b sung phn bn cha nitrat, photphat trn th trng v 1 s loi cht dinh dng khc dng vi lng. Quy trnh sn xut Biodiesel t Vi to Trang 19

GVHD: Th.S Nguyn Hu Sn Ta cn c th nui trong cc h, sng hoc b cha nc ngt hoc nc l. Nui trng i tr vi to thng khng tn nhiu chi ph lm, c th nui trng c 100 tn/nm, gi ca sn phm sinh khi vi to c tnh khong 3000$/tn, gi ny s c gim xung ng k nu quy m nui trng tng ln. Trong qu trnh nui trng - giai on sn sinh ra sinh khi, nc, cc cht dinh dng v c, cacbon dioxit v nh sng c cung cp thng xuyn. giai on phc sinh khi, cc t bo nm l lng v c tch ra khi nc v cc cht dinh dng cn d, v sau n s c ti sinh li trong giai on to sinh khi. Bc s dng sinh khi vi to: Sinh khi c s dng cho qu trnh gii phng du trong to v chuyn ha thnh biodiesel trong qu trnh phn tch. Mt s loi sinh khi c th c s dng lm thc n chn nui hoc thu hi cc sn phm khc c gi tr cao. Hu ht cc sinh khi u phi tri qua qu trnh phn hy k kh, ri sn xut kh sinh hc to ra in. Nc thi t cc l phn hy k kh c s dng nh 1 loi nc phn bn giu dinh dng. Hu ht in sinh trong sinh khi th c tiu th trong cc qu trnh sn xut hoc cc nng lng d tha th bn cho in li. Nc dng trong giai on sn xut nhin liu sinh hc cn phi c tip tc x l thu hi sinh khi. Nc v cc cht dinh dng d giai on ny s c ti sinh a vo giai on to sinh khi. Cc sinh khi tp trung s c chit vi nc, trn ln vi dung mi thch hp thu hi du to, sau s dng cc phng php chuyn ha hin nay chuyn i sang nhin liu sinh hc. Vic khai thc du trong sinh khi to rt kh thi, dung mi trong vic tch chit du (vd: hexan) c th thu hi v ti ch li s dng. Lng sinh khi cn li sau khi chit du, 1 phn c th s dng lm thc n chn nui giu protein, phn t cn li l cc sn phm c gi tr cao

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GVHD: Th.S Nguyn Hu Sn ca vi to. C 2 cch trn u to ra doanh thu t vic bn cc lng d sinh khi c th trang tri cho chi ph sn xut biodiesel. Tuy nhn, hu ht cc sinh khi d u b phn hy k kh to kh sinh hc, y chnh l ngun nng lng chnh trong hu ht cc qu trnh sn xut v ch bin sinh khi to. D kin cho phn nng lng d tha c th bn cho in li nhm nng cao hiu qu kinh t ca qu trnh tch hp ny. B sung vo doanh thu t vic bn cc nc ti hoc phn bn giu cht dinh dng c sn xut trong giai on phn hy k kh. Qui trnh phn hy k kh gii phng sinh khi rt pht trin, c th chuyn ha kh sinh hc thnh nng lng in hoc c hc rt tt. Cacbon dioxit to ra t qu trnh t chy kh sinh hc c th c ti to v s dng trc tip cho qu trnh hnh thnh sinh khi vi to. Nng lng cha trong kh sinh hc c to ra t qu trnh phn hy k kh t khong t 16200kJ/m3 n 30600kJ/m3. Hiu sut chuyn ha thnh kh sinh hc t 0.15 n 0.65m3/kg khi lng sinh khi kh. Gi s ni nng v nng sut trung bnh ca vic chuyn ha thnh kh sinh hc t nguyn liu vi to, hn 30% du c ly ra, n c th to ra t nht 9360MJ nng lng/ tn. y l 1 nng lng ng k khi ta thc hin qu trnh sn xut to sinh khi vi to. Nh vy, biodiesel t vi to c th to ra cacbon trung tnh, v tt c nng lng u cn cho qu trnh sn xut v nui trng to, c tim nng pht trin biodiesel t chnh n v metan c sn xut bng vic phn hy k kh sinh khi cn d li sau khi tch chit du. Mc d biodiesel vi to c th to ra cacbon trung tnh, n khng dn n vic gim lng kh cacbon dioxit m n s tch ly li nh l sn phm ca qu trnh t chy nhin liu ha thch. 2.1.1 Sn xut sinh khi vi to: Sn xut diesel sinh hc i hi vi to c khi lng sinh khi ln. gim thiu chi ph, sinh khi phi c sn xut bng cch s dng nh sng mt tri t do c sn v do b nh hng bi bin ng hng ngy v ma.

