LI CM N

Ti xin by t lng bit n su sc i vi PGS. TS. Trn Th Nh Mai, ngi trc tip giao ti v hng dn tn tnh v mt khoa hc trong qu trnh ti thon thin lun vn thc s. Ti cng xin gi li cm n n tt c cc thy, c trong B mn Ha hc Du m, khoa Ha hc, trng i hc Khoa hc T nhin, i hc Quc gia H Ni cng ton th bn b, anh ch em trong khoa Ha to nhng iu kin thun li ti hon thnh lun vn thc s. Cui cng, xin gi li bit n v hn n nhng ngi thn trong gia nh v bn b lun bn cnh v ng vin ti trong qu trnh hc tp, nghin cu. H Ni, thng 12 nm 2011 Hc vin

LU VN BC

MC LC Tran g
1

M u
CHNG I: TNG QUAN

7 8 8 10 10 11 15 15 16 19 19 20 21 22 22 22 26 27 30 31 33 33 33 34 35 36 38 40 41
2

1.1. Nng lng ti to, ngun nng lng cho tng lai 1.2. Nhin liu Sinh hc 1.2.1. Khi nim 1.2.2. u, nhc im ca biodiesel so vi diesel ha thch 1.3. Chuyn ha du, m ng thc vt thnh nhin liu 1.3.1. Ngun nguyn liu sinh khi 1.3.2. Mt s hng chuyn ha quan trng 1.4. Phng php este cho ha sn xut biodiesel 1.4.1. nh hng ca tp cht trong nguyn liu 1.4.2. nh hng ca nhit phn ng 1.4.3. nh hng ca thi gian phn ng 1.4.4. nh hng ca t l metanol/du 1.4.5. nh hng ca hm lng xc tc 1.5. Cc h xc tc cho phn ng este cho ha 1.5.1. So snh u, nhc im cc h xc tc cho phn ng este cho ha 1.5.2. Mt s h xc tc axt rn 1.5.3. Xc tc th h mi a oxit kim loi Zn, La/-Al2O3 1.6. Hng nghin cu ca ti
CHNG II: THC NGHIM

2.1. Tng hp xc tc 2.1.1. Tng hp -nhm oxit 2.1.2. Tng hp xc tc a oxit kim loi 2.2. c trng tnh cht vt liu 2.2.1. Phng php nhiu x tia X 2.2.2. Gii hp NH3 theo chng trnh nhit : TPD-NH3 2.2.3. Phng php tn sc nng lng tia X 2.3. Phn ng este cho ha

2.4. nh gi thnh phn sn phm

CHNG III: KT QU - THO LUN

42 42 45 45 46 47 49 49 50 57 58

3.1. Tng hp -Al2O3 3.2. Bin tnh -Al2O3 3.2.1. nh nhiu x tia X 3.2.2. Gii hp NH3 theo chng trnh nhit : TPD-NH3 3.2.2. Ph tn sc nng lng tia X 3.3. Phn ng este cho ha m b 3.3.1. Xc nh ch s axit bo t do ca m b 3.3.2. Nghin cu hot tnh xc tc vi phn ng este cho ha m b KT LUN
TI LIU THAM KHO

DANH MC HNH NH
Hinh 1.1. Nhu cu s dng nng lng trn ton th gii nm 2006. Hnh 1.2. D on v s bin i nhu cu s dng ba ngun nng lng chnh t nm 1850 n nm 2050.
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Hnh 1.3. Chu trnh sn xut v s dng biodiesel. Hnh 1.4. Hm lng CO v ht rn pht thi trong ng c s dng nhin liu diesel ha thch v cc loi nhin liu hn hp Bxx. Hnh 1.5. Hm lng NOx pht thi trong ng c s dng nhin liu diesel ha thch v cc loi nhin liu hn hp Bxx. Hnh1. 6. c lng sinh khi v cha c s dng trn ton th gii. Hnh 1.7. C ch nhit phn triglyxerit ca axit bo bo ha (Alencar, 1983). Hnh 1.8. C ch nhit phn triglyxerit (Schwab, 1998). Hnh 1.9. nh hng ca nhit n chuyn ha ca phn ng este cho ha du ht bng vi metanol, xc tc H2SO4. Hnh 1.10. Gi thit v s hnh thnh cc tm axit trong cu trc ca SO42-/ZrO2 Hnh 1.11. Mt s vt liu nn silica bin tnh bi axit sulfonic Hnh 1.12. Vt liu nn carbon bin tnh bng axit sulfuric. HNH 1.13. Xc tc lai, a oxit kim loi Ta2O5/Si(R)SiH3PW12O40 Hinh 1.14. Hai loi tm axit trn b mt -nhm oxit. Hnh 2.1. Nguyn li cu tao cua may nhiu xa tia X Hnh 2.2. Nguyn l ca php phn tch EDX. Hnh 2.3. S nguyn l ca h ghi nhn tn hiu ph EDX trong TEM. Hnh 2.4. S thit b phn ng trong phng th nghim. Hnh 3.1. nh nhiu x tia X gc rng ca mu A-10 sau khi nung. Hnh 3.2. nh nhiu x tia X gc rng ca mu A-15 sau khi nung. Hnh 3.3. nh nhiu x tia X gc rng ca mu MA. Hnh 3.4: Kt qu gii hp ammonia theo chng trnh nhit Hnh 3.5. Ph tn sc nng lng tia X ca mu MA. Hnh 3.6. Ph tn sc nng lng tia X ca mu MA. Hnh 3.7. Ph tn sc nng lng tia X ca mu MA Hnh 3.8. Sc k ca sn phm phn ng s dng xc tc MA Hnh 3.9. Ph MS ca Pentadecanoic acid, 14 methyl -, metyhyl ester c trong sn phm.
4

12 13 14 16 17 18 21 28 29 29 30 31 36 38 39 40 44 44 45 46 47 48 48 52 53

Hnh 3.10. Ph MS ca 9-Octadecenoic acid (Z), metyhyl ester c trong sn phm Hnh 3.11. So snh hin tng to nh vi phn ng s dng hai h xc tc khc nhau: MeONa (tri) v MA (phi).

54 56

DANH MC BNG
Bng 1.1. Mt s thng s vt l ca biodiesel, diesel ha thch, du thc vt. Bng 1.2. Tm tt u, nhc im ca cc h xc tc cho phn ng este cho ha. Bng 1.3. Mt vi thng s vt l ca , v -nhm oxit.
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Bng 3.1. Hin tng hnh thnh gel vi cc t l mol Al3+/ure khc nhau Bng 3.2. Kt qu phn tch hm lng nguyn t trong mu MA bng EDX Bng 3.3. Kt qu xc nh ch s axit ca m b Bng 3.4. Nghin cu nh hng ca xc tc MA vi phn ng este cho ha.
Bng 3.5. Thng s phn ng este cho ha vi xc tc MA v MeONa

43

49

50 51 55

M U
Nh chng ta bit, an ninh nng lng, an ninh lng thc v bin i kh hu ang l vn sng cn i vi ton cu. Vic tm kim nhng ngun nng lng di hn v thn thin vi mi trng dn thay th nng lng ha thch l nhim v cp thit ca nhn loi hin nay. Qu trnh chuyn ha sinh khi (transformation of biomass) v chuyn ho cc sn phm trong ng thc vt thu c cc hp cht ha hc hu dng
6

c th coi l con ng ngn nht i ti mc tiu pht trin mt cch bn vng, l xu th tt yu trong tng lai. Qu trnh ny ang thu ht c s quan tm gii khoa hc trn th gii v ang c c ng dng nhiu trong ha hc hin i. Cc sn phm chuyn ha trn c s cc axit bo t qu trnh trao i este t du m ng thc vt hin ang c s dng rt rng ri. Hai hng ng dng c coi l c tim nng nht ca qu trnh ny l iu ch dung mi v nhin liu. Biodiesel c sn xut t ngun du, m ng thc vt qua phn ng este cho ha c th c xem l con ng i ti mc tiu to ra nhin liu ti sinh nhanh nht v l xu th tt yu trong tng lai gn. nhiu ni trn th gii, biodiesel bc u c a vo ng dng thc t. Khng nm ngoi xu th pht trin chung Vit Nam bt u quan tm nghin cu v tin hnh sn xut loi nhin lin ny t cc ngun nguyn liu sn c trong nc, v d nh t cc ngun m b hoc m c basa. n Pht trin nhin liu sinh hc n nm 2015 tm nhn 2020 B Cng Thng ch tr c khi ng trong 2009. do Vit Nam, c rt nhiu nghin cu c tin hnh sn xut biodiesel thng qua phn ng este ha cho du m ng thc vt vi xc tc kim, tuy nhin theo nh gi chung th cc sn phm cha tha mn c mt s thng s k thut yu cu, nh v nht c hc, cn carbon hoc ch s axit. Xu th chung ca th gii hin nay l s dng cc xc tc axit rn d th cho cc qu trnh chuyn ha du m ng thc vt thnh nhin liu. Lun vn ny, chng ti tin hnh Nghin cu ch to xc tc axit ti rn trn c s Al 3 bin tnh bng La v Zn iu ch biodiesel t ngun m 2O ng vt qua s dng .
CHNG I: TNG QUAN

1.1. Nng lng ti to, ngun nng lng cho tng lai Vn nng lng ang l mt trong nhng mi quan tm hng u ca th gii trong nhiu nm tr li y. Hin nay, nhin liu ha thch vn ng vai tr ngun nng lng chnh cho nhn loi. Theo thng k ca C quan nng lng Quc t IEA vo nm 2006 (hnh 1.1) th nhin liu ha
7

thch cung cp khong 81 % tng nng lng tiu th ton cu (than : 26,0 %; du m: 34,4 % v kh t: 20,5 %); nng lng ht nhn chim khong 6,2 %; phn cn li t cc ngun nng lng mi nh hydro (khong 2,2 %) v cc ngun nng lng sinh khi (khong 10,7 %). [20]

Hinh 1.1. Nhu cu s dng nng lng trn ton th gii nm 2006.

