TRNG I HC M A CHT KHOA DU KH ----------------o0o----------------

TIU LUN MN HC
TNG QUAN QUY TRNH TNG HP DU DIESEL SINH HC T DU THC VT PHI THC PHM V DU PH THI

Gio vin hng dn: TS. Nguyn Xun Ni

Ngi thc hin: Hong Anh Tun Lp: Cao hc K thut Ha du 10-2

H Ni 11/2011

M U

Ngy nay, cng vi vic cn dn ca ngun nguyn liu ho thch, mt vn nng bng m loi ngi rt quan tm l hin tng nhim mi trng sinh thi ton cu, mt trong nhng nguyn nhn ch yu l do kh thi ca ng c t trong gy nn. Nhng kh thi ny v ang tch t trong bu kh quyn vt xa tiu chun cho php, e da sc kho cng ng. Ngoi ra, kh thi nh hng rt xu n cc h sinh thi v gy nn nhng bin i kh hu ton cu, c th l lm tng hiu ng nh knh, to ra nhng trn ma axit, lm suy gim tng zn, Chnh v vy, vic nghin cu tm ra cc dng nng lng mi thay th ngun nguyn liu ho thch ang ngy cng cn kit, m bo an ninh nng lng, gim thiu nhim mi trng sinh thi ang tr thnh mt vn thi s nng bng ca nhiu quc gia trn th gii. Mt trong cc dng nng lng hin ang c quan tm hn c l nhin liu sinh hc v c bit l nhin liu biodiesel do xu hng diesel ho cc loi ng c. Cng vi cc nc khc, Vit Nam cng ang phi chu s nhim mi trng v nn kinh t chu s nh hng mnh ca gi du th trn th gii. Nhm gii quyt vn ny, nhiu quc gia, vic s dng biodiesel tng mnh trong mt vi nm gn y. Qua kho st ngun cung du thc vt phi thc phm (du ht cao su, du bng, du tru,) thy rng ngun nguyn liu ny rt di do Vit Nam to iu kin thun li cho qu trnh tng hp biodiesel.

I. TNG QUAN V NHIN LIU SINH HC BIODIESEL Thc t nhin liu diesel sinh hc (biodiesel) c lch s hn 100 nm. Du lc l dng u tin ca nhin liu ny c Rudolf Diesel s dng chy ng c diesel u tin do ng ch to vo nm 1895. Tuy nhin phi n nhng nm 80 ca th k 20 biodiesel mi c nghin cu v s dng rng ri. Chu u i tin phong trong lnh vc ny cng v a s cc nc khng c ngun nguyn liu du m. Ch trong mt thi gian tng i ngn hng lot cc nh my sn xut nhin liu biodiesel quy m 100.000 tn/nm ra i, tp trung nhiu nht c, Italia, o, Php, Thy in, Ty Ban Nha. Trong khi , ti chu , vic nghin cu v ng dng biodiesel cng pht trin mnh, tiu biu nh n , Malaysia, Indonesia. Ngoi ra cc nc chu Phi cng ang bc u trin khai nhiu nghin cu v biodiesel. Hin nay trn th gii nc s dng rng ri biodiesel nht l M vi nhiu chnh sch u i ca chnh ph. Vit Nam ngay t cch y hn 20 nm bt u c nhng cng trnh nghin cu v biodiesel, tuy nhin cc kt qu nghin cu ny cha c ng dng rng ri. Trong tng lai, khi cc ngun nng lng truyn thng cn dn th kh nng s dng cc ngun nhin liu mi s c nhiu trin vng hn. Du thc vt c coi l nhin liu thay th thch hp v nhng thun li ca n so vi nhin liu diesel truyn thng l cht lng d vn chuyn, sn c, kh nng ti sinh c, nhit lng cao hn, hm lng lu hunh thp hn, hm lng cht thm thp hn, kh nng d b vi khun phn hu, nht cao hn, kh nng bay hi thp hn. Bn cnh s dng du thc vt lm nhin liu thay th cn thc y s pht trin ca ngnh nng nghip, ch ng c ngun nguyn liu, gii quyt c mi quan tm hng u ca th gii l vn nhim mi trng v hiu ng nh knh. Vn chnh lin quan n vic hn ch s dng trc tip du thc vt lm nhin liu l nht. Du thc vt c nht rt cao, ln gp 10 n 20 ln nhin liu diesel, kh nng ha hi thp dn n kh nng t bc chy km, gy cn trong ng c. khc phc nhc im ny cc nh nghin cu a ra cc bin php sau: [1,5,6] - Phng php sy nng. - Phng php pha long du thc vt. - Phng php cracking. - Phng php nh tng ha.
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- Phng php trao i este to biodiesel. Trong cc phng php trn, phng php trao i este to biodiesel l s la chn tt nht v cc c tnh vt l ca alkyl este rt gn vi nhin liu diesel thng thng v qu trnh ny cng tng i n gin, chi ph khng cao. Hn na, cc alkyl este c th chy trong ng c m khng cn phi thay i cc chi tit ca ng c vi s to cn rt thp. Bng 1. Tnh cht vt l ca diesel gc khong so vi biodiesel[1] TT 1 2 3 4 5 Tnh cht Tr s xetan Nhit chp chy, oC Khi lng ring (kg/l) nht 40oC, cSt Hm lng lu hunh, % min Diesel 40 - 55 55 0,81 0,89 2 4,5 0,05 Biodiesel 46 - 65 130 0,87 0,89 4-6 < 0,0005