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GVHD: Th.S Nguyn Hu Sn To c th tn ti bt c ni no c nh sng, k c vng hoang ho, nc mn, nc thi, li c kh nng lm sch mi trng nc thi. nui to, ch cn nh sng, CO2, nc v dinh dng c th l phn ho hc hoc phn chung. To ging thng nui trong phng th nghim, v sau c th chuyn qua b hoc ao nui. Vi to c th c trng trn quy m ln phn ng sinh quang ho. Rt nhiu thit k khc nhau ca phn ng sinh quang ho c pht trin, nhng mt phn ng sinh quang ho hnh ng c v hi lng nht cho sn xut sinh khi to vi quy m cn thit cho sn xut nhin liu sinh hc.

M hnh nui vi to bng phn ng quang sinh ha Mt phn ng sinh quang ho ng bao gm mt lot cc ng thng trong sut m thng lm bng nha hoc thy tinh. Cc ng thu nng lng mt tri ng knh nh hn 0,1 m cho php nh sng thm nhp vo mt khi lng ng k ca cc t bo. Nc cho vi to c lu thng t h cha hng nng lng mt tri. Phn ng sinh quang ho l thng hot ng lin tc trong nh sng ban ngy. ti a ha thu nh sng mt tri, cc ng trong b thu nng lng mt tri b tr sp xp nh hng ro. Cc mt t bn di cc b thu nng lng mt tri c sn mu trng hoc ph bng tm nha trng tng phn Quy trnh sn xut Biodiesel t Vi to Trang 22

GVHD: Th.S Nguyn Hu Sn x cng nh chy rt hn lon. Quang hp to ra oxy. Bui tra s bc x xy ra hu ht cc v tr, tc ti a ca sinh oxy trong mt phn ng sinh ha hnh ng in hnh c th cao ti 10 g O2 m-3 min-1. Nng xy ho tan c nhiu hn so vi gi tr bo ha khng kh s ngn cn quang hp. Hn na, nng oxy ha tan cao kt hp vi nh sng mt tri mnh sn xut thit hi cho cc t bo to. ngn chn s c ch quang hp v tn thng t bo, ti a c th chu c mc oxy ha tan khng nn vt qu 400% gi tr bo ha khng kh. loi b xy, cc cng ngh c nh k tr v khu vc kh kh, trong n l hi loi b oxy tch ly. Thng thng, mt ng chy lin tc khng vt qu 80 m. Tuy nhin, chiu di ng c th ph thuc vo nhiu yu t, bao gm c s tp trung ca cc sinh khi, cng nh sng, tc dng chy v nng oxy li vo ca ng. Ngoi vic loi b cc oxy ha tan tch ly, vng kh kh phi kh sch tt c cc bong bng kh t nc dng tr v nc ban u cho cc ng thu nng lng mt tri. S c mt ca bong bng kh qu nhiu trong cc ng nng lng mt tri s cn tr s hp th nh sng v lm gim lu lng nc dng trong ng. Mt yu cu quan trng cho mt khu vc kh kh l khi lng ca n c gi tng i nh so vi khi lng ca b thu nng lng mt tri. Mt yu t khc nh hng n hiu sut sn xut sinh khi to l pH ca mi trng. chng li iu ny, lng kh carbon dioxide c a vo khu kh kh p ng vi mt b iu khin pH. Nhit ti u cho nhiu vi to pht trin l t 20 n 30,80C. Mt nhit bn ngoi phm vi ny c th git cht hoc lm tn thng t bo. To nc dng trong ng tip xc vi nh sng mt tri s nhanh chng b nng qu, tr khi n c lm mt. Lm mt hng gi di nh sng ban ngy l iu cn thit. Hn na, kim sot nhit vo ban m cng rt hu ch ngn chn n ri rt thp gy thit hi cc t bo. Quy trnh sn xut Biodiesel t Vi to Trang 23 tng tng s nh sng c nhn bi cc ng dn.