Nng lng ha thch cung cp nng lng cho nhng phng tin giao thng, cc nh my cng nghip, si m cc to nh v sn sinh ra in nng phc v i sng con ngi. c tnh, trong khong 30 nm cui ca th k trc, nhu cu nng lng ca ton th gii tng gp i. c rt nhiu d on c a ra rng, vi tc tiu th nng lng ton cu hin nay th tr lng du v kh t nhin s thng xuyn nm trn st gim mnh trong th k XXI.

Hnh 1.2 D on v s bin i nhu cu s dng ba ngun nng lng chnh t nm 1850 n nm 2050.

Trong tng lai s vn cn nhng ngun nng lng ha thch nh du m v kh t p ng nhu cu nng lng trn ton th gii. Tuy nhin, v nhng ngun nng lng l hu hn v gy ra nhng nh hng xu n mi trng nn ngay t by gi nhn loi phi tm cch nng sao hiu qu s dng nng lng v nhanh chng tm kim nhng ngun nng lng thay th gin di nhu cu s dng nng lng ha thch. Mc d c nhiu ngun nng lng xanh v ang c con ngi sn xut v pht trin nh nng lng hydro, nhit nng bin, nhit nng t, nng lng gi, nng lng Mt tri, hay nng lng ht nhn nhng vn cha c mt ngun nng lng no kh nng thay th cho ngun nng lng ha thch ha thch. Trn th gii hin nay, c gn hai t ngi vn cha c tip cn vi nhng ngun nng lng hin i ni trn. Mt trong nhng phng n c xem l kh thi nht gii quyt bi ton tm kim ngun nhin liu thay th cho nng lng ha thch l s dng cc loi nhin liu Sinh hc, c bit l biodiesel c sn xut t ngun nguyn liu sinh khi.
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1.2. Nhin liu Sinh hc 1.2.1. Khi nim Nhin liu Sinh hc: l mt trong s nhng loi nhin liu c ngun gc t sinh khi. Thut ng ny bao gm sinh khi rn, nhin liu lng v cc loi gas Sinh hc khc. Chng l nhng cht t c bn cha carbon nm trong chu trnh quang tng hp ngn hn. Nhin liu Sinh hc c nhiu th h, ni bt trong l th h u tin vi bioancol, bioete, biodiesel, diesel xanh, du thc vt, kh t tng hp [5]. Biodisel: l hn hp cc ankyl este (thng l metyl este) ca axit bo mch di c sn xut t du thc vt hoc m ng vt, n c cc tnh cht tng ng vi diesel c sn xut t du m v c th s dng trc tip trong cc ng c diesel m khng cn phi thay i c cu ng c [21]. Biodiesel c nhng u im chnh nh im chp chy cao, ch s xetan ln, nht thp, tnh nhn cao, c th b phn hy Sinh hc, thn thin vi mi trng do trong qu trnh s dng bc x t carbon monoxit, cng nh cc kh thi khc so vi cc nhin liu ha thch thng thng [22]. Do gi thnh ca nhin liu ha thch lun mc cao nn nhin liu Sinh hc ni ln nh l mt trong nhng ngnh cng nghip c tc tng trng nhanh nht th gii hin nay. Nhiu quc gia, c bit l M v cc nc EU, v ang h tr tch cc cho cc cng ngh sn xut biodiesel t sn phm nng nghip. Nm 2006, gn 6,5 t tn biodiesel c sn xut trn ton th gii, trong sn lng ca M v khi EU chim khong 88 % (theo thng k ca Ngn hng Th gii, 2008). Biodiesel c sn xut ch yu t du, m ng thc vt v gi thnh ca ngun nguyn liu sinh khi ny chim khong 80 % gi thnh sn xut biodiesel. Gi thnh ca biodiesel hin ti vn cao hn so vi diesel ha thch. khc phc nhc im ny, mt s nh sn xut biodiesel ang nh hng cng ngh vo cc ngun nguyn liu gi thnh r nh m b. u
10

im ca vic s dng m b l lm gim gi thnh sn xut v x l c mt lng ln cht thi gy nhim mi trng. 1.2.2. u, nhc im ca biodiesel so vi diesel ha thch Cng ging nh diesel sn xut t du m, biodiesel c th s dng cho cc ng c t trong. Biodiesel c th c s dng trong cc ng c t-nn thng thng [22]. Ngoi ra, biodiesel cng c th c s dng di dng tinh khit hoc pha trn vi diesel theo mi t l (k hiu l Bxx, v d nh B30 l 30 % biodiesel trong 70 % diesel) c th lm gim lng pht thi ht rn khi ng c [16]. Bng 1.1 a ra mt s thng s vt l ca diesel, biodiesel v mt loi du thc vt (Karamja). Ch s xetan ca biodiesel cao hn diesel cho thy kh nng t chy nhin liu ca biodiesel tt hn. Cc gi tr t trng, nht v ch s HHV (Higher Heating Value) ca biodiesel tng i gn vi diesel. y l nhng yu t quan trng quyt nh kh nng thay th cho diesel lm nhin liu cho ng c t nn ca biodiesel. Ngoi ra, c th nhn ra rng nht ca du thc vt ln hn rt nhiu so vi diesel, do vy khng th trc tip s dng du thc vt thay th diesel c m phi chuyn v biodiesel. C mt im khc bit ln v tnh cht vt l ca biodiesel v diesel l im chp chy. C th, gi tr im chp chy ca biodiesel thng ln hn nhiu so vi diesel.
Bng 1.1. Mt s thng s vt l ca biodiesel, diesel ha thch, du thc vt. Tnh cht T trng (gm/cc) nht Ch s HHV (kJ/kg) Ch s xetan im chp chy (oC) Diesel 0,86 4,98 44579 47 74 Du Karamja 0,95 8,10 Biodiesl 0,87 6,22 38500 50 153

u im ca biodiesel so vi diesel ha thch

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S d vic nghin cu v pht trin cc quy trnh sn xut nhin liu Sinh hc ni chung ang thu ht c s quan tm ca cc nh nghin cu l v trn phng din l thuyt th vic s dng nhin liu Sinh hc khng lm cho hm lng kh carbonic (nguyn nhn chnh gy ra hiu ng nh knh) b tng ln trong kh quyn.

Hnh 1.3. Chu trnh sn xut v s dng biodiesel.

Chu trnh sn xut v s dng biodiesel c m hnh ha trong hnh 1.3. Ban u, kh carbonic trong kh quyn c thc vt hp th trong qu trnh quang hp. Sau , du c chit xut t ngun thc vt c chuyn ha thnh biodiesel. Khi biodiesel chy, kh carbonic c gii phng v quay tr li kh quyn. Thc vt s li hp th kh carbonic bt u mt chu trnh mi. Do vy, chu trnh ny hu nh khng lm tng hm lng khi carbonic trong kh quyn. Tuy nhin, khi t chy cc loi nhin liu ha thch nh diesel hoc than th lng carbonic pht thi ra mi trng s v cng ln. S dng biodiesel cng lm gim s pht thi carbon monoxit v cc ht cht thi rn ra mi trng. Hnh 1.4 cho thy s khc bit gia hm

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lng kh CO v cht thi rn bc x t cc loi ng c s dng nhin liu diesel ha thch vi ng c s dng nhin liu hn hp Bxx.

Hnh 1.4. Hm lng CO v ht rn pht thi trong ng c s dng nhin liu diesel ha thch v cc loi nhin liu hn hp Bxx.

Khi hm lng biodiesel trong hn hp Bxx tng th lng kh CO bc x s cng gim bi trong biodiesel c nhiu oxy hn diesel nn phn ng oxi ha gia carbon monoxit v oxy din ra hon ton to thnh kh carbonic. y l mt u im quan trng ca biodiesel do CO l mt kh rt c, gy ra nhiu bnh v ng h hp. Ngoi ra khng ch hm lng CO m hm lng cc ht kh thi rn bc x cng gim i khi s dng biodiesel, nguyn nhn c th l do biodiesel c s dng iu kin nhit cao hn nn trnh c s oxi ha khng hon ton v tch t ca cc sn phm cha carbon to thnh cc ht thi rn. Nhc im ca biodiesel so vi diesel ha thch Mc d biodiesel c nhiu c tnh vt tri hn so vi diesel ha thch nhng n cng c mt s im hn ch. Vic s dng biodiesel lm cho hm lng kh thi NOx tng ln do trong biodiesel th hm lng oxy nhiu hn so vi diesel ha thch nn trong cc qu trnh t chy th lng nhit ta ra rt
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ln, lng nhit ny lm cho nhit ca cc vng khng kh tng ln rt nhanh v thc y cc qu trnh oxi ha N2 trong khng kh thnh NOx.

Hnh 1.5. Hm lng NOx pht thi trong ng c s dng nhin liu diesel ha thch v cc loi nhin liu hn hp Bxx.