I.1. Tng hp biodiesel theo phng phap trao i este [7,9,10] Biodiesel l cc mono ankyl este mch thng c iu ch bng phn ng trao i este gia cc loi du thc vt v m ng vt vi cc loi ru mch thng (metanol, etanol,). Biodiesel c th c sn xut bi nhiu cng ngh este ho khc nhau. Bn cht ha hc ca phn ng trao i este to biodiesel nh sau:

R1COOCH2 R2COOCH R3COOCH2

Triglyxerit Ru mch thng

HOCH2 + 3ROH HOCH HOCH2

Glyxerin

R1COOR + R2COOR R1COOR

Biodiesel

Ru s dng trong cc qu trnh ny thng l cc ru n chc, cha khong t mt n tm nguyn t cacbon nh metanol, etanol, propanol, butanol, v cc amylacol. Trong , metanol v etanol l hay c s dng nht. Etanol c u im l sn phm ca nng nghip, c th ti to c, d b phn hu sinh hc, t nhim mi trng hn, nhng metanol li c s dng nhiu hn v gi thnh thp hn, cho php tch ng thi pha glyxerin do n l ru mch ngn nht v phn cc. Tuy nhin lng metanol dng phi theo t l

thch hp v nu lng metanol d nhiu s lm cho qu trnh phn lp sn phm kh khn hn, tn nhiu nng lng cho qu trnh thu hi metanol. Phn ng s dng etanol phc tp hn v n yu cu lng nc trong ru v trong du rt thp. Mt khc, kh nng tn cng ca nhm C2H5O- vo nhm cacbonyl ca phn t glyxerit to hp cht trung gian s km hn so vi nhm CH3O-. Chnh iu ny lm hiu sut to biodiesel ca ru c phn t ln ni chung v etanol ni ring tng i thp. Khi hiu sut thp, lng etanol d nhiu s ha tan vo trong lp biodiesel v glyxerin lm t trng ca glyxerin s gim xung dn n hn hp sn phm kh phn lp, gy kh khn cho qu trnh tinh ch sn phm. Ngoai ra, c th s dng cc ancol c s cacbon bng 3 hoc 4. Tuy nhin mch ca ru cng ln th tc trao i este cng nh, s phn tch pha cng km, v vy chng t c s dng [6].. Cc phng php trao i este sn xut biodiesel t du thc vt l: - Phng php siu ti hn. - Phng php Biox. - Phng php chuyn ho du thnh axit, sau este ho thnh biodiesel.. - Phng php trao i este c s dng xc tc. I.2. Xc tc ca qu trnh tng hp biodiesel bng phn ng trao i este
[4,8,11]

- Xuc tac axit. - Xuc tac baz - Xuc tac enzyme - Xuc tac di th I.3. C ch phn ng trao i este Phn ng trao i este c thc hin trn nhiu loi xc tc khc nhau nhng hin nay c ch phn ng mi c nghin cu k trn xc tc baz kim. C ch phn ng c th m t nh sau: u tin l phn ng ca phn t ru vi xc tc baz to thnh alkoxide: ROH + B RO+ BH+ (1)
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Sau gc RO- s tn cng vo nhm cacbonyl ca phn t glyxerit to hp cht trung gian:
R1COOCH2 R2COOCH2 H2C - O - CR3 O + -OR R1COOCH2 R2COOCH2 OR (2)

H2C - O - CR3 O-

Hp cht trung gian ny khng bn tip tc to ra mt anion v mt alkyl este tng ng:
R1COOCH2 R2COOCH2 OR R1COOCH2 R2COOCH2 H2C - O+ ROOCR3 (3)

