I HC QUC GIA TP.

H CH MINH

I HC BCH KHOA THNH PH H CH MINH

L TH THANH HNG

NGHIN CU TNG HP BIODIESEL BNG PHN NG ANCOL PHN T M C DA TRN NG BNG SNG CU LONG TRN XC TC AXIT V BAZ

LUN N TIN S K THUT

THNH PH H CH MINH Nm 2011

I HC QUC GIA TP. H CH MINH

I HC BCH KHOA THNH PH H CH MINH

L TH THANH HNG

NGHIN CU TNG HP BIODIESEL BNG PHN NG ANCOL PHN T M C DA TRN NG BNG SNG CU LONG TRN XC TC AXIT V BAZ

LUN N TIN S K THUT

Chuyn ngnh : Cng ngh ha hc cc cht hu c M s : 62 52 75 05

HNG DN KHOA HC:

1. PGS.TS PHAN MINH TN 2. PGS.TS TRN TH VIT HOA

THNH PH H CH MINH - Nm 2011

A.GII THIU LUN N

1.

Tnh cp thit ca lun n

Trong bi cnh bin i kh hu ton cu, th gii ang n lc tm kim cc gii php thay th cc dng nng lng i t nguyn liu ha thch bng cc nng lng sch, nng lng ti to v nhin liu sinh hc. Vit Nam c nh gi rt giu tim nng v nguyn liu sn xut nhin liu sinh hc lin quan n cc sn phm nng nghip ng u th gii nh la, thy sn, M c tra v c basa Vit Nam l ngun nguyn liu rt thch hp tng hp biodiesel v theo tnh ton ca cc nh khoa hc nu tn dng c ngun nguyn liu ny chng ta s sn xut c 300 triu lt biodiesel B 100 hay tng ng khong 6 t lt B 5. Tuy nhin hin nay lng m c ny ch yu vn c xut khu sang nhiu nc trong khu vc. Mt trong nhng nguyn nhn ca hin tng trn l cn qu t cc cng trnh nghin cu v l thuyt cng nh v ng dng quy trnh cng ngh sn xut biodiesel t m c da trn. Do vy ti lun n tin s Nghin cu tng hp biodiesel bng phn ng ancol phn m c tra v basa nui cc tnh BSCL trn xc tc axit, baz c thc hin nhm gp phn xy dng nhng c s l thuyt v xc nh mt s thng s cng ngh c bn ca qu trnh sn xut biodiesel t m c tra v c basa.
2. Mc tiu v ni dung nghin cu

Mc tiu ca lun n l nghin cu tng i ton din cc vn lin quan n phn ng ancol phn m c da trn lm c s khoa hc xc nh mt s iu kin thch hp cho qu trnh cng ngh sn xut biodiesel. Do ni dung ca lun n gm: Kho st thnh phn ha hc v tnh cht ha l c bn ca nguyn liu m c da trn nui cc tnh BSCL. Xc nh iu kin phn tch metyl este, glyxerin t do, glyxerin tng, triglyxerit, diglyxerit v monoglyxerit c trong biodiesel bng phng php GC/FID. Kho st cc loi xc tc axit v baz ng th (NaOH, KOH H2SO4, ptoluensulfonic) i vi phn ng metanol phn m c tra tng hp biodiesel ng thi kho st nh hng ca mc chuyn ha ca phn ng n cc tnh cht c bn ca biodiesel. Nghin cu iu ch v ng dng xc tc baz rn CaO v KOH/-Al2O3 i vi phn ng metanol phn m c tra qua xc nh quy trnh v cc iu kin tng hp biodiesel. Nghin cu ng dng vi sng v siu m trong phn ng tng hp biodiesel vi xc tc KOH v KOH/-Al2O3 nhm to tin cho vic p dng cng ngh xanh, thn thin vi mi trng trong sn xut biodiesel Vit Nam.

2 Nhng im mi v khoa hc ca lun n

3.

4.

Xc nh phng php v iu kin phn tch mt cch chnh xc ng thi hm lng triglyxerit, diglyxerit, monoglyxerit, glyxerin v thnh phn ca metyl este c trong biodiesel bng phng php GC. ng dng xc tc baz rn CaO v KOH/-Al2O3 trong phn ng metanol phn m c tra t khng nh tnh u vit v kh nng ng dng ca xc tc ny trong thc t sn xut. ng dng phng php vi sng v siu m vi xc tc KOH/-Al2O3 trong phn ng metanol phn m c tra.
Cu trc ca lun n

Lun n gm 127 trang (khng k ti liu tham kho v ph lc) c 27 bng, 33 hnh v v th, 218 ti liu tham kho, 10 ph lc c chia thnh cc phn nh sau: M u: 2 trang Chng 1. Tng quan v biodiesel v cc cng trnh nghin cu: 25 trang Chng 2. Thc nghim v Phng php nghin cu: 26 trang Chng 3. Kt qu v tho lun: 71 trang Kt lun v kin ngh: 3 trang

B. NI DUNG CHNH CA LUN N

Chng 1. TNG QUAN V BIODIESEL V CC CNG TRNH NGHIN CU

Tng hp v l thuyt lin quan n biodiesel (nguyn liu, phng php tng hp, xc tc,), m c da trn BSCL, cc cng trnh nghin cu Vit Nam v nc ngoi v phn ng ancol phn tng hp biodiesel xc tc axit, baz ng th v d th vi cc phng php khuy trn c hc, c s h tr siu m v vi sng.
Chng 2. THC NGHIM V PHNG PHP NGHIN CU 2.1. Nguyn liu ha cht v thit b

Nguyn liu m c da trn do Cng ty Xut nhp khu Nng nghip v Thc phm An Giang (Afiex) cung cp. Cht chun v ni chun ca Fluka (M), Sigma (M), Prolabo (c), ha cht loi phn tch NmetylN trimetylsilyltrifluoroaxetamit (MSTFA) (Sigma, M). Cc ha cht khc: CH3OH cng nghip 90 % (s dng cho kho st xc tc KOH, NaOH, KOH/-Al2O3), CH3OH 99,5 % (s dng cho kho st xc tc PTSA v CaO), axit PTSA 82 88 % (Prolabo), thy tinh lng (Vit Nam), KOH 82 %, NaOH 96 %, H2SO4 96 %, CaO 98 % (Trung Quc). Thit b sc k kh (GC) Agilent 6890N vi u d ion ha ngn la (FID) v h thng khi ph MSD 5973i, my siu m VC 750W Ultrasonic Processor (Sonics, M) 20 kHz, my c quay chn khng HELDOLPH - Laborota 4010/HB/G1, sng rung Retsch (Anh).
2.2. Cc phng php phn tch 2.2.1. Phn tch thnh phn ha hc v tnh cht ha l ca m c da trn

Thnh phn axit bo ca m c c phn tch ti Trung tm dch v phn tch th nghim (S Khoa hc v Cng ngh Tp. HCM). Cc tnh cht ha l c bn ca m c c phn tch Trung tm K thut 3. Ring m c tra c kho st nh hng ca phng php nui (ng qun, h v b) n tnh cht v thnh phn axit bo ca loi m ny.
2.2.2. Phn tch metyl este

Hm lng FAME trong biodiesel c xc nh bng phng php GC s dng ct mao qun HP INNOWax Agilent 19095123, thnh phn pha tnh 100 % polyetylen glycol (30m x 0,53mm x 1m) trn c s hiu chnh tiu chun EN 14103.
2.2.3. Phn tch glyxerin

4
2.2.3.1. Phng php mt giai on

Phng php mt giai on s dng cht NmetylN trimetylsilyltrifluoraxetamit (MSTFA) to dn xut vi diglyxerit (DG), monoglyxerit (MG) v glyxerin (G) qua xc nh ng thi hm lng TG, DG, MG v G. Phng php ny da trn c s hiu chnh tiu chun EN 14105 v ASTM D 6584 s dng phng php GC vi ct DB 5ht Agilent 1225731, thnh phn pha tnh 5 % phenyl v 95 % dimetylpolysiloxan (30 m x 0,25 mm x 0,10 m).
2.2.3.2. Phng php hai giai on