Sinh khi trm tch trong cc ng c ngn nga bng cch duy tr mt dng

GVHD: Th.S Nguyn Hu Sn C t nht mt nm mt ln, mt c s sn xut biodiesel t vi to phi c ng ca bo tr thng xuyn v lm sch. Lm sch v kh trng c yu cu cng trong trng hp tht bi ca cc cng ngh v nhim vi to khng mong mun v k sinh trng. * Yu cu chung trong nui to 1- iu kin mi trng Nhit : thch hp 20-24C,khong chu ng 16-35C mn: tt nht 20-24 cho to bin nh sng: thch hp 1.000-10.000 lux, nh sang nhn to tt nht l n neon vi chu k chiu sng 16 gi/ngy. pH: thch hp 7-9 Sc kh gip: To l lng, tip xc u vi nh sng v dinh dng, n nh nhit , cung cp CO2 v O2. 2- Mi trng dinh dng Gm hn hp cc cht a lng v vi lng. a lng gm cc cht v c nh Nitrate, Phosphore v Silicate. Vi lng gm cc mui kim loi v c th c hn hp vitamine. 3- Dng c phng tin Nui to c th c thc hin trong phng th nghim, trong tri vi mi che trong sut hay ngoi tri. Phng th nghim nn c trang b vi h thng n Neon, gi , my iu ho nhit v mt s my kh trng (UV, Ozone). Cc dng c v b nui to c th c nhiu dng, kch c v vt liu khc nhau nh ng nghim, bnh tam gic, keo ln (cho nui to trong phng th nghim), thng hay b 200 lt-10m3. Cc b c th bng ximng hay composite. Cc ti nha cng c dng nui to rt tt. H thng thi kh cng rt cn thit trong nui to nhm m bo to nui c sc kh lin tc.

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GVHD: Th.S Nguyn Hu Sn 4- Kh trng v v trng V trng l mt trong nhng khu rt quan trng trong nui to, c bit l to ging nhm trnh to b nhim tp. Cc dng c v phng php cng tng t nh k thut v trng trong phng th nghim vi sinh hay phng th nghim bnh hc. Trong phng php kh trng dng c phng th nghim nh ng nghim, bnh tam gic, keo thu tinh, que cy... cn c kh trng bng cch cho vo t sy nhit 180C trong 2 gi (Kh trng kh). Nc nui to vi th tch nh c th c kh trng bng cch cho vo t hp tit trng (Autoclave) vi nhit 120C v p sut 20 psi. Thi gian hp l 15 pht i vi th tch nh hn 1 lt hay 20-45 pht vi th tch ln 10-20 lt (kh trng t). i vi th tch ln, trc khi s dng cn x l nc bng ho cht nh Chlorine vi liu lng 1-2ppm. Nu c iu kin nn x l nc bng n cc tm (UV). * K thut nui to 1- Phn lp to ging C 3 phng php phn lp to nh sau Phng php pha long. Phn lp bng Pipette mao dn. Phn lp trn mi trng dinh dng agar. Ngoi ra, vic phn lp to cn c th p dng phng php nh dng khng sinh, phng php chiu sng tch nhng loi to c tnh hng quang v c kh nng di ng. 2- Phng php gi to ging Trn mi trng thch hoc trong mi trng lng. Gi trong ng nghim 20ml. Gi trong t lnh 4-10C c nh sng yu, khng sc kh. nh k cy chuyn trnh to gi.