H2C - O - CR3 O-

Cui cng l s hon nguyn li xc tc theo phng trnh (4):

R1COOCH2 R2COOCH2 H2C - O+ BH

R1COOCH2 R2COOCH2 H2C - OH + B (4)

Xc tc B li tip tc phn ng vi cc diglyxerit v monoglyxerit ging nh c ch trn, cui cng to ra cc alkyl este v glyxerin. I.4. u im ca biodiesel - Tr s Xetan cao - Hm lng lu hunh - Qu trnh chy sch - Kh nng bi trn gim mi mn - Kh nng phn hy sinh hc - Kh nng thch hp cho ma ng. - Gim lng kh thi c hi - Ch ng v nguyn liu
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- Lm nguyn liu cho tng hp ha hc I.5. Nhc im ca biodiesel - Gi thnh kh cao - Mun s dng biodiesel nh l mt dng nhin liu thng xuyn th cn phi quy hoch tt vng nguyn liu. - Biodiesel l alkyl este ca du thc vt nn rt d b phn hu sinh hc, biodiesel d b phn hu sinh hc gp bn ln nhin liu diesel thng thng. Hn hp B20 d b phn hu gp 2 ln nhin liu diesel thng thng, do trong biodiesel vn cn cha cc axit khng no. V vy vn bo qun tn cha biodiesel cn phi c quan tm - C th gy nhim: Nu qu trnh sn xut biodiesel khng m bo, v d ra biodiesel khng sch th khi s dng vn gy ra cc vn nhim do vn cn x phng, kim d, metanol, glyxerin t do. II. TNH HNH SN XUT V XU HNG PHT TRIN BIODIESEL