S dng nhin liu biodiesel cng gy ra mt kh khn v vn c cu ng c do n c th lm hng mt s b phn bng cao su v khng d tng thch vi ng c, do vy khi hot ng th ng c b rung ng mnh v nhanh hng hn. Ngoi ra, vic sn xut biodiesel c thc s thn thin vi mi trng hay khng vn ang l mt vn gy nn nhiu tranh ci. Mc d, a s cc nh khoa hc v nh qun l vn khuyn khch s dng nhin liu Sinh hc lm gim s pht thi kh carbonic ra ngoi kh quyn. Tuy nhin, c mt s nhm nghin cu M v Bc u vn a ra nhng khuyn co rng nhin liu Sinh hc s gp phn thc y nhanh qu trnh bin i kh hu ca Tri t. C th, nhm nghin cu ca Finn Danielsen thuc C quan Pht trin v Sinh thi hc Bc u tnh ton c rng s dng ngun nhiu liu trn cng phi mt hn 3/4 th k mi "tit kim" c mt lng kh thi CO 2 tng ng vi lng CO2 pht thi do tnh trng ph rng trng cc loi cy phc v sn xut nhin liu ny.

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1.3. Chuyn ha du, m ng thc vt thnh nhin liu 1.3.1. Ngun nguyn liu sinh khi Sinh khi: l tng trng lng ca sinh vt sng trong sinh quyn hoc s lng sinh vt sng trn mt n v din tch, th tch vng. V bn cht ha hc, sinh khi l cc phn t hu c khi lng ln, c cu trc lignoxenluloza. Sinh khi l ngun nguyn liu trin vng cho cng nghip ha cht v l ngun nng lng c kh nng ti sinh, cha nng lng ha hc - ngun nng lng t mt tri tch ly trong thc vt qua qu trnh quang hp. Nhin liu sinh khi c th dng rn, lng, kh... khi c t chy s gii phng nng lng [28]. Du, m ng thc vt: l cc lipit c ngun gc t cc vt th sng. V bn cht Ha hc, c du v m ng thc vt u c to thnh ch yu (khong 95 %) t cc triglyxerit ca nhng axit bo c phn t khi ln, thng l C12-18, v d nh axit oleic, axit linoleic, axit palmitic, axit stearic. Ngoi cc triglyxerit, trong du, m ng thc vt cn c khong 5 % axit bo t do, l loi axit n chc, mch thng v thng c s nguyn t carbon chn. Cc axit bo khng no c th cha 1, 2 hoc 3 lin kt i, chung d b oxi ho bi oxi khng kh lm cho du, m b hc ng (i, thiu), b polyme ho to thnh mng, b kh v tr ni i chuyn thnh axit bo no. Kh nng phn ng ca cc axit bo khng no tng cng vi s tng ca ni i. Tnh cht ca du, m do thnh phn v bn cht ca cc axit bo quyt nh. Ngoi cc axit bo t do, cn c mt lng nh photpho lipit, sp,

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Hnh1. 6. c lng sinh khi v cha c s dng trn ton th gii.

1.3.2. Mt s hng chuyn ha quan trng Hin nay, du, m ng thc vt c mt vai tr quan trng trong cng nghip ha cht v nhin liu. l ngun nguyn liu ln sn xut cc loi dung mi, dc phm, nha, polyme, mc, sn, m phm v c bit l cc loi nhin liu xanh nh biodiesel. Cc sn phm nhin liu c sn xut t du, m ng thc vt v cc sn phm chuyn ha ca chng ang rt c quan tm nghin cu bi kh nng ng dng thay th cho cc loi nhin liu ha thch.

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Phng php nhit phn: phng php cracking du, m ng thc vt c nghin cu b sung thm ngun nhin liu cho cc quc gia trong Chin tranh th gii th nht v th hai. Vi phng php ny, cc phn t triglyxerit nng c chuyn thnh cc phn t nh hn trong cc qu trnh nhit hoc nhit - xc tc. Qu trnh ny cng tng t nh cc qu trnh thng thng trong Ha du. c bit, nhin liu nhn c qua qu trnh ny l cc nhin liu ging diesel do c nhiu thnh phn nh olefin v paraffin, tng t nh cc loi xng du diesel. Tuy nhin, qu trnh ny i hi nhit cao, thng trong khong 300500 oC v vic c trng sn phm rt kh khn do c nhiu sn phm ph sinh ra trong qu trnh phn ng [26] v cc nh nghin cu c kt lun rng khi nhit nhit phn tng dn th lng sn phm chnh gim dn [14].

Hnh 1.7. C ch nhit phn triglyxerit ca axit bo bo ha (Alencar, 1983). [5]

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Hnh 1.8. C ch nhit phn triglyxerit (Schwab, 1998). [19]

Phng php este cho ha: l mt trong nhng phng php c s dng sn xut biodiesel c tnh thng mi cao. Cc loi ancol khc nhau nh metanol, etanol, propanol v butanol u c th c s dng. Tuy nhin, metanol v etanol l c s dng rng ri nht, c bit l metanol do gi thnh r v thun tin trong qu trnh vn chuyn v tin hnh phn ng [33]. Trong Ha hc Hu c c in, thut ng este cho ha c s dng m t phn ng m trong xy ra qu trnh trao i hp phn OR 1 ca este bi hp phn OR2 ca mt ancol. Phn ng thng c xc tc bi axit, baz hoc enzym [31].
O + R 1O R R2OH xc tc R2O R O + R1OH

ng dng ca phn ng este cho ha khng ch dng li quy m phng th nghim m cn m rng ra vi nhiu lnh vc thc t nhng quan trng nht vn l trong sn xut biodiesel v glyxerin. Ngun du m thin nhin c tinh ch loi b cc tp cht v tin hnh phn ng este ha
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cho vi cc ancol trong s c mt ca xc tc. Ton b qu trnh l mt chui gm ba phn ng lin tip v thun nghch vi cc sn phm trung gian l cc mono- v diglyxerit.
Triglyceride Diglyceride Monoglyceride + + + ROH ROH ROH Diglyceride Monoglyceride Glycerol + + + RCOOR1 RCOOR2 RCOOR3

Con ng to ra nhin liu ti sinh nhanh nht 1.4. Phng php este cho ha sn xut biodiesel 1.4.1. nh hng ca tp cht trong nguyn liu Hm lng cc tp cht, c bit l axit bo t do v nc trong nguyn liu, l thng s c bit quan trng nh hng n phn ng este cho ha. Vi xc tc baz, phn ng este cho ha din ra hon ton th hm lng axit bo t do phi thp hn 0,5 - 2 % khi lng (ty loi xc tc). Nu trong nguyn liu c nhiu axit bo th d xy ra phn ng x phng ha. y l phn ng khng mong mun, lm gim hiu sut biodiesel, n mn xc tc v gy nhiu kh khn cho vic tch loi sn phm. X phng sinh ra lm tng nht ca hn hp, to thnh gel v gy kh khn cho vic tch sn phm. Di tc dng ca nhit , x phng c th b ng rn, rt kh tch khi sn phm [10].
O HO C (CH2)7CH=CH(CH2)7CH3 axit oleic + KOH
+ -

O KO C (CH2)7CH=CH(CH2)7CH3 x phng + H 2O

Hm lng nc trong nguyn liu cng c th nh hng n hiu sut biodiesel. Khi c nc, c bit l nhit cao, c th xy ra phn ng thy phn triglyxerit to ra diglyxerit v cc axit bo t do. Di tc dng ca baz, axit bo s chuyn thnh x phng.
19

1.4.2. nh hng ca nhit phn ng Nhit c kh nng thc y tc phn ng este cho ha. Hnh 1.8 m t nh hng ca nhit n chuyn ha ca phn ng este cho ha gia du ht bng vi metanol, xc tc H2SO4. Kt qu ch ra rng chuyn ha tng ln khi nhit tng. Nguyn nhn l do khi nhit tng ln th nht ca du gim i, cc phn t tr nn linh ng hn v kh nng tip xc xy ra phn ng tng ln. Tuy nhin khi nhit tng ln vt qu mt ngng ti u no th nng sut to ra biodiesel s gim v nhit phn ng cao cng thc y cc phn ng x phng ha v thy phn metyl este. Nu nhit phn ng t n im si ca metanol, s c nhiu bong bng metanol c hnh thnh, hn ch s chuyn khi trn b mt phn cch pha. ng thi metanol b bay hi lm gim hiu sut phn ng v gy nhim mi trng bi metanol rt c hi. Theo mt s nghin cu th cc phn ng s dng xc tc baz tin hnh nhit thp hn so vi cc phn ng s dng xc tc axit [38].

20

Hnh 1.9. nh hng ca nhit n chuyn ha ca phn ng este cho ha du ht bng vi metanol, xc tc H2SO4.

1.4.3. nh hng ca thi gian phn ng Tc gi Freedman nghin cu thy rng chuyn ha ca phn ng este cho ha tng theo thi gian phn ng [11]. Ban u phn ng din ra chm do s trn ln v phn tn ca metanol vo du, m. Sau mt thi gian th tc phn ng tng ln rt nhanh. Vi xc tc axit th thi gian phn ng chm hn so vi xc tc baz. Xc tc ng th thc y phn ng nhanh hn so vi xc tc d th. Tuy nhin, thi gian phn ng qu lu th c th xy ra phn ng ngc, phn hy metyl este, lm gim hiu sut phn ng. ng thi, trong cng nghip, thi gian phn ng qu lu s tc ng n yu t kinh t.