Phng php hai giai on xc nh hm lng glyxerin t do bng GC sau x phng ha mu chuyn TG, DG, MG v dng glyxerin t do xc nh hm lng glyxerin tng. Phng php ny chng ti s dng ct DB 624 Agilent 1221334, thnh phn pha tnh 6 % cyanopropylphenyl v 94 % dimetylpolysiloxan (30 m x 0,25mm x 1,40 m). so snh s khc bit kt qu ca hai phng php trn vi tin cy 95 %, chun Fisher v chun Student c s dng kim nh tnh ng nht cc phng sai v cc gi tr trung bnh ca kt qu o.
2.2.4. Phn tch tnh cht ca biodiesel

Cht lng ca biodiesel c xc nh bng cc phng php theo quy nh ca tiu chun ASTM 6751 ring ch s xetan p dng tiu chun ASTM D 4737 (dnh cho nhin liu khng s dng cht ph gia ci thin ch s xetan). nh danh thnh phn metyl este c trong biodiesel c thc hin bng phng php phn tch sc k kh ghp khi ph (GC/MS) vi thit b Agilent 6890N, u d MSD 5973i, ct HP 5MS Agilent 19091S-433 c thnh phn 5 % phenylmetylsiloxan (30 m x 0,25 mm x 0,25 m), kh mang heli, t l chia dng 50:1, nhit bung tim mu 250 oC chng trnh nhit bt u 100 oC gi 2 pht, tng 15 oC/pht n 180 oC, gi 17 pht, tip tc tng tng 15 oC/pht n 280 oC, gi 5 pht.
2.3. Phng php nghin cu xc tc rn

Cc tnh cht c trng xc tc c xc nh bng cc phng php phn tch sau: ng nhit hp ph - gii hp ph N2 (ghi trn my NOVA 1200e Quantachrome), SEM (thit b SEM JEOL JMS 7410F), nhiu x Rnghen (ghi trn my Siemen D5000 Bruker), ph IR theo k thut p vin KBr (thit b Vector 22 Bruker), phn tch nhit TG-DTA (thit b STA 409 PC NETZSCH), gii hp NH3 theo chng trnh nhit (TPD) (phng Xc tc Vin Cng ngh ha hc), xc nh baz theo phng php Hammett, xc nh bn xc tc rn bng phng php chun vi axit benzoic. Kho st s thay i tan ca CaO trong mi trng phn ng (gm metanol v nc c trong m c) v trong sut qu trnh phn ng lm c s nh gi nh hng ca hm lng CaO tan trong MeOH (xc tc ng th) n hiu sut biodiesel. Phng php chun vi EDTA theo TCVN 6224-1996 c s dng nh

lng Ca2+. Ngoi ra, d lng Ca2+, K+ v Al3+ c trong biodiesel sn phm cng c xc nh bng phng php AAS Trung tm Cng ngh mi trng - Vin Cng ngh mi trng (s 1 Mc nh Chi, Q.1, Tp. H Ch Minh) vi thit b AA 6800 Shimadzu v phng php ICP/MS ti cng ty Hon Cu vi thit b ICP-MS Elan 6000 Perkin Elmer s dng tiu chun SMEWW 3125-2005. Cc cht chun i chng Ca(OCH3)2 v Ca(C3H7O3)2 c iu ch nh sau: i. Ca(OCH3)2: 0,1g CaO hot ha cho vo bnh cu, thm 150 g metanol, lp h thng hon lu, ci t nhit n nh 60 oC, khuy mnh bng my khuy t trong 1 gi sau c quay chn khng thu c Ca(OCH3)2 rn mu trng. Ca(C3H7O3)2: 3,34 g CaO hot ha v 12,88 g MeOH cho vo bnh cu, thm 5 g glyxerin tinh khit, lp h thng hon lu, ci t nhit n nh 60 oC v khuy mnh bng my khuy t trong 1 gi sau lc ht chn khng thu c Ca(C3H7O3)2 rn mu trng ng. Mu c lu trong bnh ht m chn khng trong 5 gi. Tnh cht ca cc cht chun c phn tch SEM, XRD, IR.
Xc tc

ii.

iii. 2.4.

2.4.1. Xc tc ng th

Kho st phn ng ancol phn m c tra s dng xc tc baz (NaOH, KOH) v axit (H2SO4, PTSA).
2.4.2. iu ch xc tc baz rn
2.4.2.1. Xc tc CaO

Trc khi s dng, CaO c nghin mn, ry v chn ht 75 m sau hot ha 1000 oC trong 4 gi loi b H2O v CO2 b hp ph trn b mt.
2.4.2.2. Xc tc K /-Al2O3
+

Cht mang -Al2O3 s dng cho nghin cu c iu ch bng cch nung Al(OH)3 650 oC trong 6 gi sau qua sng rung chn cc ht c kch thc 90 m. Pha hot tnh l hai hp cht ca kali (KOH v K2CO3). Xc tc K+/-Al2O3 c iu ch bng phng php ngm tm. Sau qu trnh tm (3 gi), xc tc c sy 24 gi 120 oC v nung hot ha trc khi s dng. Cc yu t nh hng n qu trnh iu ch xc tc c kho st l hm lng KOH hoc K2CO3 (mmol) tm trn cht mang -Al2O3 (g), nhit nung v thi gian nung. nh gi hot tnh xc tc, phn ng metanol phn c thc hin iu kin c nh: 8/1 t l mol ca MeOH/m c, 5 % xc tc, thi gian phn ng 90 pht, nhit phn ng 60 oC. Ht xc tc c to thnh bng cch trn thy tinh lng vi xc tc KOH/Al2O3 sau nung nhit cao v kho st cc thng s nh hng n qu trnh to ht.

6 2.5. Cc phng php tng hp biodiesel

2.5.1. Phng php nhit ng th

Phn ng metanol phn m c s dng xc tc axit v baz ng th c thc hin nh sau: cho xc tc v metanol vo bnh phn ng 2 c, khuy mnh 20 pht cho 0,05 mol m c vo, lp h thng hon lu v nhit k, t bnh phn ng trong ni cch thy, gia nhit v khuy mnh bng my khuy t. Nhit phn ng v tc khuy (900 rpm) c duy tr n nh trong sut thi gian phn ng. Khi phn ng kt thc, hn hp c ngui ri chuyn sang phiu chit, tch pha trong 4 gi. Pha di ch yu l glyxerin v metanol, pha trn l metyl este th sau c ra sch nhiu ln vi nc m (60 70 oC) v lm kh bng vi sng 10 pht 380 W. Vi xc tc axit H2SO4 v PTSA, trc khi tch chit, metanol d c thu hi bng thit b c quay chn khng. Cc yu t nh hng n phn ng trao i este c kho st l t l mol MeOH/m, hm lng xc tc, thi gian v nhit phn ng. Kho st nh hng ca mc phn ng n cht lng ca biodiesel, phn ng metanol phn m c c tin hnh vi cc thng s c nh 6/1 t l mol ca MeOH/m, 0,8 % xc tc KOH, thi gian phn ng 30 pht. Nhit phn ng thay i 20 60 oC.
2.5.2. Phng php nhit d th 2.5.2.1. Xc tc CaO

Phn ng metanol phn m c s dng xc tc CaO c thc hin tng t nh vi xc tc ng th (2.5.1). H thng phn ng phi kn cch ly hon ton vi khng kh. Khi phn ng kt thc, ngui, lc xc tc bng h thng lc chn khng. Cho 1ml HCl 18% vo phn dung dch sau khi lc loi ht CaO sau chuyn sang phiu chit, tch pha trong 4 gi. Pha metyl este trn c trung ha li bng dung dch KOH 0,1N. Sau khi tch metanol d bng thit b c quay chn khng, tin hnh ra v tinh ch metyl este nh phn 2.5.1. Xc tc sau khi lc c ra sch cc tp cht hu c bng metanol tinh khit, sy 60 oC trong 12 gi sau c phn tch nh SEM, ph IR v XRD. Quy trnh kho st ti s dng xc tc nh sau: sau khi lc xc tc c hot ha bng hai phng php: (i) Nung 4 gi 1000 oC (xc tc hot ha nhit); (ii) Ra vi metanol, sy 12 gi 60 oC (xc tc sau phn ng) v sy 12 gi 120 oC trc khi s dng. tnh hiu sut thu hi ca xc tc KOH/-Al2O3 trn, quy trnh c thc hin nh sau: chuyn xc tc sau khi lc vo cc s bit trc khi lng sy 24 gi 120 oC, tip tc nung 4 gi 1000 oC sau ngui v xc nh khi lng.
2.5.2.2. Xc tc K+/-Al2O3

Cc bc thc hin phn ng n giai on lc xc tc tng t nh vi xc tc CaO (2.5.2.1). Tin hnh tch pha 4 gi trong phu chit. Sau khi tch metanol d bng phng php c quay chn khng, ra v tinh ch metyl este nh phn 2.5.1.