II.1. Tnh hnh sn xut v xu hng pht trin biodiesel trn th gii Trong nhng nm gn y rt nhiu nc trn th gii quan tm n vic sn xut ra cc loi nhin liu sch, trong biodiesel l mt dng nhin liu sinh hc c quan tm hn c do xu hng diesel ho ng c. Ti chu u, t nm 1992 bt u sn xut biodiesel quy m cng nghip. Nguyn liu cho sn xut biodiesel chu u l du thc vt, trong a s l du ht ci v du hng dng. Hin nay c trn 40 nh my ln vi cng sut vi trm nghn tn/nm. Nhng nh my ny tp trung c, o, Italia, Php, Thy in. T nm 2001, Anh cng a ra th trng nhin liu cha 5% biodiesel. Nguyn liu chnh sn xut biodiesel Anh l ngun du m ph thi v cy ci du vi sn lng hn 600.000 tn biodiesel/nm. Cn ti Php, mc tiu th biodiesel cng tng mnh trong vi nm gn y, t 250.000 tn vo nm 1998, tng ln 387.000 tn vo nm 2004 v 960.000 tn vo nm 2008. Ti M, nm 1992, y ban biodiesel quc gia c thnh lp nhm phi hp thc hin cc chng trnh k thut v iu phi biodiesel. Vic nghin cu, sn xut, kinh doanh v th nghim biodiesel c pht trin rng khp nhiu bang nh California, Nevada, Alaska,
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Canada l nc xut khu du canola ln (ch yu sang Nht). Cng ngh sn xut biodiesel ca Canada tp trung theo hng lm sch du thc vt bng hydro to xetan sinh hc ri pha vo diesel, gi l diesel xanh. Ti chu , nghin cu v biodiesel pht trin mnh n , Malaysia, Indonesia, Nht Bn, Australia, Hin nay Australia ang sn xut biodiesel theo tiu chun EU t du n ph thi vi sn lng tiu th khong trn 100.000 tn biodiesel/nm. n l nc tiu th nhin liu diesel ln (40 triu tn hng nm) c k hoch pht trin cc n in trng cy Jatropha nhng vng t kh cn ch cung cp nguyn liu sn xut biodiesel. Jatropha l loi cy lu nm v chu hn tt, theo tnh ton t nm th hai bt u cho ht v t nm th nm cho sn lng n nh 1 2 tn ht/hecta/nm. Trung Quc, Hng Kng cng th nghim dng biodiesel cho xe ti, xe bus. Biodiesel y ch yu c sn xut t du v m thi. Ngoi ra cc nc ng Nam cng bt u quan tm n sn xut biodiesel, c bit l t du c (Thi Lan, Malaysia) v du da (Philippin). B nng lng Thi Lan t mc tiu, n 2011, lng biodiesel s t 3% (tng ng 2,4 triu lt/ngy) tng lng diesel tiu th trn c nc v nm 2012, t l ny s t 10% (tng ng 8,5 triu lt/ngy). II.2. Tnh hnh nghin cu v sn xut biodiesel Vit nam [2,3] Vit Nam, vic iu ch v th nghim biodiesel t du thc vt bt u c quan tm t nhng nm 1980. Trong khong 5 nm gn y cc nghin cu v iu ch biodiesel c ch nhiu, ch yu l theo phng php chuyn ha este vi ngun nguyn liu t du da, du u nnh, du n ph thi, m ng vt. T thng 8-2007, mt h thng sn xut nhin liu sinh hc t du n ph thi vi cng sut 2 tn/ngy trin khai ti cng ty Ph Xng, thnh ph H Ch Minh. Ti An Giang, ti nghin cu khoa hc ca tc gi H Xun Thin cng mt s cn b k thut thuc cng ty c phn xut nhp khu thy sn An Giang (AGIFISH) nghin cu cng ngh sn xut biodiesel t m c tra, c ba sa hin ang oc p dng cc cng ty trong khu vc ng bng sng Cu Long nh: cng ty AGIFISH, cng ty MINH T, v cc c s sn xut nh l khc Nhm nghin cu do TS. H Sn Lm Phn vin khoa hc vt liu Thnh ph H Ch Minh thuc Vin Khoa hc v cng ngh Vit Nam ch tr nghin cu qu trnh sn xut biodiesel t du n ph thi v mt s loi du khc nh du u nnh, du ht cao su, Nm 2008, s Khoa
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hc cng ngh Thnh ph H Ch Minh cng hon thnh d n sn xut biodiesel t du n qua s dng v ch to thnh cng dy chuyn sn xut 2.000 lt du biodiesel/ngy v hin d n c giao cho cng ty TNHH Hng Qung Minh thc hin.. Tuy nhin, mt s phng n v pht trin v sn xut biodiesel quy m ln nc ta vn mi ang trong giai on khi u hay chun b khi hnh. T kho st thc cc ngun du nguyn liu Vit Nam thy rng trong thi gian ti nn nh hng nghin cu sn xut biodiesel t du n ph thi v cc loi du thc vt phi thc phm nh du ht cao su, du bng, III. GII THIU MT S CNG NGH TNG HP BIODIESEL sn xut biodiesel c th s dng cc cng ngh sau: - Cng ngh gin on. - Cng ngh lin tc Do th trng nhin liu biodiesel cn hn ch nn hu ht cc x nghip ca M s dng cng ngh gin on. Cng ngh lin tc c s dng chu u v mt s qu trnh cng nghip M. Cng ngh gin on to iu kin tt cho vic kim tra cht lng sn phm khi c s thay i ngun nguyn liu. Mc tiu ca tt c cc cng ngh ny l sn xut ra sn phm t tiu chun nhin liu sinh hc v cc tnh cht ca n phi tha mn cc tiu chun c quy nh. III.1. Cng ngh sn xut gin on Du nguyn liu c lc v x l trc loi nc v tp cht, sau c a vo thit b phn ng trc tin, sau l xc tc v ru. Thit b phn ng c gia nhit v khuy trn trong sut thi gian phn ng. Sau khi phn ng kt thc, hn hp c n nh cho phn lp hoc bm vo bnh cha hay phn ring tng pha nh my ly tm. Ru c c hai pha c loi b bng cch chng ct. Pha este c trung ha v ra bng nc nng c tnh axit nh loi b kim v phn ru cn li. Sau chng tch nc thu hi sn phm biodiesel. Pha glyxerin c trung ha v a i tinh ch thu glyxerin tinh khit.