21

1.4.4. nh hng ca t l metanol/du Trong phn ng este cho ha, t s hp thc ca metanol v du l 3:1. V vy theo nguyn l chuyn dch cn bng th s dng lng d metanol s u tin to ra metyl este. Mc d vy, nu dng d nhiu metanol th s gy kh khn cho vic tch v tinh ch sn phm. T l metanol/du c s dng ty thuc vo hm lng xc tc. Vi xc tc baz ng th th ch cn t l khong 6:1, vi xc tc d th nh CaO hay SrO th t l tng ln khong 9:1 hoc 12:1. Nu s dng xc tc axit, c bit l cc axit d th nh Amberlyst 15th t l metanol/du i hi rt cao, thm ch c th ti khong 300:1. 1.4.5. nh hng ca hm lng xc tc Cng ngh sn xut biodiesel hin nay ch yu s dng xc tc baz ng th, c bit l natri hydroxit. Hm lng xc tc ti u i vi NaOH l khong 1,0 - 1,5 % khi lng, cn vi KOH l khong 0,5 - 2,0 % khi lng. Thng thng, khi hm lng xc tc tng ln th hiu sut biodiesel s tng. Tuy nhin vi xc tc baz ng th th hm lng xc tc qu ln s to iu kin thun li cho phn ng x phng ha, lm gim hiu sut phn ng v hao mn xc tc. Vi xc tc axit th cn hm lng cao hn nhng s gy ra nhng vn nghim trng nh n mn thit b v nhim mi trng. 1.5. Cc h xc tc cho phn ng este cho ha Phn ng este cho ha khng xc tc din ra chm v thng cn nhit v p sut cao phn ng din ra hon ton. Kusdiana v Saka [8] a du ht ci vo mt qu trnh este cho ha khi khng c mt xc tc trong methanol siu ti hn v h nhn thy rng lng nc trong phn ng khng nh hng n s chuyn ha du. Ngc li, s hin din ca mt lng nc nht nh lm gia tng s hnh thnh cc metyl este v qu trnh este ha ca cc axit bo t do din ra ng thi trong mt giai on. Mc d sn phm c th phn tch d dng do khng c xc tc axit hoc
22

baz nhng qu trnh siu ti hn ny cn c tin hnh di iu kin nhit v p sut cao (250 400 oC v 35 60 MPa).

Nhng kho st c ngha c tin hnh trong phn ng ester cho ha du thc vt vi xc tc axit v baz ng th. Axit sulfuric v hidrocloric thng c s dng lm xc tc axit, c bit l khi du c cha nhiu axit bo t do v nc, do cc axit ny c kh nng iu khin ng thi phn ng phn ng este ha v este cho ha ca triglyxerit. Tuy nhin, qu trnh ny i hi t l metanol/du ln v thi gian phn ng lu [9]. Bn cnh , di cc iu kin ny th tt c cc thit b cn phi chng chu c s n mn do mi trng acid [34]. NaOH v KOH l nhng v d in hnh v cc xc tc baz ng th thng xuyn c s dng trong cng ngh [25, 18]. Phn ng este cho ha c th c thc hin trong mt thi gian ngn hn v cc iu kin phn ng tng i khim tn [14]. Mc d vi iu ny th lng nc v axit bo t do cha trong du phi rt thp bi s hnh thnh x phng c th tiu th cht xc tc v do lm gim hiu sut ca metyl este. Mt trong nhng nhc im ln nht ca xc tc ng th l chng khng th ti s dng hoc ti sinh, bi xc tc b tiu th trong phn ng v vic tch loi xc tc khi sn phm l rt kh khn v i hi nhiu dng c th nghim hn, dn n nhng chi ph sn xut cao hn [9]. Hn na, qu trnh ny khng thn thin vi mi trng bi c mt lng ln nc thi c to ra trong qu trnh tch loi sn phm [30]. Da vo nhng tin trn, vic pht trin mt xc tc rn c v nh l mt gii php thch hp khc phc nhng vn lin quan n xc tc ng th. Cc hydroxit kim loi [33], phc cht kim loi [10], oxit kim loi nh CaO [38], MgO [11], ZrO2 [17] v cc xc tc cht mang [27] c kho st nh cc xc tc rn. Xc tc ny khng b tiu th hoc ha tan trong phn ng v do c th d dng tch loi khi sn phm. Kt qu l sn phm khng cha cc tp cht ca xc tc v chi ph ca giai on tch loi cui cng s c gim xung. Xc tc cng c th d dng ti to v ti
23

s dng v n cng thn thin vi mi trng hn do khng cn x l axit hoc nc trong giai on tch loi [35]. Tuy nhin, mt trong nhng vn ln lin quan n xc tc d th l s hnh thnh ca ba pha vi ancol v du dn ti nhng gii hn khuch tn, do lm gim tc phn ng. Mt phng n khc phc vn chuyn khi i vi xc tc d th l s dng mt lng nht nh dung mi h tr (ng dung mi, co-solvent) thc y kh nng trn ln ca du v metanol, qua y nhanh tc phn ng. Tetrahydrofuran (THF), dimetyl sulfoxit (DMSO), n-hexan v etanol c s dng thng xuyn hn vi vai tr ca mt dung mi h tr trong phn ng este cho ha ca du thc vt v metanol vi xc tc rn. Gryglewicz [38] s dng CaO nh l mt xc tc baz rn cho phn ng este cho ha ca du ht ci vi metanol v sau khi phn ng din ra 170 pht, lng metyl este nhn c t hiu sut 93 %. Tuy nhin, bng cch thm mt lng nht nh THF vo hn hp du-metanol th cng vi hiu sut 93 % nhng thi gian phn ng ch cn l 120 pht. Mt phng n khc thc y cc qu trnh chuyn khi lin quan ti xc tc d th l s dng cc cht tr hot ha cu trc (structure promoter) hoc cc xc tc cht mang c th to ra din tch b mt ring ln hn v nhiu l rng hn, thc y kh nng thu ht v phn ng vi cc phn t triglyxerit c kch thc ln. Nhiu nghin cu c tin hnh tng hp v pht trin cc xc tc rn cho cc phn ng este cho ha khc phc cc nhc im t vic s dng xc tc d th v c kh nng gim chi ph sn xut biodiesel xung thp hn. Bournay pht minh ra mt qu trnh mi sn xut biodiesel lin tc c tnh thng mi, trong qu trnh ny cc xc tc rn cha oxit km v nhm c s dng v kt qu cho thy rng qu trnh ny khng i hi bt k mt x l no loi b xc tc khi biodiesel v lng metyl este, gn vi gi tr l thuyt, t c nhit v p sut cao. Hn na, glyxerol nhn c trong qu trnh ny c tinh khit xp x 98 %.

24

ng dng ca xc tc d th sn xut biodiesel c xem xt bi mt s nh nghin cu nh nhng kho st ca Di Serio v Lotero, c ch ca xc tc axit v baz rn cng ng hc phn ng este cho ha ca chng a phn c lm sng t. Tuy nhin, trong bi bo ny, ng dng ca cc loi xc tc rn khc, c bit l oxit kim loi v cht mang oxit kim loi, trong phn ng este cho ha ca du thc vt sn xut biodiesel c xem xt tm thy nhng xc tc, cht mang axit v baz ph hp nht v thng s hiu qu nht i vi hot tnh xc tc.

25

1.5.1. So snh u, nhc im cc h xc tc cho phn ng este cho ha

Bng 1.2. Tm tt u, nhc im ca cc h xc tc cho phn ng este cho ha. Xc tc u im Tc phn ng nhanh gp hng nghn ln so vi xc tc axit. Xc tc baz ng th Phn ng c th din ra iu kin m du v mc hao tn nng lng thp. Cc xc tc kim nh NaOH, KOH c gi thnh tng i r v c thng mi ha rng ri. Tc phn ng nhanh hn so vi xc tc axit. Phn ng c th din ra iu kin m du v mc hao tn nng lng thp. D tch xc tc ra khi sn phm. Xc tc d ti sinh v ti s dng. Khng b nh hng bi hm lng axit bo t do. Thch hp cho phn ng i t du, m km cht lng. Khng b nh hng bi hm lng axit bo t do. Thch hp cho phn ng i t du, m km cht lng. D tch xc tc khi sn phm. Xc tc d ti sinh v ti s dng. Khng b nh hng bi hm lng nc v axit bo t do. Xc tc enzym Thch hp cho phn ng i t du, m km cht lng.
26

Nhc im B nh hng nhiu bi hm lng nc v axit bo t do (FFA) trong nguyn liu. Khi hm lng FFA > 2 % s xy ra hin tng x phng ha. Nu c nhiu x phng sinh ra s lm gim hiu sut biodiesel v gy kh khn cho qu trnh tinh ch sn phm. Xc tc d b ng c khi tip xc vi khng kh. B nh hng nhiu bi hm lng nc v axit bo t do (FFA) trong nguyn liu. Nu c nhiu x phng sinh ra s lm gim hiu sut biodiesel v gy kh khn cho qu trnh tinh ch sn phm. Tc phn ng rt chm. Xc tc c th gy n mn thit b. Kh tch xc tc khi sn phm. Gi thnh cao. i hi nhit phn ng cao, t l mol ancol/du ln v thi gian phn ng lu. Mc hao tn nng lng cao. Sinh ra nhiu tp cht do s ra tri cc tm xc tc. Tc phn ng rt chm, thm ch l chm hn so vi xc tc axit d th. Gi thnh cao.

Xc tc baz d th

Xc tc axit ng th

Xc tc axit d th

 Phn ng din ra nhit thp, thm ch l thp hn so vi xc tc baz ng th. D tinh ch sn phm.

Ancol, c bit l metanol, c th lm gim hot tnh enzym.