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GVHD: Th.S Nguyn Hu Sn 3- Cc phng php nui Nui kn nui h Nui trong phng nui ngoi tri Nui tng t nui bn lin tc lin tc Nui chung nui ring 4- Cch thu hoch C th thu hoach vi to bng 1 trong 2 phng php sau: L hc: bm trc tip, lc, ly tm. Ho hc: Al2(SO4)3 nng 150 ppm: to ni trn b mt hoc FeCl3,
NaOH: to kt ta kch thc (khng thch hp cho cc loi n l lng).

Gi to ging trong t lnh hoc trong ng nghim

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GVHD: Th.S Nguyn Hu Sn Sau y l hnh nh mt s h thng nui to:

Quy trnh sn xut Biodiesel t Vi to

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GVHD: Th.S Nguyn Hu Sn

B nui to Bnh thun- Vit Nam

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GVHD: Th.S Nguyn Hu Sn 2.2 Quy trnh sn xut biodiesel t vi to

Sn xut Biodiesel t to vi cng ngh siu m: Du to l ngun nguyn liu th dng sn xut bio diesel.

Du chit xut t vi to

Quy trnh sn xut Biodiesel t Vi to

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GVHD: Th.S Nguyn Hu Sn Cng ngh siu m tng s chit xut du t cc t bo to v lm qu trnh chuyn bin thnh bio diesel nhanh hn. Cng nh cc loi thc vt khc, to d tr nng lng di dng lipide. C nhiu phng php chit du ra khi cc t bo nh p, ra vi hexan hoc .. chit xut vi siu m. Chit xut vi phng php siu m: Khi p dng m thanh vo trong cht lng, cc sng m thanh s c to thnh v di chuyn trong nc, thay i u t tnh trng p xut cao qua p xut thp. giai on p xut thp, trong nc hnh thnh cc bt chn khng cha nhiu nng lng. Khi bt chn khng ln chng s n bng vo bn trong (implode) trong giai on p xut cao. Khi n cc lc c nng lng cao c gii phng v s to ra cc khong khng b p. Ti vng b pht n s hnh thnh p xut rt cao, cc lc p s lm v t bo v to iu kin trao i cht d dng hn. Hiu ng ny h tr s chit xut cht lipide ca to c d dng hn. Chun b siu m cho phng php p ngui. Khi p to, iu kin c bn l kim tra c qu trnh ph v cc t bo trnh tnh trng bin dng cc cht ni bo. Khi hy cc t bo, lipide s d dng c p ra theo tc ng ca p xut bn ngoi. Ra chit vi cng ngh siu m: Trong giai on p xut cao, siu m h tr qu trnh phn tn dung dch nh Hexan trong cc t bo. Lc c to thnh ph v thnh t bo v to iu kin ha trn thun tin cho lipid vi dung dch. Khi cht bo ha tan trong Cyclohexan, ngi ta c th lc xc t bo ra ngoi, tch Hexan ra khi cht bo qua qu trnh bc hi .. Dng enzyme chit xut vi cng ngh siu m: Nu p dng phng php chit xut bng enzyme, th lc p siu m c th h tr enzyme thm nhp vo t bo mt cch d dng. Qua , gii php ny s cho ra kt qu tt hn v nc s ng vai tr ha tan nh cc dung dch khc trong khi enzyme phn hy cc thnh t bo.