Ru

Nc Biodiesel Lm kh

Du thc vt

Ester Ru Nc ra

Ru Xc tc Thit b phn ng

Tch glyxerin
Glyxerin tinh khit

Glyxerin th

Thit b tinh ch glyxerin

Hnh 1. Cng ngh sn xut biodiesel theo phng php gin on Ni chung cng ngh sn xut gin on n gin, ch ph thp, c th s dng nhiu ngun nguyn liu khc nhau. Tuy nhin, vi lng nguyn liu u vo cao, th tch thit b cng knh nn cng ngh ny ch thch hp sn xut quy m nh. III.2. Cng ngh sn xut lin tc III.2.1. Cng ngh sn xut lin tc c s dng xc tc Phng php sn xut lin tc c hiu sut cao hn phng php gin on do sau khi phn ng xong trong thit b phn ng th nht li tip tc c a vo thit b tip theo phn ng trit hn. Phng php ny c th t ti hiu sut 98%. Ni chung phng php ny c th thc hin vi cng sut ln, d t ng ha ton b quy trnh v gim chi ph sn xut, tuy nhin li i hi ch ph u t ban u cao vo vic xy dng h thng l phn ng.
R u D u th c vt N c B iodiesel L m kh R u X c tc T hit b phn ng 1 R u R u T ch T hit b phn ng 2 glyxerin G lyxerin G lyxerin th G lyxerin tinh khit N c ra

E ster

E ster

S lng l phn ng trung gian n = 2.n

T hit b tinh ch glyxerin

Hnh 2. Cng ngh tng hp biodiesel theo phng php lin tc

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Nu nguyn liu ban u c nhiu axit bo t do th axit bo s phn ng vi xc tc to x phng (nu phn ng s dng xc tc kim). Lng axit bo t do ti a i vi phn ng c xc tc kim l 2%, nhng tt nht l di 1%. Tuy nhin nhiu nguyn liu u vo c hm lng axit bo t do cao hn nhiu nn cn phi 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 lng axit bo t do xung di 1%, sau tin hnh phn ng trao i este bng xc tc kim. Trong phn ng este ha cc axit bo c to ra mt lng nc nht nh cn phi c loi b bng cch cho bay hi. Axit hay s dng lm xc tc l axit sunfuric hoc axit photphoric. III.2.2. Cng ngh siu ti hn khng s dng xc tc Phng php ny oi hoi s dng t l metanol/du kh cao (t 20/1 30/1) v c tin hnh di iu kin siu ti hn (t 350400 oC, p sut > 80 at). Hn hp phn ng phi c lm lnh nhanh trnh phn hy[1,20]. Do tin hnh trong iu kin khc nghit nh vy nn cng ngh ny i hi chi ph rt tn km.

Methanol Nc Du thc vt Pha du

TB phn tch

Thu hi Methanol

Thit b lm sch Biodiesel

Thit b phn ng 1 thu phn

TB phn Thit b phn ng 2 tch

ester ho Pha nc X l nc thi Glyxerin

Hnh 3. Cng ngh tng hp biodiesel theo phng php siu ti hn IV. NGHIN CU X L DU THC VT NGUYN LIU

Du thc vt thu c t nguyn liu bng cc phng php khc nhau (p, trch ly, chng ct) mi ch qua lm sch s b gi l du th. Trong thnh phn ca du th cn c nhiu loi tp cht khc nhau cn phi c loi b ty theo mc ch s dng, c bit l cc axit t do. y l yu t nh hng rt ln ti phn ng tng hp biodiesel. Nu trong du th c nhiu axit bo t do
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s lm gim hiu sut ca phan ng tng hp biodiesel, thm ch phn ng khng thc hin c do hn hp ng c li nu s dng xc tc kim (do axit bo tc dng vi xc tc kim to x phng). Vit Nam l mt nc nng nghip, c li th v cc loi cy c ht v du phong ph. Tr lng ca mt s loi du thc vt phi thc phm hng nm Vit Nam c ch ra trong bng 2. Bng 2. Tr lng ca mt s loi du thc vt phi thc phm Vit Nam TT 1 2 3 4 5 Loi du Du ht cao su Du ht bng Du tru Du v iu Du n ph thi Tr lng (tn/nm) 25.000 740 200 1.700 85.000