1.5.2. Mt s h xc tc axit rn Do nhng hn ch ca cc h xc tc baz v xc tc ng th nn cn quan tm hn n vic pht trin cc xc tc axit rn nh l mt gii php thch hp khc phc nhng vn lin quan n xc tc ng th, c bit l cc xc tc c tnh baz. u im ca xc tc axit rn d th l khng b tiu th hoc ha tan trong phn ng v do c th d dng tch loi khi sn phm. Kt qu l sn phm khng cha cc tp cht ca xc tc v chi ph ca giai on tch loi cui cng s c gim xung, qu trnh cng c th c thc hin lin tc. Xc tc c th d dng ti sinh v ti s dng, ng thi cng thn thin vi mi trng hn do khng cn x l tch loi xc tc [29]. Hin nay, c nhiu hydroxit kim loi [3, 37], phc kim loi [12], oxit kim loi [6, 7, 23, 36, 37] v ang c th nghim v kim chng v hot tnh xc tc ca chng i vi phn ng este cho ha triglyxerit, nhng kt qu nhn c l tng i kh thi. Nhiu oxit kim loi, bao gm cc oxit kim loi kim th v oxit kim loi chuyn tip c kho st vi phn ng este cho ha ca du. Cu trc ca cc oxit kim loi c to thnh t cc ion kim loi tch in dng (cation)-axit Lewis v cc ion oxy tch in m (anion)-baz Lewis. Trong phn ng este cho ha du, n cung cp tm hp ph cho metanol, ti lin kt -OH d b b gy thnh anion metoxit v cation H+ (Hnh 2). V vy, ngay sau cc anion metoxide phn ng vi cc phn t triglyxerit to thnh metyl este ca axit tng ng .
CH3 H
+

O M+ O M+

Cc oxit kim loi chuyn tip nh ZrO2, TiO2 hay ZnO v ang c nghin cu ng dng lm xc tc cho phn ng este cho ha do tnh
27

axit mnh ca chng [17, 18]. Tnh axit ca cc oxit kim loi chuyn tip c th tng ln khi c bin tnh bi cc tc nhn nh sulfat, phosphat.
O S O Zr O H Zr Zr O O O O O O O Zr Zr H O O H Zr - H 2O Zr O Zr O OH O S O O OH

* *
O O

Zr

Zr

(1)

(3)

- H 2O

+ H2 O

- H2 O

O S O Zr O H O Zr O Zr O

O S

OH

* *
O O

Zr

O Zr O

H O O Zr

H Zr O O O Zr

O Zr

H O O

(2)

Zr

(4)

Hnh 1.10. Gi thit v s hnh thnh cc tm axit trong cu trc ca SO42-/ZrO2

Vt liu mao qun trung bnh silica nguyn cht ch c cc nhm silanol trn b mt, c tnh axit yu v khng c hot tnh xc tc. V vy, lm cho cc vt liu ny c th ng dng trong lnh vc xc tc, cc tm axit mnh hn c a vo mng cu trc ca chng. Thng thng, s thay th ca cc nguyn t khc vi ha tr thp hn ha tr ca silic to ra in tch m trong mng li, in tch ny c th c trung ha bi proton, do to ra tnh axit cho vt liu. c c xc tc ph hp cho phn ng este cho ha, cc vt liu mao qun trung bnh nn silica c th c bin tnh bi nhng nhm chc v c/hu c ph hp nh axit sulfonic hoc cc kim loi chuyn tip. V d nh vi xc tc SBA-15 c bin tnh bi axit
28

propylsulfonic th phn ng este cho ha m b t hiu sut khong 95 % (nhit phn ng 120 oC, thi gian phn ng 30 pht, t l metanol/m 20:1).

Hnh 1.11. Mt s vt liu nn silica bin tnh bi axit sulfonic.

Ngoi vt liu nn silica, vt liu nn carbon cng c nghin cu bin tnh lm xc tc cho phn ng este cho ha. Trc tin, carbon ha khng hon ton ng hoc xenlulozo khong 500 oC ch to nn carbon. Nhng vt liu nn carbon vo axit sulfuric 96 % v un nng 150 oC trong 15 gi di kh quyn N2, thu c vt liu nn carbon c bin tnh bng axit sulfuric, cha ng thi hai nhm chc axit -COOH v -SO3H. Vt liu ny c tnh axit rt mnh, ch s Ho khong -8 n -11, v c nghin cu ng dng cho phn ng este cho ha m b, hiu sut phn ng t khong 92 % (nhit phn ng 80 oC, thi gian phn ng 8 gi, t l metanol/du 30:1).

29

Hnh 1.12. Vt liu nn carbon bin tnh bng axit sulfuric.

Gn y, cc th h xc tc lai, a oxit kim loi nh H3PW12O4 cng c quan tm nghin cu nhiu v cho thy nhiu trin vng lm xc tc cho phn ng este cho ha du, m ng thc vt.

HNH 1.13. Xc tc lai, a oxit kim loi Ta2O5/Si(R)SiH3PW12O40

1.5.3. Xc tc th h mi a oxit kim loi Zn, La/-Al2O3 Nhm oxit: trong thin nhin c nhiu dng th hnh (a hnh) nhng ba dng quan trng nht l alpha (), theta () v gamma (). Trong ba dng th hnh chnh, -nhm oxit l dng bn nhit nht vi nhit nng chy ln ti khong 2051 oC, cc dng cn li l nhng dng gi bn.
Bng 1.3. Mt vi thng s vt l ca , v -nhm oxit.
30

Thng s vt l -nhm oxit -nhm oxit Khi lng ring (kg/m3) 3980 - 3990 3560 - 3600 Sut n hi (GPa) 409 - 441 cng (GPa) 28 H s bin i th tch 239 (GPa) Nng lng vng cm (eV) Nhit nng chy (oC) 8,8 2051 7,4 : 1050

-nhm oxit 3200 - 3700 : 700 800

- nhm oxit thng c s dng lm cht mang xc tc do c nng lng b mt nh, din tch b mt ln (100 - 250 m2/g) v th tch mao qun ln (0,3 - 1,0 cm3/g). Cc h xc tc trn nn -nhm oxit c s dng rng ri trong nhiu qu trnh cng nghip nh hydro desulfur ha, hon v, cracking. Tnh axit-baz ca -nhm oxit ty thuc vo phi tr ca nhm, mc dehydrate-dehydroxyl ha, tc nhn bin tnh, iu kin phn ng v phng php x l sau tng hp [18].
tm Lewis OH Al O tm Bronsted Al O tm Lewis OH Al

Hinh 1.14. Hai loi tm axit trn b mt -nhm oxit.

Bin tnh -Al2O3 Nhm oxit, c bit l dng , thng c s dng lm cht mang xc tc trong cng nghip do din tch b mt ring ln v c th to thnh d dng m khng cn dng ti cht kt dnh. Phng php bin i cu trc v hot tnh ca nhm oxit bng cc kim loi nh Fe, Mn, Zn v ang c nghin cu nhiu, c bit l trong lnh vc xc tc. Qu trnh bin tnh bng kim loi lm thay i kt cu mng tinh th ca nhm oxit: xy ra s thay th ng hnh nguyn t nhm bi cc kim loi khc hoc c s hnh thnh pha spinel trn b mt. Nhng bin i nh hng n hot tnh ca xc tc, c bit l lc axit.
31

1.6. Hng nghin cu ca ti M b l este ca glyxerol vi axit bo, ch yu l axit stearic ngoi ra cn mt s axit khc nh palmitic, oleic. Axit bo no trnh nhiu phn ng ph nh phn ng trng hp, oxi ha, Tuy nhin do c gc hidrocacbon di nn tnh a du tt nhng tnh a nc km. Hin nay Vit Nam, ti cc l m, m b gy nhim mi trng rt ln. Vic s dng m b iu ch monoglyxerit lm biodiesel v cc sn phm ha hc khc c ngha rt ln cho khoa hc, kinh t v mi trng. Ni dung ca lun vn ny l trnh by phng php tng hp xc tc a oxit kim loi Zn, La/-Al2O3. Vt liu nn -Al2O3 c tng hp bng phng php sol-gel t tin cht Al(NO3)3.9H2O v ure, sau bin tnh bng mui km, lantan. Xc tc tng hp c nghin cu cc c trng cu trc bng phng php nhiu x tia X, tn sc nng lng tia X v TPD NH3. Thc hin phn ng este cho ha m b vi h xc tc tng hp. Nghin cu nh hng ca t l mol methanol/m v thi gian n phn ng ester cho ha. nh gi sn phm qua s to nh khi ra v phn tch thnh phn sn phm bng phng php sc k kh - khi ph.