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GVHD: Th.S Nguyn Hu Sn Du sinh hc, bio diesel t to: ng dng siu m trong qui trnh sn xut du diesel sinh hc khng ch hn ch trong lnh vc chit xut du Bio diesel t to c hnh thnh qua phn ng thay i bnh din ha hc. Cho d cc yu thun tin nh nhit , tc ng c nh khuy trn v cc ha cht xc tc khc, th qu trnh ny cng cn phi c thi gian phn ng t 4 -6 ting. Siu m tng kh nng ha trn ca cc thnh phn v to iu kin thun tin cho vic phn ng. Thi gian phn ng khi p dng siu m s gim n 90% v y l mt ng dng c tim nng trong lnh vc sn xut du sinh hc. Thay v phi bm cc thnh phn t bn ny sang bn kia th cc thnh phn c trn xuyn sut ngy t u v bm qua bn phn ng lin tc. Sau khong mt ting l phn ng hon tt v c dn n h thng my ly tm tch glycerin. Du dc ra v xy l hon tt s dng. Bn cnh , qua h tr ca siu m mc phn ng cao hn v chng ta cn t cn hn, gi thnh qua s gim v mc nhim cng s gim theo. 2.3 Sn phm v ng dng Trong bng di y gii thiu mt s ch tiu cht lng i vi du diesel (tiu chun EN 590) v biodiesel (tiu chun EN 14214, ASTM D6751)

Ch tiu T trng 150C, kg/m3 nht 400C, mm2/s im chp chy, 0C, min Lu hunh, mg/kg, max Ch s ceatn, min Nc, mg/kg, max Ester, % khi lng, min Methanol, % khi lng, max Monoglyxerit, % khi lng, max Quy trnh sn xut Biodiesel t Vi to

EN 590 820-845 2,0-4,5 55 50 51 200 -

EN 14214 860-900 3,5-5,0 120 10 51 500 96,5 0,2 0,8

ASTM D.6751 1,9-6,0 130 15 45 500 Trang 31

GVHD: Th.S Nguyn Hu Sn Diglyxerit, % khi lng, max Triglyxerit, % khi lng, max Glyxerin t do, % khi lng, max Tng lng glyxerin, % khi lng, max 0,2 0,2 0,02 0,25 0,02 0,24

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GVHD: Th.S Nguyn Hu Sn Chng 3. Ph lc Mt s quy trnh cng ngh sn xut biodiesel khc 3.1 Cng ngh nui trng to bin bng kh thi CO2 t cc nh my nhit in ca Cng Ty TNHH Seambiotic (Israel). Vi to bin c nui trng bng kh thi CO2 t cc nh my nhit in s lm gim ng k lng kh CO2 thi ra ngoi khng kh, lm gim tc ng hiu ng nh knh v gp phn lm sch mi trng. Theo nghin cu cho thy khi c nui trong b h bng kh CO2, vi to ny s sinh trng ln hn gp 1 triu ln so vi khi chng sng di y bin. V vi to bin pht trin tt v nhanh hn khi s dng kh CO2 thi ra t cc nh my nhit in. Theo cc nh khoa hc ca Seambiotic Ltd, nng sut nui vi to t c l 20g to trn 1m2 b nui trong 1 ngy. Trong , ngi ta c th sn xut ra 1 lt nhin liu t 5kg to bin v gi ca nhin liu sinh hc l khong 1000$/tn. D n nui to bin s gp phn to cng n vic lm v pht trin kinh t x hi ti khu vc ven bin ni gp kh khn trong trng cy nng nghip. Gp phn pht trin kinh t t nc. Chin lc kinh doanh ti Vit Nam Cng ty TNHH Seambiotic (Israel) v Cng ty C phn JIVC (Vit Nam) k kt tho thun hp tc thnh lp mt trang tri nui trng to bin ti Vit Nam vi quy m d kin nh sau: - Tng din tch: 02 hecta cho d n th im; 10hecta cho d n sn xut i tr - Tng mc vn u t d kin: 3 6 triu USD (50-100 t VND - V tr d kin: Thnh lp ti gn cc nh my nhit in, gn bin v c kh hu thun li...