(Ngun : Tng cc thng k v Vin nghin cu du v cy c du) Qua kho st ngun du thc vt phi thc phm thy rng du ht cao su v du n ph thi l ngun nguyn liu sn c v c sn lng ln. Cn du bng tuy c sn lng nh hn nhng trong du bng c cha thnh phn axit bo khng no cao (to iu kin cho phn ng vi tc nhn nucleophin) nn hiu sut trao i este cao. IV.1. X l du n ph thi Qu trnh tinh ch du n ph thi s dng phn ng trung ha bng kim c th tm tt nh sau: - ong 100 ml du ph thi ( c lc b cc cn bn v tp cht rn) vo cc 250 ml, khuy nh v gia nhit n 60C. - Dng buret nh t t 40 ml dung dch kim vi nng c tinh toan theo y khao sat, khuy nh v duy tr phn ng 60C trong 15 pht. - Khi kt thc phn ng, chuyn hn hp dung dch vo phu chit hn hp tach pha. Chit ly phn dung dch pha trn v ra dung dch ny bng 100 ml nc nng loi b kim d v x phng. - Lc b phn kt ta, tip tc ra sn phm bng nc nng cho n khi loi ht kim d (dng ch th phenolphtalein kim tra). trnh nc ra b
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nh ha do lng x phng cn li, ra tip sn phm bng dung dch mui natri sunphat nng 5% cho n khi nc ra c mi trng trung tnh. - Tip tc ra bng nc nng cho n khi kh ht ion sunphat. Sau ui nc n 130oC s thu c du t yu cu. Qu trnh x l du n ph thi chu nh hng ca bn yu t chnh: tc nhn trung ha, nng tc nhn trung ha, nhit nc ra v s ln ra [10,20]. IV.2. X l du ht cao su Do du ht cao su c ch s axit rt cao nn nu s dng kim trung ha axit bo t do c trong du th s mt rt nhiu thi gian thu c du c ch s axit t yu cu lm nguyn liu cho phn ng tng hp biodiesel. Do vy, phng php c la chn l s dng phn ng trao i este trn xc tc axit sunfuric (H2SO4) c. Qu trnh tin hnh nh sau: Ly 100 ml du ht cao su cho vo bnh cu ba c c lp sinh hnh hi lu v nhit k. H thng ny c t trn my khuy t v c gia nhit ln n 40 oC v khuy vi tc nh trc. Sau cho metanol v mt lng axit H2SO4 nht nh vo bnh phn ng. Tip tc gia nhit n nhit phn ng v gi nguyn nhit trong sut thi gian phn ng. lng hn hp thu c sau phn ng, tch ri tinh ch s thu c sn phm du trung tnh lm nguyn liu cho phn ng tng hp biodiesel. Qu trnh ny c th coi nh l giai on 1 ca phn ng tng hp biodiesel t du ht cao su v n chu nh hng ca nhiu yu t nh: t l metanol/du, hm lng H2SO4, thi gian phn ng,

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V. TNG HP BIODIESEL T DU THC VT PHI THC PHM V DU N PH THI Quy trnh tng hp biodiesel c th m t bng s sau:

Metanol

Xc tc

Du thc vt

Chuyn ho este [khuy trn, gia nhit]

Xc tc

Thu hi metanol t biodiesel

Tch pha

Thu hi xc tc v glyxerin

Ra nc

Thu hi metanol

ui nc Tinh ch glyxerin Biodiesel tinh ch Glyxerin tinh ch

Hnh 4. S cng ngh sn sut biodiesel Nh vy, qu trnh tng hp biodiesel s cho hai sn phm chnh l biodiesel v glyxerin. Glyxerin cng l mt sn phm c gi tr kinh t cao, tuy nhin, do thi gian c hn nn trong phm vi ti ny s khng nghin cu thu hi glyxerin. H thng phn ng l mt bnh ba c, dung tch 500 ml. Mt c cm nhit k 100 khng ch nhit theo yu cu, mt c lp sinh hn ngng t metanol bay hi ln quay li thit b phn ng, mt c np hn hp metanol v xc tc vo thit b phn ng, mt my khuy t c b phn gia nhit. Bnh phn ng c t trn my khuy t gia nhit c iu chnh c tc khuy cng nh tc gia nhit.
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Ngoi ra cn c mt bnh tam gic 250 ml, cc 500ml, phu chit 500ml, my khuy, v cc thuc th cn thit nh giy pH. Trc khi tin hnh phn ng cc dng c u phi c lm sch trit , khng c ln bi v nc vo lm chm qu trnh phn ng.

1. Thit b khuy t c b phn gia nhit 2. Bnh phn ng 3. Sinh hn 4. Nhit k 5. Con khuy t

Hnh 5. Thit b tng hp biodiesel trong phng th nghim chuyn ha ca sn phm c th tnh theo cng thc sau: C = mbio. Cbio/Mbio/{mdu/(Mdu.3)} Trong :
-

(1)

mbio , mdu: Khi lng sn phm v khi lng nguyn liu, g. Cbio: Hm lng biodiesel trong sn phm. Mdu, Mbio: Khi lng phn t trung bnh ca du v biodiesel.