32

CHNG II:

THC NGHIM

2.1. Tng hp xc tc 2.1.1. Tng hp -nhm oxit Vt liu nn -nhm oxit c tng hp bng phng php sol-gel . Hoa tan PEG vao nc ct, Ha tan nhm nitrat nanohydrate (Al(NO3)3.9H2O, ha cht dng cho phn tch) vo nc ct ti gn bo ha (khong 70 g/100 g H2O) v khuy u nhit phng. Cho t t ure (CO(NH 2)2, ha cht dng cho phn tch) vo dung dch theo t l mol Al3+/ure ty chn, khuy u trong 1 gi. n nh hn hp phn ng trong 1 gi v gi ha 90 oC trong 12 gi, thu c gel alumina. Nung gel t nhit phng ln ti khong 450 oC (tc gia nhit 5 oC/ pht) v gi trong 3 gi, thu c nhm oxit bt xp. PEG Al(NO3)3.9H20

Pha vo nc ct

Ure

Khuy u trong 1gi, n nh trong 1gi

Thy nhit di p sut t sinh trong autoclave 900C trong 12 gi

Nung 4500C trong 3gi

-Al2O3

33

2.1.2. Tng hp xc tc a oxit kim loi Ha tan hyrat km axetat Zn(CH3COO)2.2H2O va La(NO3)3.6H2O vo dung dch KOH (lng KOH ly d gp i so vi lng km v s mol), khuy trong 2 gi nhit khong 80 - 90 oC. Sau cho hn hp vao mu nhm oxit tng hp ( mu nhm ang hoat hoa), ng thi iu chnh pH dung dch ~ 9 (bng NH3). Lc tch kt ta, ra, sy 90 oC trong 12 gi. Kt ta sau khi lm kh c nung t nhit phng ln 450 oC (tc gia nhit 5 oC/pht) v gi nhit ny trong 5 gi. Thu c xc tc rn a oxit kim loi Zn, La/-Al2O3 (k hiu l MA, modified alumina).
Zn(CH3COO)2.2H2O
iu chinh pH ~ 9 (bng

NH3) La(NO3)3.6H2O Pha vao dung dch KOH, khuy trong 2 gi 80-900C

-Al2O3 hot ha

Lc tch kt ta, ra, sy 90 oC trong 12 gi

Nung nhit 450 oC trong 5 gi

Xuc tac Zn, La/-Al2O3

T l phn trm khi lng cc ha cht s dng (quy i v khi lng oxit vi nhm): H a ch t Z n (C HC O O2).2H2O1 Z n(C HC O O2).2H2O2 L a(N O)3.6H2O 3 3 3
34

A l2O3

K h i l n g (g am ) P h n trm (tn h th e o o)xit

0 ,1 9 1 3 ,7 8 %

0,15 10,88 %

0,13 9,60 %

0,51 65,74%

2.2. c trng tnh cht vt liu 2.2.1. Phng php nhiu x tia X [1, 2] Phng php nhiu x tia X (XRD) l mt cng ngh c s dng rng ri trong khoa hc vt liu xc nh tinh th v tnh cht cu trc v pht hin ra s khim khuyt tinh th. Theo l thuyt cu to tinh th, mng tinh th c xy dng t cc nguyn t hay ion phn b u n trong khng gian theo mt quy lut xac inh. Mi mt mng nh mt lp phn x cc tia X khi chng chiu vo cc mt ny. Chm tia X ti b mt tinh th v i su vo bn trong mng li th mng li ng vai tr nh mt cch t nhiu x c bit. Cc nguyn t, ion b kch thch bi chm tia X s thnh cc tm pht ra cc tia phn x. Khi cc tia ny giao thoa vi nhau ta s thu c cc cc i nhiu x, lc bc sng ca tia X phi tho mn phng trnh Vulf-Bragg, phng trnh c bn nghin cu cu trc mng tinh th.

= 2.dhkim loi.sinhkim loi = n

35

Hnh 2.1. Nguyn li cu tao cua may nhiu xa tia X

Phng phap nay a cung cp cac thng tin ro rang v cac phn t co t l thnh phn khi lng trong hp cht u ln. Tuy nhin i vi cac hat co ti l thanh phn khi lng 5% hoc v inh hinh thi khng th phat hin c. Do o khng bao gi chc chn rng khng co pha la khi s dung phng phap XRD. Mc khac, b mt ni tp trung hoat tinh xuc tac cung khng nhn bit qua nhiu xa tia X. nh nhiu x tia X ca cc vt liu tng hp c ghi bng thc o nhiu x bt tia X Bruker D4 s dng bc x Cu-K , ti khoa Ha hc, trng i hc Khoa hc T nhin, i hc Quc gia H Ni. 2.2.2. Gii hp NH3 theo chng trnh nhit : TPD-NH3 [1, 2] Phng php gii hp NH3 theo chng trnh nhit (TPDTemperature Programmed Desorption) c tm ra vo nm 1960 xc nh lc axit v lng cc tm axit tng ng trn xc tc. Ngi ta s dng NH 3 nh l mt cht d, c hp th bo ha trn cc tm axit ca b mt xc tc. Cc mu xc tc sau khi hp th cn bng NH3 di iu kin xc nh s c gia nhit theo chng trnh nhit . Khi nng lng nhit cung cp ln
36

hn nng lng hp th. Cc phn t NH3 gii hp khi b mt cht hp th v c kh mang a qua detector xc nh lng. Lp th biu din s ph thuc gia lng NH3 gii hp theo nhit . Trong qu trnh gi hp NH3 theo nhit , trn nhng tm axit yu s gii hp NH3 trc, trn nhng tm axit mnh s gii hp NH3 sau. Nh vy, cc tm c lc axit mnh s c Tmax ln v ngc li. Tng din tch pic NH3 cho bit lng kh b hp th v t c th tnh c [H+] (S tm axit) trn mt n v khi lng cht xc tc (mmol/g). .Mi quan h gia nhit gii hp v nng lng (Nhit) gii hp c biu din theo phng trnh sau: Log(Tp2/) = - Ed /2,302. RTP + log(EdA/RC) Trong : : Tc gia nhit tuyn tnh . TP : Nhit ca pic. Ed : Nng lng gii hp. A : Lng cht b hp ph bo ha . C : Hng s tc gii hp. Nh vy, th log(Tp2/) theo 1/TP s l ng thng ch quan h tuyn tnh gia hai i lng ny trong qu trnh gii hp theo chng trnh nhit v t c th xc nh gi tr Ed t dc ca th. Da vo din tch peak gii hp ti cc nhit khc nhau ta c th xc nh c lng NH3 tiu th v t nh gi c lc axit v s lng cc tm axit tng ng. Cc tm axit yu s gii hp NH3 nhit thp v ngc li cc tm axit mnh hn gii hp NH3 nhit cao hn. Tm axit yu gii hp ti nhit 2000C Tm axit trung bnh gii hp nhit t 200-4000C
37

Cc tm axit mnh gii hp nhit 4000C mnh ca mt axit c nh ngha bi kh nng chuyn ha mt baz hp th n trn b mt n thnh axit lin hp tng ng. Nu s chuyn ha bao gm s chuyn proton sang cht b hp th th khi cht hp th c trng cho loi axit c gi l axit Bronsted. Ngc li, nu b mt chia s cc cp electron ca n cho cht b hp ph th n c trng cho loi axit c gi l Lewis. Khi baz s dng l NH3, ta c th m t hai phn ng minh ha cho hai loi axit nu nh sau : Axit Bronsted : Axit Lewis : A-H+ + NH3 A-NH4+ A + NH3 A.NH3

A : l tm axit Bronsted hoc Lewis. 2.2.3. Phng php tn sc nng lng tia X [1, 2] Ph tn sc nng lng tia X (EDX) l k thut phn tch thnh phn Ha hc ca vt rn da vo vic ghi li ph tia X pht ra t vt rn do tng tc vi cc bc x (m ch yu l chm electron c nng lng cao trong cc knh hin vi in t).

Hnh 2.2. Nguyn l ca php phn tch EDX.

38

Anh vi cu trc vt rn c ghi li thng qua vic s dng chm in t c nng lng cao tng tc vi vt rn. Khi chm in t c nng lng ln c chiu vo vt rn, n s m xuyn su vo nguyn t vt rn v tng tc vi cc lp in t bn trong ca nguyn t. Tng tc ny dn n vic to ra cc tia X c bc sng c trng t l vi nguyn t s (Z) ca nguyn t theo nh lut Mosley[1]:

C ngha l, tn s tia X pht ra l c trng vi nguyn t ca mi cht c mt trong cht rn. Vic ghi nhn ph tia X pht ra t vt rn s cho thng tin v cc nguyn t ha hc c mt trong mu ng thi cho cc thng tin v t phn cc nguyn t ny

Hnh 2.3. S nguyn l ca h ghi nhn tn hiu ph EDX trong TEM.

Tia X pht ra t vt rn (do tng tc vi chm in t) s c nng lng bin thin trong di rng, s c a n h tn sc v ghi nhn (nng lng) nh detector dch chuyn (thng l Si, Ge, Li...) c lm lnh bng nit lng, l mt con chip nh to ra in t th cp do tng tc vi tia X, ri c li vo mt ant nh. Cng tia X t l vi t phn nguyn t c mt trong mu. phn gii ca php phn tch ph thuc vo kch c chm in t v nhy ca detector (vng hot ng tch cc ca detector). chnh xc ca EDX cp mt vi phn trm (thng thng ghi nhn c s c mt ca cc nguyn t c t phn c 3-5% tr ln). Tuy
39

nhin, EDX t ra khng hiu qu vi cc nguyn t nh (v d B, C...) v thng xut hin hiu ng trng chp cc nh tia X ca cc nguyn t khc nhau (mt nguyn t thng pht ra nhiu nh c trng K, K..., v cc nh ca cc nguyn t khc nhau c th chng chp ln nhau gy kh khn cho phn tch). Ph tn sc nng lng tia X ca cc vt liu c ghi li bi my phn tch JEOL JED-2300 Analysis Station ti Vin Khoa hc Vt liu, Vin Khoa hc - Cng ngh Vit Nam. 2.3. Phn ng este cho ha Nguyn liu cho phn ng este cho ha l m b loi cn bng phng php lc v ht m bng silica gel. Lp h thng thit b phn ng este cho ha nh hnh di y. Cho xc tc v metanol vo bnh cu, khuy u trong khong 15 pht. Cho t t m b vo, khuy u hn hp phn ng v duy tr nhit trong khong 60 - 65 oC.
H2C HC H2C OCOR1 OCOR2 OCOR3 + 3CH3OH xc tc H2C HC H2C OH OH OH + R1COOCH3 R2COOCH3 R3COOCH3 metyl este (biodiesel)

triglyxerit

Cc phn ng c tin hnh nhng iu kin khc nhau nghin cu nh hng ca cc yu t nh hng ti phn ng este cho ha.

40

Hnh 2.4. S thit b phn ng trong phng th nghim.