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GVHD: Th.S Nguyn Hu Sn

y l mt D n Xanh rt tim nng vi hiu qu cao v kinh t ng thi mang li rt nhiu li ch v mt mi trng v x hi. 3.2 Sn xut biodiesel t to bin Vit Nam TS. Trng Vnh v cc cng s H Nng Lm TP.HCM va c nhng kt qu nghin cu cho thy to bin Chlorella c nhiu trin vng ng dng ti VN, l ngun sn xut biodiesel phong ph m khng xm hi an ninh lng thc nh nhng loi cy trng ly du biodiesel khc. Ngoi vic dng vi to sn xut nhin liu, c th dng bi to kh t trong cc ng c diesel thay th cho than bi. c bit, to c hm lng du cao c th dng chit tch ly du. Nghin cu s dng ngun to ging Chlorella trong nc, c cung cp t Khoa Thu sn Trng H Nng Lm TP.HCM, Khoa Thu sn Trng H Cn Th v Trung tm Quc gia ging Hi sn Nam B. Th nghim cho thy to Chlorella cho du c mu vng sm, nng sut chuyn i du thnh biodiesel l 97% sau 2 gi phn ng. Hm lng du trong to tnh trung bnh trn th gii t 15 - 77% tu loi. Qua th nghim ca nhm nghin cu Trng H Nng Lm cho thy,

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GVHD: Th.S Nguyn Hu Sn hm lng du to ti VN cn thp, cn c nhng bc ci tin nng hm lng du ln. Theo tnh ton ca cc nh khoa hc M, dng vi to li hn cc loi cy c du khc do nng sut du cao gp 19 - 23 ln trn cng mt din tch t trng. TS. Trng Vnh ngh, nn nhp cc ging to hm lng du cao cc n v thu sn nghin cu trin khai nui trng cc vng ngp mn, hoang ho. ng thi cn nghin cu ng dng cc thit b nui quang hp, chit tch du t ch to, gim gi thnh sn xut biodiesl trong tng lai.

To c nui trong phng th nghim. Du nguyn liu, ru v cht xc tc c trn trong l phn ng trong thi gian thch hp (1-2gi) nhit khong 60OC. Trn thc t qu trnh thng c thc hin lin tc qua hai giai on (2 l phn ng): khong 80% lng ru v xc tc c dng l phn ng th nht. Hn hp phn ng sau khi tch khi pha glixerin c a vo l phn ng th hai kt thc phn ng vi lng ru v xc tc cn li.

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GVHD: Th.S Nguyn Hu Sn Glixerin to thnh c tch ra khi pha este my phn ly hoc my ly tm. Qu trnh tch thng xy ra d dng v glixerin hu nh khng tan trong este. Lng ru d c th lm chm qu trnh tch v ru ha tan tt c glixerin ln este. Nhng khng th ui lng ru d trc qu trnh tch pha v nh th s dch chuyn cn bng v pha to ra triglixerit. Este sau khi tch khi glixerin c a n khu trung ha v qua thp tch metanol. khu trung ha ngi ta dng axit nh HCl, axit xitric trung ha lng xc tc kim d v lng x phng to thnh. Tt c lng d xc tc, x phng, mui, metanol v glixerin t do c tch khi biodiesel bng qu trnh ra nc. Trung ha bng axit trc khi ra nc nhm gim ti a lng x phng v lng nc ra cn dng do hn ch c qu trnh to nh tng (nc trong biodiesel vi tc nhn to nh tng l x phng), gy kh khn cho vic tch nc khi biodiesel. Biodiesel c lm sch nc trong thp bay hi. Nu sn xut qui m nh ngi ta thng dng cc mui kh ht nc. Mt s ngun nguyn liu cha mt lng ln axit bo t do. Axit bo t do phn ng vi xc tc kim sinh ra x phng v nc. Thc t cho thy rng qu trnh thu biodiesel c th xy ra bnh thng vi hm lng axit bo t do thp hn 5%. Khi , cn dng thm xc tc trung ha axit bo t do. Lng x phng to ra nm mc cho php. Khi hm lng axit bo t do ln hn 5%, lng x phng to ra lm chm qu trnh tch pha este v glixerin, ng thi tng mnh s to nh tng trong qu trnh ra nc. gim hm lng axit bo t do, trc phn ng chuyn v este, ngi ta dng xc tc axit, nh H2SO4, chuyn ha axit bo t do thnh este (phn ng este ha). V vy, hm lng axit bo t do l yu t chnh trong vic la chn cng ngh cho qu trnh sn xut biodiesel 3.3 Argentina sn xut nhin liu sinh hc t to bin Cng ty Oilfox S.A ca Argentina va khnh thnh nh my sn xut diesel sinh hc t to u tin ti khu vc M Latinh, vi mc tiu thay th dn cho vic sn xut nhin liu sinh hc t du u tng. Quy trnh sn xut Biodiesel t Vi to Trang 36