Xc tc sau khi lc c ra sch bng metanol, chuyn vo cc s, sy 12 gi 120 o C, ngui v xc nh khi lng. Trc khi ti s dng, xc tc c hot ha li. Ti u ha phn ng tng hp biodiesel xc tc KOH/-Al2O3 bng phng php quy hoch thc nghim s dng phn mm Statgraphics phn tch v tnh ton.
2.5.3. Phng php s dng sng siu m

H thng phn ng siu m tn s thp 20 kHz vi thng s c nh cng sut 100 %, ch pulse 5 giy/5 giy (on/off). Bnh phn ng thy tinh (13,6 cm x 7,9 cm) hai lp c n nhit bng nc. Thanh siu m ci t c nh ngp su 10 cm trong dung dch phn ng. Nng lng sng siu m v nhit phn ng c hin th t ng trn mn hnh ca thit b v nhit k khi thay i bin sng v thi gian phn ng. Xc tc c kho st l KOH v KOH/-Al2O3. Cc bc tinh ch sn phm ging nh phn 2.5.1 v 2.5.2.2. Tch pha 2 gi i vi c hai loi xc tc.
2.5.4. Phng php s dng vi sng

H thng phn ng c ci tin t l vi sng gia nh vi bnh phn ng 250 mL bng thy tinh hai lp, n nhit bng h thng nc hon lu v khuy trn bng my khuy t 400 rmp. Cc bc thc hin ging nh phn 2.5.3. Xc tc c kho st gm KOH v K+/-Al2O3 vi thi gian tch pha 2 gi.
Chng 3. KT QU V BN LUN 3.1. Phn tch thnh phn v tnh cht nguyn liu m c da trn

Thnh phn axit bo ca m c tra v basa c kho st hai tnh An Giang v Cn Th cho thy hai loi m c thnh phn axit bo ging nhau: axit bo khng no chim 57,97 % (m c tra) v 64,17 % (m c basa) vi thnh phn ch yu l axit oleic (C18:1) chim 39,34 % (m c tra) v 46,62 % (m c basa). Thnh phn axit bo no ch yu l axit palmitic (C16:0) vi 28,87 % (m c tra) v 25,30 % (m c basa). Khng thy c s khc bit v thnh phn axit bo gia cc phng php v a bn nui ca c tra. Hm lng nc c trong m c tra v m c basa kh nh v nm trong gii hn c ngh ca cc bo co trc y ( 0,5 %) nhng hm lng FFA li hi ln ( 1 2 mg KOH/g). Nh vy thnh phn ha hc v tnh cht ha l ca m c tra v c basa hon ton p ng yu cu s dng lm nguyn liu ban u iu ch biodiesel.
3.2. Cc phng php phn tch thnh phn ha hc ca biodiesel
3.2.1. Phn tch cc metyl este

Nghin cu xc nh c ch phn tch FAME trong biodiesel s dng ni chun metyl hexanoat: vi tc kh mang 20,0 mL/pht, t l chia dng 50:1, nhit bung tim mu 210 oC, nhit u d 250 oC v chng trnh nhit l ct

bt u 120 oC gi 2 pht, tng 7 oC/pht n 230 oC gi 15 pht. Vi ch ny, ni chun, dung mi v cc thnh phn C12:0 C22:6 c xc nh r rng, ph hp vi thnh phn axit bo c trong m c nguyn liu.
3.2.2. Phn tch glyxerin t do v glyxerin tng

Phng php mt giai on phn tch ng thi TG, DG, MG v G c xc nh nh sau: nhit bung tim mu 350 C, nhit u d 380 C, tc kh mang 4,0 mL/pht, t l chia dng 5:1, chng trnh nhit bt u 60 oC gi 1 pht, tng 15 oC/pht n 180 oC, tng 7 oC/pht n 230 oC, tng 10 oC/pht n 330 oC, tng 15 oC/pht n 375 oC gi 4 pht. Phng php ny c thi gian phn tch ngn, xc nh c ng thi TG, DG, MG v G nhng tn km do phi s dng cht to dn xut MSTFA, cc cht chun v ni chun. Phng php hai giai on phn tch glyxerin t do v glyxerin tng vi ch phn tch glyxerin t do nh sau: nhit bung tim 230 C, nhit u d 250 C, tc kh mang 1,0 mL/pht, t l chia dng 10:1, chng trnh nhit bt u 100 oC, tng 15 oC/pht n 180 oC gi 1 pht, tip tc tng 20 oC/pht n 230 oC gi 3 pht. Phn tch hai giai on i hi thi gian nhiu hn cho phn ng x phng ha mu nhng li tn km ha cht, cht chun v ni chun. Hiu sut thu hi ca hai phng php cao, ngng pht hin (LOD) v ngng nh lng (LOQ) u thp (Bng 3.1). Kim nh bng chun Fischer v Student cho thy kt qu phn tch hm lng glyxerin t do v glyxerin tng theo hai phng php ny tng ng nhau.
Bng 3.1. Kt qu LOD, LOQ v hiu sut thu hi ca phng php Cht chun Thng s Hiu sut thu hi (%) LOD (mg/kg) LOQ (mg/kg) Glyxerin 98,670,44 0,033 0,11 Mt giai on Monoolein 96,220,91 7,27 24,22 Diolein 97,493,08 7,63 25,45 Triolein 94,764,52 45,00 150,03 Hai giai on Glyxerin 97,571,8 0,85 2,8

3.3. Kho st phn ng metanol phn m c tra vi xc tc ng th baz (NaOH, KOH) v axit (H2SO4 v PTSA)

Kt qu cho thy cc xc tc ng th baz (NaOH, KOH) v axit (PTSA, H2SO4) u c hot tnh cao i vi phn ng metanol phn m c tra (Bng 3.2). Mc d c ch s axit cao hn (> 1 %) v hm lng metanol thp hn (90 %) so vi khuyn co ca cc nghin cu trc y, nguyn liu m c tra s dng xc tc baz NaOH v KOH vn cho hiu sut biodiesel bng vi hiu sut bnh qun ca th gii i vi cc loi nguyn liu khc nh du u nnh, du ci, ... iu kin thi gian v nhit thp hn. S dng xc tc axit i hi thi gian phn ng di hn v t l

mol ca MeOH/m cao hn nhiu so vi xc tc kim. So vi cc loi du thc vt, m c tra s dng xc tc PTSA hoc H2SO4 tng hp biodiesel u gim c t l mol ca MeOH/m v rt ngn ng k thi gian phn ng. Hiu sut t cao nht khong 93 % (KOH v NaOH) v 98 99 % (H2SO4 v PTSA).
Bng 3.2. Kt qu kho st xc tc baz (NaOH v KOH) v axit (PTSA hoc H2SO4) Thng s phn ng T l mol MeOH/m Hm lng xc tc (%) Thi gian phn ng (pht) Nhit phn ng (oC) Hiu sut biodiesel (%) Xc tc NaOH 6/1 0,8 50 50 92,08 KOH 6/1 0,8 50 50 92,88 PTSA 6/1 4 12 70 98,73 H2SO4 22/1 3 25 65 98,90