- H s 3 xut hin trong phng trnh v mi phn t triglyxerit to ra 3 phn t metyl este. Hiu sut ca phn ng c xc nh theo cng thc: H = mbio/mdu
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mbio: Khi lng sn phm thu c, g. mdu: Khi lng du em phn ng, g. chuyn ho ca sn phm cng c th c tnh theo lng glyxerin to thnh: C = mgly/{92(mdu/Mdu)} Trong :
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(2)

mdu: Khi lng du em phn ng, g. Mdu: Khi lng phn t trung bnh ca du thc vt. mgly: Khi lng glyxerin thu c. S 92 l phn t lng ca glyxerin. VI. QUY TRNH CNG NGH TNG HP BIODIESEL T DU THC VT PHI THC PHM V DU N PH THI

- Quy trnh 1: x l du thc vt nhm thu nguyn liu t yu cu cho qu trnh tng hp biodiesel (p dng vi du n ph thi v du ht cao su, cn du bng t yu cu v ch s axit nn c th s dng ngay tng hp biodiesel m khng cn phi x l) - Quy trnh 2: tng hp biodiesel. VI.1. Quy trnh x l du thc vt VI.1.1. Quy trnh x l du n ph thi S nguyn l chung cho quy trnh x l du n ph thi nh sau: Du n ph thi NaOH Nc

Du x l 1 Tp cht 5 2 Dung dch thi 6 Hnh 6. S nguyn l h thng x l du n ph thi 1. Thit b tch tp cht 2. Thit b trung ha axit bo t do 3. Thit b ra 4. Thit b sy 5. Thit b cha cn 6. Thit b x l nc thi 3 Nc thi 4

Trc tin, du n ph thi c a vo thit b s 1 tch tp cht. Sau khong 1 gi lng, tch tp cht sang thit b s 5 v du c bm sang thit b s 2. Ti y, cc axit bo t do trong du c trung ha bng cch
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bm t t dung dch NaOH 10% theo t l 40% th tch so vi du. Khuy v duy tr phn ng nhit 60oC trong 15 pht. Sau khi trung ha, tch cn x phng bng cch lng hn hp trong vng 2 gi ri loi b phn dung dch thi di. Du tip tc c bm sang thit b s 3 tin hnh ra nhm loi tr trit x phng. Qu trnh ra c tin hnh 3 ln bng nc nng 80oC v ra thm 2 ln bng dung dch mui natri sunphat (Na2SO4) 5%. Ra li bng nc nng kh ion sunphat. Sau mi ln ra, hn hp c lng 30 pht ri tho nc ra vo thit b s 6. Du sau khi ra c bm sang thit b s 4 tch hi nc. Sn phm thu c s c s dng lm nguyn liu cho qu trnh tng hp biodiesel. VI.1.2. Quy trnh x l du ht cao su Qu trnh x l du ht cao su da trn phn ng trao i este vi xc tc l axit sunfuric c. Qu trnh ny c th coi nh l giai on 1 ca phn ng tng hp biodiesel. S nguyn l ca qu trnh nh sau:
Metanol hi lu

Metanol Du ht cao su H2SO4

3 1 2
Cht thi Nc

4
Cht thi Nc ra

Du ht cao su x l

6 Hnh 7. S nguyn l h thng x l du ht cao su 1. Thit b phn ng 2. Thit b tch metanol 3. Thit b chng ct metanol 4. Thit b ra 5. Thit b sy 6. Thit b x l nc thi

- Du ht cao su c a vo thit b s 1, khuy vi tc 600 vng/pht v gia nhit n 40oC. Sau thm metanol v axit sunfuric vo theo t l ln lt l 30% v 1,5% th tch du. Tip tc gia nhit n 60 oC v duy tr nhit phn ng ny trong 2 gi. Sau khi kt thc phn ng, hn hp sn phm
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c bm sang thit b s 2 tch metanol. Metanol ngng t trong thit b ny s c chuyn sang thit b ct thu hi metanol (s 3) v metanol tinh khit thu c s hi lu tr li thit b phn ng 1. Phn cn, cht thi y thp chng ct c chuyn n thit b x l nc thi 6.
- Hn hp sn phm sau khi tch metanol lng trong 1 gi loi