GVHD: Th.S Nguyn Hu Sn Ch tch Oilfox S.A Jorge Kaloustian nh gi diesel sinh hc chit xut t to c coi nh mt s la chn hiu qu thay th vic sn xut t du u tng v cc loi du thc vt khc bi v khng cn s dng t nng nghip v tnh nng kh ioxt ccbon thi ra t cc nh my cng nghip.

To c trng ti bn cha trong cc nh knh sn xut ra mt cht du xanh trong qu trnh hp th nh sng to ra hydrocarbon v tng trng rt nhanh trong thi gian ngn. Hn th na, to c th pht trin c trong cc mi trng khc nhau nh nc mn hay nc b nhim. Jonh Williams, pht ngn vin ca t chc to bin BioMass, cho bit nu tnh trn 1ha gieo trng th t to bin c th sn xut ra lng diesel sinh hc ln gp 10 ln so vi u tng. Sn xut diesel sinh hc t to bin c gi thnh rt ph hp, iu ny khin cho rt nhiu cng ty trn th gii ang ln k hoch pht trin loi nhin liu ti sinh ny. ng Kaloustian thng bo Oilfox k mt tha thun vi cng ty nng lng hng u Argentina l YPF sn xut 50.000 tn diesel sinh hc/nm. Theo lut ca Argentina, n cui nm nay, tt c cc cng ty xng du phi pha 10% diesel sinh hc trong nhin liu. 3.4 Cc vn khi chuyn sang dng diesel sinh hc

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GVHD: Th.S Nguyn Hu Sn Khi mun chuyn sang s dng diesel sinh hc th chnh sch thng tin ca nh sn xut xe c th tr thnh mt vn ln. Thng th ch sau khi tn nhiu thi gian kin tr t cu hi ngi ta mi nhn c thng tin v vic l liu mt kiu xe nht nh c cho php dng diesel sinh hc hay khng v mc d l diesel sinh hc c trn th trng t 10 nm nay nhng phn ln cc t c sn xut hng lot u khng thch nghi vi diesel sinh hc. Khi dng nhin liu diesel sinh hc cho mt xe c gii khng thch nghi vi PME, diesel sinh hc s ph hy cc ng dn nhin liu v cc vng m bng cao su. Nguyn nhn l do diesel sinh hc c tnh cht ha hc ca mt cht lm mm, cht cng c trong cc ng dn nhin liu v vng m bng cao su. Diesel sinh hc s thay th cc cht lm mm trong cc ng v vng m ny, vt liu lc u s phng ln, lc ny nu dng du diesel c ngun gc t du m th du diesel ny s ra sch diesel sinh hc. Khng c cht lm mm vt liu s cng v b thm thu nc. Mt vn khc l vic nhin liu i vo nht ng c ti cc ng c Diesel c b phun nhin liu trc tip. Vn ny thng xy ra trong thi gian vn hnh khi ng c c vn hnh c nhng thi gian chy khng ti lu di. Lng nhin liu phun cng t th cht lng phn tn ca ming phun cng gim v v th c xu hng hnh thnh nhng git nhin liu khng chy bm vo thnh ca xi lanh nhiu hn v sau l i vo h thng tun hon bi trn. Ti y bn ha hc km ca RME l mt nhc im: RME b phn hy dn trong h tun hon bi trn v nhit cao ti y, dn n cc cht cn th rn hay dng keo. Vn ny v tnh bi trn km i ca nht ng c khi c nng nhin liu cao c th dn n vic ng c b hao mn nhiu hn, v th m ngi ta khuyn l khi vn hnh bng PME nn rt ngn thi k thay nht. Mt u im ca PME c th li tr thnh nhc im khi c s dng thc t cc loi xe c gii: d b phn hy bng sinh hc v i cng l khng bn lu. xi ha v nc tch t s lm xu i cc tnh cht ca PME sau mt thi gian tn tr. V th m PME thng t c khuyn dng cho cc xe t c vn hnh. Quy trnh sn xut Biodiesel t Vi to Trang 38