Sau khi quay ly tm loi xc tc, hn hp sau phn ng c chuyn sang phu chit, lng trong 12 gi. Sau khi hn hp phn ng tch lp th ra bng nc nng nhiu ln tch metyl este. Sn phm sau khi ra c cho vo cc thy tinh v sy khong 100 oC loi nc. Sau cng, em hp ph bng silica gel loi ht phn nc d cn li. 2.4. nh gi thnh phn sn phm Sn phm ca phn ng c thc hin trong iu kin ti u c t trng bng phng php Sc k - Khi ph GC - MS. Mu c phn tch trn my GC-MS System - Hewlett HP 6800, Mass selective detector Hewlett HP 5973. Ct tch HP - 5 MS crosslinked PH 5 % PE Siloxane, 30m 0,32m. Ti Trung tm Ho du, Khoa Ho hc, Trng i hc Khoa hc T Nhin, i hc Quc Gia H Ni.

41

CHNG III: KT QU - THO LUN

3.1. Tng hp -Al2O3 Ure l mt baz yu, ng vai tr l tc nhn thy phn to gel alumina. Trong qu trnh tng hp, ure tan trong nc b thy phn to ra cc in carbonat v hydroxit.
C O(NH2)2 C O(NH2)2 + + H+ + 2H2O 2H2O 2NH4+ 2NH4+ + + HC O 3H2C O 3

2H+ +

Dung dch nhm nitrat ban u c mi trng axit (xc nh bng giy ch th pH cho kt qu khong 2,0), do vy carbonat thot ra khi dung dch di dng kh carbon dioxit, cn hydroxit s tham gia vo qu trnh trng hp cc cation cha nhm v lm tng pH ca dung dch. Theo tc gi S. Ramanathan [35] th trong iu kin ny s hnh thnh cc oligome nh Al3(OH)9(H2O)4 di tc dng ca cc mm keo t. Khi pH ca dung dch t ti khong 6,5 th bt u xy ra qu trnh gel ha, cc oligome tham gia vo mt chui cc phn ng chuyn v, ngng t vi nhau thng qua cc lin kt cu oxy Al-O-Al hoc cu hydroxy Al-OH-Al.

Al

HO

Al

Al

Al

Trong phn ng, PEG

c vai tr l cht nh hng cho cc

ion, gip qu trnh thy phn din ra t t. Nhm oxit c tng hp bng phng php sol-gel vi tc nhn thy phn ure. Thc hin 3 th nghim, ure c cho t t vo dung dch nhm nitrat bo ha vi t l mol Al3+/ure mi th nghim ln lt l l 1:5; 1:10 v 1:15. Khuy u hn hp phn ng trong 1 gi, sau gi ha 90 oC trong 12 gi, thu c gel alumina. Cc kt qu quan st c a ra bng sau y:
42

Bng 3.1. Hin tng hnh thnh gel vi cc t l mol Al3+/ure khc nhau. M u A-5 A-10 A-15 T l mol Al3+/ure 1:5 1:10 1:15 Hin tng hnh thnh gel Gel alumina hnh thnh t Hnh thnh gel, mu trng Hnh thnh gel mu trng, hi c

Hai mu gel A-10 v A-15 c lm kh, nung t nhit phng ln ti khong 450 oC (tc gia nhit 5 oC/ pht) v gi trong 3 gi th thu c bt mn mu trng. nh nhiu x tia X gc rng (2 = 20 80 o) ca hai mu A-10 v A-15 sau khi nung c a ra hnh 19 v 20. Mu A-10 sau khi nung thu c nhm oxit c cu trc gamma, tng ng vi cc tn hiu nhiu x ti 2 ~ 38o, 46o v 67o; c trng cho cc mt nhiu x tng ng (311), (400) v (440) [34]. Cc tn hiu c trng xut hin kh r, chng t c s hnh thnh cc tinh th nano. Kt qu quan st s hnh thnh gel nhm oxit kt hp vi nh nhiu x tia X ca gel sau khi nung cho thy rng t l mol Al3+/ure = 1:10 l tng i gn vi gi tr ti u to ra -nhm oxit c tinh th cao. Nu t l Al3+/ure qu thp th rt kh hnh thnh gel alumina (mu A-5), nguyn nhn c th l do nng ure khng ln t ti ngng to gel. Cn nu qu d ure th pH ca dung dch s tng ln rt nhanh, lm cho qu trnh ngng t cc oligome cha nhm din ra khng ng nht. Ngoi ra, mt lng ure khng kp thy phn hon ton s nm li trong cu trc gel, di tc dng nhit s phn hy thnh kh CO2 v NH3, ng thi lm sp cu trc tinh th. Kt qu l gel sau khi nung s to ra nhm oxit v nh hnh (mu A-15).

43

Hnh 3.1. Gian nhiu x tia X gc rng ca mu A-10 sau khi nung.

Hnh 3.2. Gian nhiu x tia X gc rng ca mu A-15 sau khi nung.

3.2. Bin tnh -Al2O3 3.2.1. nh nhiu x tia X

44

nh nhiu x tia X gc rng (2 = 20 80 o) ca mu MA c a ra hnh 18. Trn ph xut hin cc tn hiu c trng cho cu trc ca nhm oxit gi tr 2 ~ 38,5o v 67o. Cc tn hiu nhiu x ca mu MA khng r rng nh i vi -nhm oxit tinh khit (mu A-10 sau khi nung, xem hnh 19), chng t rng sau khi bin tnh th tinh th ca nn nhm oxit b gim.

Hnh 3.3. Gian nhiu x tia X gc rng ca mu MA.

45

D on rng Zn v La i vo cu trc di dng v nh hnh. Tuy nhin, nhiu ti liu nghin cu ch ra rng d dng v nh hnh nhng cc nguyn t c orbital d vn gy ra cc hiu ng in t lm tng lc axit b mt ca vt liu [17, 35], do vy lm tng hot tnh xc tc ca vt liu. c bit, ZnO l mt oxit lng tnh, va c hiu ng lm tng lc axit, ng thi cng c tnh baz thc y phn ng este cho ha din ra nhanh hn. 3.2.2. Gii hp NH3 theo chng trnh nhit : TPD-NH3 Kt qu gii hp ammonia theo chng trnh nhit , TPD-NH3

Hnh 3.4: Kt qu gii hp ammonia theo chng trnh nhit

Nhit u: 102,4 oC Nhit cui: 599,8 oC Tc gia nhit: 7,2 oC

Bng 3.2: Kt ca phn tch TPD-NH3

tomax (oC) 188,4

Loi tm axit Yu

Th tch ammonia (mL/g) 3,68029

46

557,3

Mnh

1,27263

Xc tc c hai loi tm axit, tng ng vi nhit gii hp 188,4 oC, th tch NH3 l 3,68028 (ml/g) (tm axit yu) v 557,3 oC,th tch NH3 l 1,27263 (ml/g) (tm axit mnh) . 3.2.3. Ph tn sc nng lng tia X Hm lng cc nguyn t trong mu MA c xc nh bi phng php tn sc nng lng tia X (phng php EDX). Ph EDX cho thy s tn ti ca cc kim loi Zn v La trong mu nhm oxit bin tnh.
1000 900 OKa LaMz CuLl CuLa ZnLl LaMa LaMr ZnLa 800 700 600 Counts 500 400 300 200 100 0 0.00 1.00 2.00 3.00 4.00 5.00 keV 6.00 7.00 8.00 9.00 10.00 AlKa KKesc 003

AlKsum KKa KKb CaKa CaKb LaLl

LaLa LaLb LaLb2 LaLr LaLr3

KKsum

ZnKa CuKa CuKb ZnKb

Hnh 3.5. Ph tn sc nng lng tia X ca mu MA. (1)

47

7200 6400 5600 4800 Counts 4000 3200 2400 1600 800 0

005

OKa LaMz CuLl CuLa ZnLl LaMa ZnLa LaMr AlKa KKesc

AlKsum KKa KKb CaKa CaKb LaLl

LaLr3

LaLa LaLb LaLb2 LaLr

KKsum

CuKb 9.00
ZnKa CuKb 9.00

ZnKa 7.00 8.00 CuKa ZnKb 10.00

ZnKb 10.00 KKsum 7.00 8.00 CuKa

0.00

1.00

2.00

3.00

4.00

5.00 keV

6.00

Hnh 3.6. Ph tn sc nng lng tia X ca mu MA. (2)