b dung dch bn. Phn sn phm trn tip tc c chuyn sang thit b s 4 lm sch sn phm ra bng nc nng khong 70 oC cho n khi c mi trng trung tnh, sau sn phm tip tc c chuyn sang thit b sy (5) loi nc. Nc ra ca ton b qu trnh s c thu gom v v thit b x l nc thi x l trc khi thi ra mi trng. Du ht cao su x l hm lng axit bo t do c s dng lm nguyn liu cho qu trnh tng hp biodiesel. VI.2. Quy trnh tng hp biodiesel Biodiesel c tng hp theo s cng ngh nh hnh 8. Trc tin du thc vt cng vi xc tc v metanol c a vo thit b phn ng 1. Sau khi kt thc phn ng, hn hp sn phm c bm sang thit b s 2 tch metanol. Metanol ngng t ti thit b ny s c chuyn sang thit b ct thu hi metanol (s 3) v metanol tinh khit thu c s hi lu tr li thit b phn ng. Phn cn, cht thi y thp chng ct c chuyn n thit b x l nc thi 8. Hn hp sn phm sau khi tch metanol tip tc c chuyn sang thit b lng, tch (4) tch xc tc v glyxerin khi metyl este. Xc tc c a i x l tip tc ti s dng hoc ti sinh. Glyxerin c chuyn sang thit b tinh ch glyxerin (s 7). Sau khi tch xc tc v glyxerin, metyl este c chuyn sang thit b s 5 ra bng nc nng khong 70oC cho n khi c mi trng trung tnh (pH 7), sau sn phm tip tc c chuyn sang thit b sy (6) loi nc. Nc thi t thit b tinh ch metyl este s c a v thit b x l nc thi x l trc khi thi ra mi trng.

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Metanol hi lu

Metanol Du thc vt Xc tc

3 1 2
Cht thi

Nc

4
Xc tc

Biodiesel

Cht thi

Nc ra

Glyxerin tinh ch

Hnh 8. S nguyn l h thng thit b sn xut biodiesel 1. Thit b phn ng 2. Thit b tch metanol 3. Thit b chng ct metanol 4. Thit b lng tch 5. Thit b tinh ch metyl este 6. Thit b sy 7. Thit b tinh ch glyxerin 8. Thit b x l nc thi

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KT LUN Qua tham kho cc ti liu v tnh hnh trin khai sn xut diesel, tiu lun tng hp v nu ra c cc ni dung chnh sau y:
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Nghin cu tnh hnh sn xut biodiesel trong nc cng nh trn th gii. Nghin cu phng php trao i este v c ch ca phn ng trao i este tng hp biodiesel Nghin cu mt s cng ngh sn xut biodiesel trn th gii, qua xut cc quy trnh tng hp biodiesel t ngun nguyn liu sn c ti Vit Nam: du phi thc phm v du n ph thi.

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TI LIU THAM KHO

[1] inh Th Ng, Nguyn Khnh Diu Hng. Nhin liu sch v cc qu trnh x l trong ha du. Nh xut bn khoa hc v k thut, 2008. [2] TCVN 7717 : 2007. Nhin liu diesel sinh hc gc (B100). Yu cu k thut. [3] V Th Thu H, L Kim Din (2006). Nghin cu hon thin cng ngh sn xut Biodiesel t cc ngun nguyn liu khc nhau v nh gi tnh cht ca hn hp nhin liu biodiesel/diesel. Vin ha hc cng nghip, H Ni. [4] Adam Khan (2002). Research into Biodiesel catalyst screening & development. Brisbane, Queensland, Australia. [5] A.S.Ramadhas, C.Muraleedharan, S.Jayaraj (2005). Performance and emission evaluation of a diesel engine fueled with methyl esters of rubbes seed oil, National Institute of Technology Calicut, India. [6] Gerhard Knothe, Robert O. Dunn and Marvin O. Bagby (2002). The Use of Vegetable Oils and Their Derivatives as Alternative Diesel Fuels. Oil Chemical Research, National Center for Agricultural Utilization Research, Agricultural Research Service, U.S. Department of Agriculture, Peoria, IL 61604. [7] Gerhard Knothe, John Van Gerpen, Jergen Krahl (2005). The biodiesel handbook, USA. [8] G.R. Peterson, W.P. Scarrah (2005). Rapeseed Oil transesterification by heterogeneous catalysis. Montana State University, Bozeman. [9] J. Van Gerpen, B.Shanks, and R.Pruszko (July 2004). Biodiesel Production Technology. Renewable Products Development Laboratory, U.S. Department of Energy, Office of Scientific and Technical Information, P.O. Box 62, Oak Ridge, TN 37831-0062. [10] Hideki Fukuda et all (2001). Review Biodiessel fuel production by tranesterification of oil. J. Biosci. Bioeng., p. 405 416.

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[11] Wei Du, Yuan Xu, Jing Zeng and De- hua Liu (2004). Novozym 435catalysed transesterification of crude soya bean oils for biodiesel production in a solvent-free medium. Biotechnol, Appi, Biochem, Great Britain.

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