GVHD: Th.S Nguyn Hu Sn Ngoi ra th v vic t chy khc nhau nn cc ng c mi khng c chng nhn l thch nghi vi PME c th c vn vi cc b phn in t ca ng c, nhng thit b m c iu chnh dng vi diesel thng thng. c bit l nhng xe c gii c trang b b lc mui than trong kh thi thng hay c vn v nhng h thng ny c iu chnh trc tng lng nhin liu phun sau mi 500 n 1.000 km nhm t cc ht mui than trong b lc. iu tt v c l nu dng diesel thng thng ny li tr thnh iu xu khi dng diesel sinh hc: nu s dng diesel sinh hc th vic tng lng nhin liu phun s lm long nht ng c. Nu s dng thun ty diesel sinh hc th vic t cc ht mui than trong b lc tr thnh khng cn thit na. V th trong tng lai s c nhng thit b cm bin nhin liu dng nhn bit cht lng ca nhin liu. Lng v thi im phun nhin liu u c th c ti u ha. Kinh nghim trong lnh vc xe chuyn ch cho thy l vic s dng diesel sinh hc nhiu nm c th dn n h hng bm nhin liu, c bit l nhng ng c c b phn bmphun nhin liu trc tip. Xe ny tuy c cho php vn hnh vi diesel sinh hc nhng nh sn xut b phn bm phun (Bosch AG) th li khng cho php cng khai dng vi RME. Ngi ta ni l v phn t RME c ln khc vi diesel thng thng v cc phn t RME trong cc knh dn tinh vi khng c kh nng bi trn y p sut cao v v th l nguyn nhn dn n hao mn nhanh hn. So snh vi loi du thc vt tt nht, th nhin liu sinh hc t vi to c kh nng thay th cho ngun nhin liu t du m m khng h nh hng n cc ngun cung cp thc phm v cc sn phm nng nghip khc. cng chnh l 1 bng chng khc chng minh, biodiesel t vi to l la chn tt hn so vi etanol sinh hc, trong thi im hin nay, khi m vic s dng nhin liu sinh hc tr nn rng ri hn.

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GVHD: Th.S Nguyn Hu Sn

KT LUN
Vic sn xut biodiesl t to khng cnh tranh vi t trng cho thc phm v gp phn gim thiu kh nh knh lm sch mi trng. y l mt hng i trin vng m nhiu nc trn th gii i. Trong thnh phn t nhin ca vi to c cha du nng v nh c tng hp trong qu trnh quang hp. Du chit xut c t vi to chnh l ngun nguyn liu sn xut biodiesel. So vi cc du thc vt c nghin cu sn xut diesel sinh hc th du vi to c nhiu u im nht v c kh nng thay th c diesel sn xut t du m. Hin nay c rt nhiu nh khoa hc nghin cu v cng ngh sn xut biodiesel t vi to cho ra c kt qu tt. Do vy chc chn trong tng lai khng xa loi nhin liu ny s rt ph bin trn th trng v c nhiu ngi n nhn bi nhng li ch kinh t cng nh vic bo v mi trng.

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