6400 5600 4800 4000 Counts 3200 2400 1600 800 0

006

OKa LaMz CuLl CuLa ZnLl LaMa ZnLa LaMr AlKa KKesc

AlKsum KKa KKb CaKa CaKb LaLl

0.00

1.00

2.00

3.00

4.00

Hnh 3.7. Ph tn sc nng lng tia X ca mu MA. (3) 48

LaLa LaLb LaLb2 LaLr 5.00 keV 6.00

LaLr3

Bng 3.2. Kt qu phn tch hm lng nguyn t trong mu MA bng EDX. Nguyn t Zn La Al Hm lng (ln 1) 8,46 % 4,67 % 46.61 % Hm lng (ln 2) 8,18 % 4,35 % 47,09 % Hm lng (ln 3) 10,70 % 4,51 % 45,03 %

kt qu phn tch c khch quan v chnh xc, php phn tch EDX c thc hin ba ln i vi ba im bt k trn mu nhm oxit. C ba ln phn tch u cho kt qu v hm lng Zn, La, Al trong mu MA kh ging nhau, chng t rng cc nguyn t Zn v La c phn tn trong cu trc nhm oxit tng i ng nht. Ngoi nhng nguyn t chnh trn, cn c ln mt s nguyn t khc nh K, Ca, Cu vi hm lng rt nh. S xut hin cc nguyn t ny c th l do ln tp cht trong nguyn liu hoc sai s ca php o. Tuy nhin, s tn ti ca cc nguyn t ny khng gy nh hng c hi n hot tnh xc tc ca vt liu. Ngc li, mt s nguyn t nh K hay Ca di dng oxit cn ng vai tr cht tr, lm tng bn c hc cho xc tc. Phng php EDX ch gip xc nh hm lng nguyn t trong mu MA ch khng cho bit trng thi tn ti (tinh th hay v nh hnh) ca chng. Mun khng nh v trng thi tn ti ca cc nguyn t Zn, La cn kt hp c d liu nhiu x XRD trn. 3.3. Phn ng este cho ha m b 3.3.1. Xc nh ch s axit bo t do ca m b Cn 3-5g mu vo bnh nn, thm vo 50mL dung mi hn hp gm ete etylic v mt phn etanol, lc cho tan du. Trong trng hp du khng tan ht phi va lc, va un nh trn bp cch thy ri lm ngui n
49

nhit 20oC. Sau cho vo bnh 5 git ch th phenolphtalein (vi du thm mu, dng thimolphtalein) v chun b bng KOH 0,1N cho n khi xut hin mu hng nht bn trong 30 giy. Ch s axit ca m c tnh bng cng thc:

X=
Trong :

5,611.K.V m

V ~ S ml dung dich KOH 0,1N dng chun K ~ H s hiu chnh ca dung dch KOH 0,1 N 5,611 ~ S mg KOH c trong 1 mL dung dch KOH 0,1 N M ~ lng mu th, g Mi mu c xc inh ba ln, kt qu cui cng l trung bnh cng ca kt qu ba ln th. Chnh lch gia kt qu ba ln th khng ln hn 1 mg i vi m tinh ch.

Bng 3.3. Kt qu xc nh ch s axit ca m b

Ch s axit ca mu m b Ln 1 M b Ln 2 Ln 3 Ch s axit t do trung bnh

5,37

5,24

5,43

5,35

3.3.2. Nghin cu hot tnh xc tc vi phn ng este cho ha m b Xc tc axit rn a oxit kim loi Zn, La/-Al2O3 (MA) tng hp c s dng lm xc tc cho phn ng este cho ha m b (ch s axit bo t do 5,35 mgKOH/g). Hot tnh xc tc c nghin cu thng qua nh hng ca thi gian phn ng n hiu sut ca phn ng. Hot tnh ca xc tc rn d th MA cng c so snh vi cc xc tc baz ng th (natri menolat, MeONa). Sn phm phn ng este cho ha c phn tch thnh phn bng phng php sc k kh - khi ph.
50

3.3.2.1. Kho st nh hng ca thi gian ti phn ng este cho ha m b Thc hin 3 phn ng este cho ha m b bng xc tc MA theo cc thi gian phn ng khc nhau. Mi mu phn ng c tin hnh vi t l metanol/m b 18:1 (40 mL du, D 0,9 g/mL v 30 mL metanol, M 0,8 g/mL); hm lng xc tc 3% so vi khi lng m; nhit phn ng trong khong 6065oC. Hiu sut phn ng c th c nh ga thng qua khi lng metyl este sau x l v hin tng to nh khi ra. Kt qu phn ng c a ra bng 3.4.
Bng 3.4. Nghin cu nh hng ca xc tc MA vi phn ng este cho ha. Mu metyl este M-2 M-6 M-10 Thi gian 2 gi 8gi 10 gi nh gi hin tng to nh khi ra To nh nhiu, nhanh ng rn Hu nh khng to nh Hu nh khng to nh

Kt qu cho thy mu M-2, tng ng vi thi gian phn ng 2 gi, t hiu sut rt thp, do thi gian phn ng qu ngn, cha trn ln hon ton cc cht phn ng v xc tc vi nhau. c bit l vi phn ng ca m b (cha nhiu hp cht c phn t khi cao, mch carbon di nn nht rt ln) th tc phn ng ban u din ra rt chm. Mu M-6, M-10, tng ng vi thi gian phn ng t 8 10gi, t hiu sut tng i tt, hu nh khng to nh khi ra. Cc mu sn phm c hiu sut thp thng cha cc mono, i glyxerit. y l cc cht c khi lng phn t tng i ln, kh bay hi. Chnh v vy nu phn tch GC cc sn phm ny rt d nm li trong ct sc k, lm nh hng n kt qu phn tch. Do , ch c php tin hnh phn tch GC vi cc mu c hiu sut cao. Phn tch GC-MS vi cc mu sn phm c thnh phn n nh, cho thy cc sn phm thu c c thnh phn
51

chnh l cc este ca axit bo. Do vy, rt thch hp cho vic s dng lm biodiese. Tin hnh phn tch thnh phn mu M-6 t hiu sut cao c thnh phn chnh l: 11-Hexadecenoic acid, methyl ester ~ 4,27 % Pentadecanoic acid, 14 methyl -, methyl ester ~ 21,48 % 9-Octadecenoic acid (Z) , methyl ester ~ 35,92 % Octadecanoic acid, methyl ester ~ 18,15%

Hnh 3.8. Sc k ca sn phm phn ng s dng xc tc MA (mu M-6).

Sc k c ng nn phng, cc pic sc nhn, chng t sn phm sch v c rt t cc sn phm ph (monoglyxerit, axit, ). Cc thnh phn chnh ca sn phm c xc nh bng ph MS vi i tin cy cao.

52

Hnh 3.9. Ph MS ca Pentadecanoic acid, 14 methyl -, metyhyl ester c trong sn phm. 53

Hnh 3.10. Ph MS ca 9-Octadecenoic acid (Z), metyhyl ester c trong sn phm 54

3.3.2.2. So snh hot tnh xc tc MA vi xc tc baz ng th Thc hin phn ng este cho ha m b (40 mL) vi metanol, s dng hai h xc tc axit rn MA v natri melonat (MeONa). Cc thng s phn ng v kt qu c a ra bng 3.5. Vi xc tc baz ng th MeONa, do m b c hm lng axit bo t do rt cao (ch s FFA 5,35 mg KOH/g), nn phn ng sinh ra nhiu x phng.
Bng 3.5. Thng s phn ng este cho ha vi xc tc MA v MeONa Xc tc MA T l metanol/d u 18:1 Hm lng xc tc 3 % .kl Nhit phn ng 60 - 65
o

Thi gian phn ng 8 gi

Hin tng to nh Hu nh khng to nh Sn phm c nhiu nh, nhanh b ng rn

C 4 gi

MeO Na

9:1

3 % .kl

60 - 65
o

Ngoi ra, m b sau x l vn khng khan hon ton, vn cn ln mt lng nc, di tc dng ca xc tc baz s thc y phn ng thy phn triglyxerit thnh axit bo v diglyxerit, khi ra bng nc th c hin tng to nh nhiu. y l nguyn nhn lm gim hiu sut phn ng to metyl este. Ngoi ra, cc mono- v diglyxerit l nhng c khi lng phn t tng i ln, kh bay hi, chnh v vy nu phn tch bng GC cc sn phm ny s rt d nm li trong ct sc k, lm nh hng ti kt qu phn tch.
H2C HC H2C OCOR1 OCOR2 OCOR3 + H2O NaOH H2C HC H2C OH OCOR2 OCOR3 + R1COOH NaOH R1COONa

triglyxerit

So vi xc tc MeONa, xc tc d th MA cn thi gian tin hnh phn

55

ng lu hn do m b cha nhiu phn t hu c c gc hydrocarbon mch di (nh axit oleci, axit stearic, ...) lm cho m c nht rt ln v lm hn ch qu trnh phn tn pha. Tuy nhin vi phn ng dng xc tc MA, lng metyl este sau khi x l nhiu hn so vi trng hp s dng xc tc MeONa do phn ng to nh rt t.

Hnh 3.12. So snh hin tng to nh vi phn ng s dng hai h xc tc khc nhau: MeONa (tri) v MA (phi).

56

CHNG IV: KT LUN

1. Nghin cu ch to xc tc axit rn trn c s Al2O3 bin tnh bng La v Zn. Vt liu nn -nhm oxit c tng hp bng phng php sol-gel t Al(NO3)3.9H2O vi tc nhn thy phn ure, t l mol Al 3+/ure = 1:10. Vt liu nn c bin tnh bi mui Zn(CH3COO)2.2H2O v mui La(NO3)3.6H2O. 2. c trng tnh cht ca h xc tc bng cc phng php Vt l hin i. Kt qu cho thy xc tc vn gi c cu trc nh vt liu nn. phn tn thnh cng Zn, La vo vt liu. Vt liu tn ti hai loi tm axit: mnh v yu, tng ng vi nhit gii hp 188,4 v 557,3 oC. 3. Thc hin phn ng este cho ha m b vi t l mol metanol/du = 18:1, hm lng xc tc 3 % .kl, nhit khong 60-65 oC th thi gian phn ng ko di trong khong 8 gi s thu c metyl este vi hiu sut tng i cao, t to nh. So snh xc tc ca MA vi MeONa, nhn thy phn ng dng xc tc MA hn so vi xc tc baz ng th MeONa nhng rt t to nh. 4. Phn tch thnh phn sn phm phn ng bng phng php sc k kh khi ph. Kt qu cho thy phn ng dng xc tc axit rn c chn lc cao, sn phm c thnh phn chnh l cc methyl este ca 9-Octadecenoic acid, Octadecanoic acid, 11-Hexadecenoic acid

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TI LIU THAM KHO

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