3.4. nh hng mc chuyn ha ca phn ng metanol phn m c tra n cc tnh cht c bn ca biodiesel (xc tc KOH)

t cht lng biodiesel theo tiu chun ASTM D 6751, hm lng FAME phi t 99,74 %. Mc tiu ca nghin cu ny nhm kho st nh hng mc chuyn ha thng qua hiu sut biodiesel ca phn ng metanol phn m c tra (xc tc KOH) n cc tnh cht c bn ca biodiesel. Kt qu mc chuyn ha este tc ng ln nht n hm lng G tng v nht ca biodiesel. Khi hiu sut biodiesel 90 %, hm lng G tng mi t yu cu ca tiu chun ASTM D 6751 tng ng vi nht 4,4 mm2/s v khi lng ring 0,868 kg/L. Cc thng s cht lng khc nh nht, AV, hm lng nc v tp cht, hm lng cn cacbon v G t do t tiu chun ASTM D 6751 khi hiu sut biodiesel ch 78 %. Nh vy nh gi hiu sut biodiesel ca phn ng metanol phn cn phi xc nh chnh xc hm lng FAME bng cc phng php phn tch hn l xc nh thng qua cc thng s khc nh nht hay hm lng glyxerin.
3.5. Tng hp biodiesel vi xc tc baz rn
3.5.1. Tng hp biodiesel vi xc tc CaO 3.5.1.1. Kho st hot tnh xc tc CaO i vi phn ng metanol phn m c tra

Kt qu phn tch xc tc CaO tan 0,1 % (w/w) trong mi trng phn ng, baz 15 < pH < 18,4, din tch b mt ring 2,459 (m2/g), th tch l xp 0,002 cm3/g. Gin phn b ng knh l xp, mao qun ca xc tc CaO thuc loi trung bnh, tp trung khong 27,690 A0 rt thun li lm xc tc cho phn ng trao i este. Phn tch XRD, IR v TGA-DTA cho thy xc tc CaO c s dng tinh khit v hon

10

ton khan nc khi nung 1000 oC. Tm li xc tc CaO s dng cho nghin cu ny l mt baz rn, mnh v tan rt t trong metanol. Kt qu kho st nh hng ca cc yu t phn ng cho thy xc tc CaO c hot tnh cao vi phn ng metanol phn m c tra vi hiu sut biodiesel cao nht t khong 93 % iu kin 8/1 t l mol ca MeOH/m c, 6 % xc tc CaO, thi gian phn ng 90 pht, nhit phn ng 60 oC.
3.5.1.2. C ch phn ng metanol phn m c tra xc tc CaO

Xc tc CaO c theo di s bin i thnh phn ha hc trong sut thi gian phn ng qua phn tch XRD (Hnh 3.1), IR (Hnh 3.2) v SEM (Hnh 3.3).

a.

d.

b.

e.

c.

f.

a.Xc tc CaO trc phn ng b.Xc tc sau 20 pht phn ng c.Xc tc sau 30 pht phn ng

d.Xc tc sau phn ng e.CaO khuy trn vi metanol f. Ca(C3H7O3)2 i chiu

Hnh 3.1. XRD ca xc tc CaO trong qu trnh phn ng trao i este So snh hnh 3.1a v 3.1b vi 3.1c cho thy mt lng nh CaO tham gia phn ng vi MeOH hoc H2O c trong khng kh hoc tc cht to ra Ca(CH3O)2 vi 2 11o, 21o, 28o v Ca(OH)2 vi 2 18o, 34o (Hnh 3.1b). Sau 30 pht phn ng, thnh phn xc tc xut hin canxi diglyxeroxit Ca(C3H7O3)2 vi 2 8o, 10o v 24o v mt s mi nh ca CaO v Ca(OH)2 (Hnh 3.1c). Khi phn ng kt thc, so snh vi XRD ca Ca(C3H7O3)2 chun (Hnh 3.1f), trn hnh 3.1d ch tm thy mt hp cht

11

Ca(C3H7O3)2. Nh vy xc tc CaO c s thay i thnh phn ha hc trong qu trnh phn ng. So snh vi ph IR ca xc tc CaO trc phn ng (Hnh 3.2a), xc tc sau 20 pht phn ng (Hnh 3.2b) c mt vn hp th nhn tn s 3640 cm-1 c trng cho dao ng ca lin kt OH, cc vn 2815, 2920 v 1418 cm-1 c trng cho dao ng lin kt CH3 v vn 1080 cm-1 c trng cho dao ng CO. iu ny ph hp vi s c mt ca Ca(OH)2 v Ca(CH3O)2. Ph IR ca xc tc thu c sau phn ng (Hnh 3.2c) ging ph IR ca Ca(C3H7O3)2 (Hnh 3.2e) vi vn t hp th mnh tn s 3348 cm-1 c trng cho dao ng ca OH c lin kt hydro, cc vn vng 2840 2930 cm-1 c trng cho dao ng CH no v >CH2, vn tn s 1423 cm-1 tng ng vi dao ng ca nhm OCaO, vn vng 1448 1470 cm-1 c trng cho dao ng ca nhm >CH2 v vn vng 1075 1132 cm-1 tng ng vi dao ng ca nhm CO. Kt qu phn tch IR ph hp vi s tn ti ca Ca(C3H7O3)2 l thnh phn xc tc thu c sau phn ng.

a.Xc tc CaO trc phn ng

b.Xc tc sau 20 pht phn ng

c.Xc tc sau phn ng

d. Xc tc hot ha nhit

e.Ca(C3H7O3)2 i chng

Hnh 3.2. Ph IR th hin s thay i thnh phn ha hc ca xc tc CaO trong phn ng trao i este

12

nh SEM ca xc tc sau phn ng v Ca(C3H7O3)2 i chiu tng t nhau v hnh dng tinh th, cu trc v khc vi xc tc CaO ban u (Hnh 3.3).

a. Xc tc CaO

b. Ca(C3H7O3)2 chun

c. Xc tc sau phn ng

Hnh 3.3. SEM ca xc tc CaO, xc tc sau phn ng v Ca(C3H7O3)2 i chng nh gi vai tr xc tc ng th ca lng CaO b ha tan, chng ti kho st s thay i tan ca CaO trong sut qu trnh phn ng. thi im bt u phn ng, xc tc CaO tan 0,1 % sau tng ln 0,92 % sau 40 pht v 1,43 % sau 90 pht. Thc hin cc phn ng metanol phn vi iu kin c nh t l mol 8/1 ca MeOH/m, thi gian phn ng 90 pht 60 oC vi hm lng CaO ln lt l 0,005 g (>> 0,003 g 0,1 %), 0,5 g (>> 0,03 g 1 %) v 3,34 g ( 6 %). Hiu sut biodiesel t tng ng 1,73 %, 34,70 % v 93 %. C th thy phn tan ca xc tc CaO trong mi trng phn ng ng gp khng ng k vo s hnh thnh hiu sut biodiesel (1,73 %). T kt qu phn tch trn, c ch phn ng trao i este ngh c trnh by hnh 3.4. Giai on 1: CaO + H2O = Ca(OH)2 Ca(OH)2 + 2CH3OH CaO + 2CH3OH
CH2OCOR Ca(CH3O)2 CHOCOR + 3 CH3OH CH2OCOR 3 RCOOCH3 + C3H8O3

(3. 1. 1) Ca(CH3O)2 + 2H2O (3. 1. 2) (3. 1. 3)

Ca(CH3O)2 + H2O

(3. 1. 4) (3. 1. 5) (3. 1. 6)

Ca(CH3O)2 + 2C3H8O3 Ca(C3H7O3)2 + 2CH3OH CaO + 2C3H8O3 Ca(C3H7O3)2 + H2O Giai on 2:

13

CH2O CHOH CH2OH

Ca + CH3OH

CH2O CHOH + CH2OH2

Ca

CH2O + CHOH2 CH2OH

Ca + CH3O-

(3. 1. 7)
O CH2O CHO C R1 CH2O CHOH + CH2OH2 Ca CH2O + CHOH2 CH2OH Ca

COR2 + CH3O-

CH2O COR3
CH2O CHOH + CH2OH2 OCH2O CHO C R1 Ca

CH2 O + O- H2OCH CH2O CHO C R1

Ca

CH2 OH

OCH3 COR2

OCH3 COR2

CH2O

COR3

CH2O

COR3

(3. 1. 8)

CH2 O R1 COOCH3 + CHOH CH2 OH

Ca +

CH2OH CHO COR2 CH2O COR3

(3. 1. 9)

Hnh 3.4. C ch ngh ca phn ng trao i este s dng xc tc CaO Giai on u, mt lng nh CaO phn ng vi nc trong khng kh hoc tc cht to thnh Ca(OH)2. Sau CaO v Ca(OH)2 phn ng vi metanol to thnh Ca(CH3O)2 c hot tnh cao hn v xc tc cho phn ng trao i este to thnh glyxerin v FAME. Giai on ny phn ng xy ra chm, hiu sut thp. Khi glyxerin sinh ra s phn ng vi CaO hoc Ca(CH3O)2 to thnh Ca(C3H7O3)2. Giai on tip theo Ca(C3H7O3)2 phn ng vi metanol to ra CH3O- y nhanh phn ng to thnh FAME v DG v c ti to sau phn ng. Qu trnh ny c lp li cho n FAME

14

v glyxerin c to thnh. Nh vy, c ch hot ng ny th hin tnh d th ca xc tc CaO trong phn ng metanol phn tng hp biodiesel.
3.5.1.3. Ti s dng xc tc

Kt qu kho st cho thy bn cht ha hc ca xc tc ti s dng ph thuc vo iu kin hot ha li xc tc. T XRD v IR ca xc tc sau phn ng v xc tc hot ha nhit c th kt lun rng xc tc sau phn ng Ca(C3H7O3)2 rt nhy cm vi nhit : khi sy 80 oC xc tc sau phn ng bt u b bin i mt phn thnh CaO, 120 oC th hm lng CaO xut hin nhiu hn cn nung nhit 1000 oC, xc tc b phn hy hon ton thnh CaO. Tinh th ca xc tc hot ha nhit c hnh dng ging vi xc tc CaO ban u v khc vi xc tc sau phn ng (Hnh 3.5). Nhng khi nh khng c hnh dng nht nh bn cnh cc tinh th xc tc thu hi c th l tp cht cht hu c cha c ra ht. Din tch b mt ring ca xc tc hot ha nhit (5,020 m2/g) v xc tc sau phn ng (8,904 m2/g) u ln hn so vi xc tc CaO (2,459 m2/g). ng ng nhit hp ph ca cc xc tc trn c dng tr, do u thuc loi mao qun trung bnh. Gin phn b ng knh l xp cho thy xc tc sau phn ng c ng knh l xp khong 26,427 A0 tng ng vi xc tc CaO hot ha nhit v hi nh hn so vi xc tc CaO ban u nhng th tch l xp ln hn (0,008 cm3/g so vi 0,003 cm3/g v 0,002 cm3/g), kch thc ht u hn. Nh vy xc tc hot ha nhit v xc tc sau phn ng c cc tnh cht b mt rt thun li lm xc tc cho phn ng trao i este. Kt qu phn tch cho thy baz ca xc tc hot ha nhit CaO (15 < pH < 18,4) cao hn so vi ca xc tc sau phn ng Ca(C3H7O3)2 (9,8 < pH < 12). Mc d c tnh baz yu hn CaO nhng Ca(C3H7O3)2 vn c hot tnh xc tc mnh v hai nhm OH ca n c kh nng to lin kt hydro vi MeOH lm tng kh nng tch proton ca phn t MeOH to ra ion CH3O- d dng.

a. Xc tc hot ha nhit

b. Xc tc sau phn ng

Hnh 3.5. nh SEM ca xc tc hot ha nhit v sau phn ng Trc khi thc hin phn ng xc tc sau phn ng c sy 120 oC, hiu sut biodiesel thu c tng ng vi xc tc hot ha nhit (khong 90 %) nhng lc thnh phn ca xc tc thu hi ngoi Ca(C3H7O3)2 cn c CaO. Phng php thu hi (xc tc sau phn ng) t hao tn nng lng nhng cn mt lng MeOH ln

15

ra sch cc tp cht hu c. Phng php hot ha nhit s dng nhiu nng lng nhng tit kim MeOH hn v cc cht hu c tp cht s b chy trong qu trnh nung. Do chng ti chn xc tc hot ha nhit tip tc nghin cu ti s dng. Kt qu cho thy xc tc CaO c th s dng 5 ln vi hiu sut thu hi xc tc kh cao > 88 % v hiu sut biodiesel > 87 % (sau ln th 5).
3.5.2. Tng hp biodiesel vi xc tc baz rn K+/-Al2O3
3.5.2.1. iu kin iu ch v so snh hot tnh ca cc xc tc K+/-Al2O3

Kt qu kho st tm thy xc tc KOH/-Al2O3 v K2CO3/-Al2O3 c cng iu kin tt nht iu ch: hm lng tm 7 mmol/g ca KOH hoc K2CO3/Al2O3, nhit nung 550 oC, thi gian nung 2 gi. Sau khi so snh hot tnh da vo hiu sut biodiesel v bn trong mi trng nc ca xc tc chng ti la chn KOH/-Al2O3 l xc tc baz rn cho cc nghin cu tip.
3.5.2.2. Kho st tnh cht ca xc tc K+/-Al2O3

nh SEM cho thy -Al2O3 (hnh 3.6a) c cu trc tinh th, kh ng u. Khong trng gia cc tinh th -Al2O3 to iu kin tinh th KOH bm dnh khi b thiu kt, lm thay i cu trc b mt ca -Al2O3 (Hnh 3.6b).

a. -Al2O3

b. B mt KOH/-Al2O3 v tinh th KOH/-Al2O3

Hnh 3.6. nh SEM ca cht mang -Al2O3 v xc tc KOH/-Al2O3 Kt qu o BET a im ca -Al2O3, KOH/-Al2O3 vi hm lng tm 5 mmol/g v 7 mmol/g KOH c trnh by bng 3.3. Bng 3.3. Kt qu o BET ca -Al2O3 v xc tc KOH/-Al2O3 Din tch b mt ring (m2/g)
-Al2O3 KOH/-Al2O3_5mmol/g KOH/-Al2O3_7 mmol/g

Th tch l xp (cm3/g) 0,062 0,019 0,008

ng knh l xp (A0) 37,944 26,472 26,472

100,384 32,893 14,296

ng ng nhit hp ph ca c ba loi c dng tr, u thuc dng mao qun trung bnh. Khi tm KOH ln -Al2O3, din tch b mt ring, th tch l xp v

16

ng knh l xp u gim. iu ny c th do mt phn KOH bm dnh trn b mt v mt phn chui vo cc mao qun ca -Al2O3. Khi hm lng tm KOH tng 5 7 mmol/g, din tch b mt ring v th tch l xp ca xc tc KOH/-Al2O3 u gim nhng ng knh l xp khng thay i (26,472 A0). S thay i thnh phn pha hot tnh trong qu trnh iu ch xc tc th hin qua vic phn tch XRD ca -Al2O3 v xc tc KOH/-Al2O3 vi lng tm KOH t 5 8 mmol/g. Kt qu hnh 3.7 cho thy cc XRD u c nhng pic c trng ca Al2O3 vi 2 = 37o, 46o, 67o. Nh vy -Al2O3 bn vi nhit cao, duy tr c b mt ring ln, ph hp s dng lm cht mang cho phn ng iu ch biodiesel. Vi hm lng tm 5 mmol/g KOH, XRD ngoi cc pic c trng ca -Al2O3, khng thy cc pic c trng ca KOH hay ca cc hp cht kali khc. Khi lng KOH tm tng t 6 7 mmol/g, trn XRD xut hin cc pic mi c trng cho hp cht kali polyaluminat K12Al21O38 2 = 33o, 44o, 66o, K6Al2O6 2 = 32o, 38o, 40o, 43o v KO3 2 = 33o, 43o, 62o. S xut hin cc pha ny l nguyn nhn to ra cc tm baz hot ng v lm tng hot tnh xc tc. Hiu sut biodiesel t 90,74 % 7 mmol/g KOH so vi 85,25 % 6 mmol/g KOH. Vi lng tm 8 mmol/g ca KOH, trn XRD xut hin nhiu pic c trng ca K12Al21O38, K6Al2O6, KO3 v KOH chng t rng lng KOH lc ny nhiu hn kh nng phn tn t nhin, vt qua trng thi n lp b mt v mt s nm li trn b mt -Al2O3, khi phn hy, thiu kt to thnh a lp trn b mt xc tc. Hiu sut biodiesel t l ny ch t 86,62 %. T cc kt qu trn cho thy kh nng phn tn ca KOH trn cht mang -Al2O3 tt nht hm lng 7 mmol/g.

Hnh 3.7. Nhiu x XRD ca -Al2O3 v xc tc KOH/-Al2O3 Tin hnh phn tch DTA ca xc tc KOH/-Al2O3 iu ch iu kin 7 mmol/g ca KOH, thi gian nung 2 gi, nhit nung 550 oC. Gin TGA- DTA c hai giai on gim khi lng t 100 650 oC. Giai on 100 310 oC ch yu xy ra hiu ng thu nhit ng vi qu trnh tch nc vt l trn b mt. Ti khong nhit 185 oC, hiu ng ta nhit xy ra c th l qu trnh phn hy KO3 c to thnh trc t phn ng oxy ha KOH nhit thng vi ozon thnh K2O. Giai on 310 550 oC xy ra hiu ng thu nhit mnh m c th xy ra phn ng tch nc ca cc nhm hydroxyl trn b mt -Al2O3 v KOH hoc cc hp cht ca kali nh KO3,

17

K2O kt hp vi cht mang -Al2O3 to thnh hp cht kali polyaluminat hnh thnh lin kt AlOK. Kt qu ny ph hp vi XRD ca xc tc KOH/-Al2O3, khng nh s c mt ca lin kt AlOK trn b mt xc tc KOH/-Al2O3. KOH + Al OH Al O K + H2O K2O + 2Al OH 2 Al O K + H2O 4KO3 + 4Al OH 4Al O K + 5O2 + 2H2O (3. 2. 1) (3. 2. 2) (3. 2. 3)

Nghin cu cc lin kt ha hc ca -Al2O3 v xc tc KOH/-Al2O3 nung cc nhit khc nhau c phn tch bng ph IR v trnh by hnh 3.8. Ph IR ca -Al2O3 c vn hp th tn s 3500 cm1 c trng cho dao ng lin kt ca nhm OH lin kt vi b mt -Al2O3. Khi a KOH ln b mt -Al2O3, vn ny b lch v pha tn s thp hn cho thy c s kh nc ca cc nhm hydroxyl trn b mt Al2O3. Vn hp th cng yu tn s 1643 cm-1 l c trng dao ng lin kt O H ca cc phn t H2O hp ph vt l trn b mt -Al2O3 v khi tng nhit nung xc tc, vn ny yu dn v mt hn 550 oC. Hai vn hp th cng mnh tn s 580 v 778 cm-1 l c trng dao ng ca lin kt AlO. Khi tm KOH, hai vn ny bin mt v xut hin hai vn hp th vng tn s 720 cm-1 v 890 cm-1 c cho l dao ng ca lin kt AlOK. Nh vy, kt qu ph IR cho thy r rng s tn ti lin kt AlOK ca xc tc KOH/-Al2O3 v vic la chn nhit nung xc tc 500 oC l hp l.

Hnh 3.8. Ph IR ca -Al2O3 v xc tc KOH/-Al2O3 Phng php gii hp theo chng trnh nhit (TPD-NH3) cho thy s thay i mt tm axit khi tm cc hm lng KOH khc nhau (Bng 3.4). Bng 3.4. Kt qu gii hp theo chng trnh nhit (TPD-NH3) Nhit gii hp trung bnh (oC) 200 375 525 mnh tm axit Yu Trung bnh Mnh Mt tng loi tm axit (mmol/100g) -Al2O3 1,27 1,67 0,59 KOH/-Al2O3 (5 mmol/g) 0,34 0,34 0,47 KOH/-Al2O3 (7 mmol/g) 0,24 0,11 0,15

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-Al2O3 c ba khong gii hp ng vi cc tm axit yu, trung bnh v mnh trong ch yu tm axit yu v trung bnh. Khi tm KOH vi hm lng 5 7 (mmol/g) ln b mt ca -Al2O3, mt ca ba loi tm axit ny u b gim. iu ny do cc tm axit b KOH trung ha mt phn hnh thnh cc tm baz hot ng AlOK.
3.5.2.3. C ch ngh phn ng metanol phn xc tc KOH/-Al2O3

C ch ba giai on ca phn ng metanol phn s dng xc tc KOH/Al2O3 c ngh nh sau (Hnh 3.9). Di tc dng ca cc tm baz hot ng AlOK, metanol d dng b mt H+ to thnh ion metoxit CH3O- l tc nhn ca phn ng trao i este (3.3.1). Sau CH3O- tn cng vo nhm cacbonyl ca TG to thnh hp cht trung gian c cacbon t din khng bn d dng chuyn thnh este ca axit bo v anion ca DG (3.3.2). Cui cng giai on hon nguyn xc tc v to thnh DG (3.3.3). Xc tc li tip tc thc hin phn ng theo c ch ln lt vi DG to thnh MG v cui cng l glyxerin.
OH Al O OK Al CH3OH OH Al O OH Al + CH3O- + K+

(3. 3. 1)
O OO R1 O CH3
-

O O

R3 O O R1
-

O OCH3 O O

R3

R3 O + O O O R2
O

O R1 O CH3

O R2
O

O R2

(3. 3. 2)

R3
-O

O + O O R2

OH Al O

OH Al

+ K+

R3 OH

O + O R2 O

OH Al O

OK Al

(3. 3. 3)

Hnh 3.9. C ch ngh phn ng tng hp biodiesel xc tc KOH/-Al2O3

3.5.2.4. Kho st iu kin ti u ca phn ng metanol phn m c tra bng phng php quy hoch thc nghim

T phng trnh hi quy, gii bi ton ti u bng phn mm Statgraphics xc nh c cc iu kin ti u ca phn ng metanol phn m c tra s dng xc tc baz rn KOH/-Al2O3 t l mol 8,26/1 ca MeOH/m, 5,79 % xc tc, thi gian phn ng 96 pht, nhit phn ng 59,6 oC v hiu sut biodiesel t 92,8 %.

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Hm lng xc tc c nh hng ln nht i vi hiu sut biodiesel i vi c bc 1 (tch cc) v bc 2 (tiu cc), sau l nh hng tch cc bc 1 ca t l mol MeOH/m v nh hng tiu cc bc 2 ca nhit phn ng. Thi gian phn ng c mc nh hng thp nht so vi bn nhn t c kho st k c bc 1 (tch cc) v bc 2 (tiu cc). Trong vng kho st, cp nhn t hm lng xc tc v nhit phn ng c nh hng tiu cc ln nht so vi nh hng ca cc cp nhn t khc.
3.5.2.5. Ti s dng xc tc KOH/-Al2O3

Thc nghim cho thy xc tc KOH/-Al2O3 c th ti s dng khng qu 4 ln vi hiu sut thu hi xc tc > 80 % v hiu sut biodiesel t > 87 %. Hot tnh ca xc tc b gim do cc tm baz b u c bi tp cht bn ng thi mt phn pha hot tnh b mt i trong qu trnh phn ng lp li nhiu ln.
3.5.2.6. To ht xc tc KOH/-Al2O3 bng thy tinh lng

Xc tc ht c to thnh bng cch trn xc tc KOH/-Al2O3 vi thy tinh lng. Kt qu kho st cc yu t nh hng n cht lng to ht xc tc tm thy iu kin to ht tt nht t l phi trn 1/3 theo khi lng ca thy tinh lng vi KOH/-Al2O3, thi gian nung 4 gi, nhit nung 400 oC. Hiu sut to ht ca xc tc cha phn loi kch thc t t l 82,54 % nhng hiu sut biodiesel s dng xc tc ny ch t 88,94 %. S dng xc tc c kch thc ht cha phn loi hoc c kch thc ht nh ( 500 m), sau khi phn ng kt thc phi thc hin giai on lc tch xc tc. Xc tc c kch thc 500 m mc d c hiu sut to ht 45,93 % nhng hiu sut biodiesel t 91,8 % v vic lng tch xc tc sau phn ng rt n gin, gim c giai on lc ht chn khng. nh SEM ca xc tc ht khi cha phn loi c kch thc khng ng u so vi ht xc tc kch thc 850 500 m (Hnh 3.10).

a. B mt ht xc tc

b. Xc tc khng phn loi c. Xc tc 850 500 m

Hnh 3.10. nh SEM ca xc tc ht KOH/-Al2O3 So vi KOH/-Al2O3, trn ph IR ca xc tc ht xut hin vn nh tn s 535 cm v 733 cm-1 l dao ng c trng ca lin kt SiO. Nhiu x XRD ca xc tc ht vn c cc pic c trng ca -Al2O3 vi 2 = 37o, 46o, 67o v KO3 vi 2 = 33o, 43o, 62o. Xc tc ht c din tch b mt ring 10,80 m2/g, mao qun trung bnh, ng knh l xp khong 26,46 Ao v th tch l xp 0,007 cm3/g, mt cc loi
-1

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tm axit ca xc tc ht u tng so KOH/-Al2O3 v cao nht tm axit yu. Tuy nhin hiu sut biodiesel t tng ng vi xc tc KOH/-Al2O3 chng t s c mt ca thy tinh lng khng lm gim hot tnh xc tc.
3.5.2.7. So snh hot tnh xc tc KOH vi KOH/-Al2O3 v CaO

Kt qu kho st cho thy phn ng metanol phn m c tra xc tc KOH v xc tc CaO, KOH/-Al2O3 u xy ra nhit trung bnh, p sut kh quyn. T l mol MeOH/m, nhit phn ng i vi xc tc baz rn cao hn khng nhiu so vi xc tc baz ng th nhng hm lng xc tc baz rn s dng ln hn v thi gian ca phn ng di hn. Vi hiu sut biodiesel khong 92 93 %, iu kin phn ng i vi xc tc baz ng th (KOH) v xc tc baz rn (KOH/-Al2O3 v CaO) c trnh by bng 3.5. iu kin ny, xc tc CaO v KOH/-Al2O3 vn c nhiu u im hn v kh nng ti s dng nhiu ln, n gin qu trnh tch lc xc tc v tinh ch biodiesel, gim ng k lng nc thi ra mi trng. Bng 3.5. So snh hot tnh xc tc KOH, KOH/-Al2O3 v CaO
Xc tc KOH KOH/-Al2O3 CaO T l mol MeOH/m 6/1 8/1 8/1 Hm lng xc tc (%) 0,8 6,0 6,0 Thi gian phn ng (pht) 50 90 90 Nhit Hiu sut phn ng biodiesel (oC) (%) 50 60 60 92,90 92,63 92,95 Ln s dng 1 5 5

3.6. Tng hp biodiesel s dng xc tc KOH v KOH/-Al2O3 vi s h tr ca sng siu m

Kho st phn ng metanol phn m c tra s dng xc tc baz ng th KOH v baz rn KOH/-Al2O3 c s h tr ca sng siu m thu c cc kt qu sau: Vi xc tc KOH v KOH/-Al2O3, hiu sut biodiesel t 92 93 % khi thc hin phn ng bin sng 70 % v thi gian phn ng 20 pht. So vi phng php truyn thng, thi gian phn ng gim 60 % (20 pht so vi 50 pht) vi xc tc KOH v gim 78 % (20 pht so vi 90 pht) vi xc tc KOH/-Al2O3, thi gian tch pha gim 50 % (2 gi so vi 4 gi). nh hng n hiu sut biodiesel ngoi cc yu t thuc v ca phn ng trao i este nh t l mol MeOH/m, hm lng xc tc, thi gian v nhit phn ng cn c cc yu t thuc v h thng phn ng nh bin v nng lng sng siu m. i vi c xc tc KOH v KOH/-Al2O3, bin sng cao v thi gian phn ng di u c tc dng lm gim hiu sut biodiesel. Sng siu m khng lm nh hng n thnh phn axit bo ca FAME nhng lm mt hot tnh ca xc tc ti s dng.

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nh SEM (Hnh 3.11) ca xc tc sau phn ng cho b mt xc tc KOH/Al2O3 b xi mn, thay i r rt v gn ging nh cht mang -Al2O3.

a. -Al2O3

b. KOH/-Al2O3 sau phn ng siu m

Hnh 3.11. nh SEM ca xc tc KOH/-Al2O3 sau phn ng siu m Kt qu XRD ca -Al2O3 v KOH/-Al2O3 sau phn ng hnh 3.12 khng tm thy KOH trong thnh phn ca xc tc sau phn ng.

Hnh 3.12. Nhiu x XRD ca xc tc KOH/-Al2O3 sau phn ng siu m iu ny do sng siu m truyn qua dung dch phn ng gy ra hin tng hnh thnh, ln ln v v n cc bt bong bng to ra p sut nn cc b tc ng vo mi trng phn ng, hnh thnh cc lung cht lng va p vi vn tc rt ln vo b mt, gy xi mn ti v tr va chm tch KOH ra khi b mt ca cht mang -Al2O3. Do vy iu kin siu m xc tc KOH/-Al2O3 khng th ti s dng.
3.7. Tng hp biodiesel s dng xc tc KOH v KOH/-Al2O3 vi s h tr ca vi sng

Kt qu kho st nh hng ca vi sng n phn ng metanol phn m c tra s dng xc tc KOH v KOH/-Al2O3 c tm tt nh sau: Vi sng c tc dng thc y nhanh phn ng trao i este, rt ngn ng k thi gian phn ng i vi c xc tc ng th v d th. Hiu sut biodiesel ph thuc vo t l mol MeOH/m, hm lng xc tc, thi gian phn ng v cng sut l.

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Vi sng lm gim hot tnh xc tc KOH/-Al2O3 ti s dng do lm bong mt phn KOH ra khi b mt cht mang nhng khng lm thay i thnh phn axit bo ca FAME trong biodiesel. Vi xc tc KOH v KOH/-Al2O3 iu kin 8/1 ca t l mol MeOH/m, hm lng xc tc tng ng l 0,8 % v 6 %, thi gian phn ng 20 pht, cng sut l 600 W, hiu sut biodiesel t 93,2 % (KOH) v 89,93 % (KOH/-Al2O3). Xc tc KOH/-Al2O3 c th s dng 3 ln vi hiu sut biodiesel > 84 %.

3.8. Xc nh cc ch tiu cht lng biodiesel iu ch t m c tra

Kt qu phn tch ph IR, GC v GC-MS ca sn phm biodiesel c thnh phn metyl etse tng t vi thnh phn axit bo ca nguyn liu m c tra. Cc ch tiu ca biodiesel sn phm u t tiu chun ASTM D 6751. c bit kt qu ny l xc nh c hm lng G t do v G tng l hai thng s quan trng nh gi mc hon thnh ca phn ng trao i este. Ch s xetan ca sn phm biodiesel (53,98) tnh ton theo tiu chun ASM D 4737. Khng pht hin c d lng cc ion kim loi Ca2+, Al3+ hay K+ trong biodiesel sn phm.
Chng 4. KT LUN

Trn c s kt qu nghin cu trn, chng ti rt ra mt s kt lun sau: 1. xc nh thnh phn ha hc v tnh cht ha l ca m c tra v c basa vi cc iu kin nui trng khc nhau. Cc kt qu thu c cho thy thnh phn ha hc v tnh cht ha l ca m c tra v m c basa hon ton p ng yu cu s dng lm nguyn liu ban u iu ch biodiesel. xc nh iu kin c th nh lng FAME, nh lng ng thi TG, DG, MG, G v c bit l glyxerin t do cng nh glyxerin tng trong hn hp phn ng hoc trong biodiesel sn phm bng phng php GC. s dng 4 loi xc tc ng th l KOH, NaOH, H2SO4, PTSA trong phn ng tng hp biodiesel t m c tra. Cc kt qu thu c cng khng nh hot tnh rt cao ca cc loi xc tc ny, hiu sut chuyn ha biodiesel c th t n 92 93 % (NaOH v KOH) v 98 % (H2SO4 v PTSA). Tuy nhin s dng xc tc axit i hi thi gian phn ng di hn v t l mol ca MeOH/m cao hn nhiu so vi xc tc kim. iu kin ny hn ch kh nng s dng thc t xc tc axit trong sn xut biodiesel. Nghin cu tng i ton din vic s dng xc tc rn CaO v KOH/Al2O3 trong phn ng tng hp biodiesel t m c tra bt u t khu iu ch, to ht, xc nh cc tnh cht ha l c trng v hot tnh ca xc tc cho n kho st cc yu t nh hng n hiu sut phn ng to thnh biodiesel. C s phn tch cc s liu thc nghim cho thy c ch hot ng ca cc xc tc rn CaO v KOH/-Al2O3 nh l xc tc d th v c hot

2.

3.

4.

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tnh hon ton tng ng (hiu sut 92 93 %) vi cc xc tc baz ng th, trong khi u im ni tri ca loi xc tc ny l kh nng ti s dng nhiu ln, vic tch ra khi hn hp phn ng d dng, gim thiu kh nng gy nhim mi trng do nc thi c kim cao. 5. Trn c s tham kho ti liu v kt qu kho st s bin i ca xc tc trong qu trnh phn ng ngh c ch chi tit i vi phn ng metanol phn m c tra s dng baz rn CaO v KOH/-Al2O3. kho st nh hng ca siu m v vi sng i vi phn ng metanol phn m c tra s dng xc tc baz ng th KOH v baz rn KOH/Al2O3. Khi c s h tr ca siu m v vi sng, hiu sut biodiesel t 90 93 % vi thi gian phn ng 20 pht. Siu m v vi sng khng lm thay i thnh phn ha hc ca FAME. Siu m lm mt hot tnh ca xc tc KOH/-Al2O3 ti s dng nhng vi sng ch lm gim hot tnh ca xc tc ny. Nh vy i vi xc tc KOH ng th v baz rn KOH/-Al2O3, s dng phng php ha hc xanh c s h tr siu m v vi sng s rt ngn 60 % v 80 % thi gian phn ng so vi phng php thng thng. Kt qu nghin cu ny m ra kh nng ng dng sng siu m tn s thp tng hp biodiesel t m c tra s dng xc tc KOH vi quy m cng nghip.

6.

Tm li, cc ni dung nghin cu ca lun n lin quan trc tip n vic khai thc s dng ngun nguyn liu m c tra v basa rt c gi tr vi s lng ln sn xut biodiesel trong nc thay th cho xut khu nguyn liu th hin nay, gp phn nng cao hiu qu kinh t cho ngnh sn xut thy sn ng thi trin khai chng trnh quc gia v pht trin nng lng ti to v nhin liu sinh hc nhm gim thiu pht thi kh gy hiu ng nh knh v bin i kh hu.

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DANH MC CNG TRNH CNG B LIN QUAN N TI

1.

L Th Thanh Hng, Phn tch biodiesel, Tuyn tp cc cng trnh Hi ngh khoa hc v cng ngh Ha hc Hu c ton quc ln th IV, NXB i hc Quc gia H Ni, 618-623 (2007). Trn Th Vit Hoa, L Th Thanh Hng, Phan Minh Tn, Trng V Thanh, iu ch biodiesel t m c basa xc tc p-toluensulfonic, Tuyn tp cc cng trnh Hi ngh khoa hc v cng ngh Ha hc Hu c ton quc ln th IV, NXB i hc Quc gia H Ni, 834-839 (2007).

2.

3.

Le Thi Thanh Huong, Phan Minh Tan, Tran Thi Viet Hoa, Biodiesel production from fat of tra catfish and basa catfish using alkaline catalysts, Journal of the Korean Oil ChemistsSoiety, (KOCS), 25(3), 299-312 (2008).

4.

Le Thi Thanh Huong, Phan Minh Tan, Tran Thi Viet Hoa, Kinetics of the KOH catalyzed methanolysis for biodiesel production from fat of tra catfish, Journal of the Korean Oil ChemistsSoiety, (KOCS), 25(4), 418-428 (2008).

5.

Le Thi Thanh Huong, Phan Minh Tan, Tran Thi Viet Hoa, Biodiesel refining and glycerin recovering process of transesterification from tra catfish fat, Journal of the Korean Oil ChemistsSoiety, (KOCS), 26(1), 1-9 (2009). Trn Nguyn An Sa, L Th Thanh Hng, Nguyn Th Xun Mai, Phan Minh Tn, Phn tch glyxerin tng v glyxerin t do trong biodiesel bng phng php GC/FID, Tp ch Ha hc, 47(2A), 447-452 (2009). L Th Thanh Hng, Phan Minh Tn, Trn Th Vit Hoa, Biodiesel production from fat of tra catfish with KOH catalyst assisted by microwave, Tp ch Ha hc, 47(2A), 447-452 (2009). L Th Thanh Hng, Phan Minh Tn, Trn Th Vit Hoa, Biodiesel from Tra fat with methanol using KOH catalyst assisted ultrasonic, Tp ch Ha hc, 47(4A),101-106 (2009). L Th Thanh Hng, Phan Minh Tn, Trn Th Vit Hoa, nh hng ca mc chuyn ha este n cc tnh cht c bn ca biodiesel c iu ch t m c Tra, Tp ch Ha hc, 47(4A),107-112 (2009).

6.

7.

8.

9.

25 10.

L Th Thanh Hng, Phan Minh Tn, Trn Th Vit Hoa, Biodiesel from Tra fat with methanol using KOH/-Al2O3 catalyst assisted microwave, Tp ch Ha hc, 47(4A), 113-118 (2009). L Th Thanh Hng, Hunh Vn Tin, Phan Minh Tn, Trn Th Vit Hoa, Calcium oxid as solid base catalyst for transesterification of tra catfish fat, Tp ch Khoa hc v Cng ngh, 47(5A), 472-479 (2009) (S c bit ca 2nd Regional Conference on Chemical Engineering) v Tp ch Pht trin KH&CN, 12(17), 91-99, (2009). L Th Thanh Hng, L Vit Tn, Phan Minh Tn, Trn Th Vit Hoa, Ti u ha qu trnh iu ch biodiesel t m c tra xc tc KOH/-Al2O3, Tp ch Pht trin Khoa hc v Cng ngh, 12(13), 69-76 (2009). L Th Thanh Hng, Hunh Phng Ngn, Phan Minh Tn, Trn Th Vit Hoa, iu ch biodiesel t m c tra xc tc KOH/-Al2O3 s dng sng siu m, Tp ch Pht trin KH&CN, K3(13), 72-80 (2010). K yu ti hi ngh International Workshop on Advanced Materials and Nanotechnology t chc ngy 24-25/11/2009 ti H Ni. L Th Thanh Hng, Phan Minh Tn, Trn Th Vit Hoa, iu ch biodiesel t m c tra xc tc d th KOH/-Al2O3 (Sp ng Tp ch Khoa hc v Cng ngh, Vin Khoa hc v Cng ngh Quc gia).

11.

12.

13.

14.