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MC LC DANH MC CC T VIT TT DANH MC BNG BIU DANH MC HèNH LI M U CHNG TNG QUAN V GTBE 1.1 GII THIU 1.2 TNH CHT VT Lí V HểA HC CA GTBE 1.2.1 TNH CHT VT Lí 1.2.2 TNH CHT HểA HC 1.3 NG DNG CA GTBE 10 1.4 CC PHNG PHP SN XUT GTBE 11 1.4.1 PHNG PHP ETE HểA GLYCEROL 12 1.4.2 PHNG PHP ALKYL HểA VI TC NHN OLEFIN 13 1.5 NGUYấN LIU SN XUT GTBE THEO PHNG PHP ETE HểA 15 1.5.1 GLYCEROL 15 1.5.1.1 TNH CHT VT Lí CA GLYCEROL 15 1.5.1.2 TNH CHT HểA HC CA GLYCEROL 16 1.5.1.3 CC NG DNG CA GLYCEROL 17 1.5.1.4 CC NGUN CUNG CP GLYCEROL CHO TNG HP GTBE 18 1.5.2 TBA 19 1.5.2.1 TNH CHT VT Lí 19 1.5.2.2 TNH CHT HểA HC 20 1.5.2.3 NG DNG CA TBA 21 1.6 XC TC CHO TNG HP GTBE 21 1.6.1 CC LOI XC TC C S DNG 21 1.6.1.1 P-TOLUEN SUNFONIC AXIT 21 1.6.1.2 ZEOLIT BETA 21 1.6.1.3 HT NHA TRAO I ION (AMBERLYST) 23 1.6.1.4 SO SNH, NH GI V LA CHN XC TC 24 1.7 CC YU T NH HNG N QU TRèNH 26 1.7.1 1.7.2 1.7.3 1.7.4 1.7.5 1.7.6 HM LNG XC TC 26 THI GIAN PHN NG 27 T L NGUYấN LIU 27 NHIT 28 P SUT 29 TC KHUY TRN 31 Trang 1.8 MC TIấU NGHIấN CU CA TI 31 CHNG 2: THC NGHIM 32 2.1 HểA CHT, THIT B V DNG C 32 2.1.1 HểA CHT 32 2.1.2 THIT B V DNG C 32 2.2 QUY TRèNH TNG HP GTBE 32 2.2.1 QUY TRèNH THC HIN S DNG XC TC AMBERLYST 36 33 2.2.2 QUY TRèNH THC HIN S DNG XC TC ZEOLIT BETA 35 2.3 PHNG PHP PHN TCH NH GI SN PHM GTBE 36 2.3.1 CHUN B MU PHN TCH 36 2.3.1.1 MU NGUYấN LIU 36 2.3.1.2 MU SN PHM 36 2.3.2 THễNG S GC-MS 37 2.4 QUY TRèNH TNH TON 38 2.4.1 XC NH CHUYN HểA 38 2.4.2 XC NH CHN LC SN PHM ME TRONG SN PHM 38 CHNG 3: KT QU V THO LUN 41 3.1 NGHIấN CU CC YU T NH HNG N QU TRèNH TNG HP GTBE TRấN XC TC AMBERLYST 36 M 41 3.1.1 NH HNG CA T L XC TC SO VI GLYCEROL 41 3.1.2 NH HNG CA THI GIAN PHN NG 45 3.1.3 NH HNG CA T L NGUYấN LIU 47 3.1.4 NH HNG CA NHIT 50 3.2 NGHIấN CU CC YU T NH HNG N QU TRèNH TNG HP GTBE TRấN XC TC ZEOLIT BETA 55 3.2.1 NH HNG CA NHIT 55 3.2.2 NH HNG CA T L NGUYấN LIU 59 3.2.3 NH HNG CA T L XC TC SO VI GLYCEROL 61 3.2.4 NH HNG CA THI GIAN PHN NG 64 KT LUN 67 TI LIU THAM KHO 68 Trang DANH MC CC T VIT TT GTBE Glycerol tert-butyl ete ME Glycerol mono-tert-butyl ete DE Glycerol di-tert-butyl ete TE Glycerol tri-tert-butyl ete MTBE Methyl tert-butyl ete ETBE Ethyl tert-butyl ete TAME Tertiary amyl methyl ete TBA tert-butyl ancol DGBE di-etylen Glycol mono-Butyl ete A15, 35, 36, 39 Amberlyst 15, 35, 36, 39 PTSA p-toluen sunfonic axit ppm Parts per million (1/1 000 000) RVP Reid vapor pressure ASTM American Society for Testing and Materials Trang DANH MC BNG BIU Bng 1.1: Tớnh cht ca cỏc ng phõn GTBE [2, 3, 4] Bng 1.2: Tớnh cht vt lý ca Glycerol 16 Bng 1.3: Tớnh cht k thut ca zeolit H- (ngun: zeolyst.com) .22 Bng 1.4: Tớnh cht ca mt s loi xỳc tỏc Amberlyst [10] 23 Bng 1.5: Hiu qu phn ng tng hp GTBE trờn cỏc loi xỳc tỏc [15] 24 Bng 1.6: Thụng s k thut ca xỳc tỏc Amberlyst 36-wet (ngun: Sigmaaldrich.com) 25 Bng 2.1: Thụng s sc ký GC-MS s dng quỏ trỡnh phõn tớch .37 Bng 3.1: Hiu qu ca phn ng ete húa glycerol bi TBA vi cỏc hm lng xỳc tỏc khỏc 41 Bng 3.2: nh hng ca t l nguyờn liu n chuyn húa v chn lc sn phm 47 Bng 3.3: nh hng ca nhit n chuyn húa v chn lc sn phm 51 Bng 3.4: nh hng ca nhit n chuyn húa v chn lc sn phm 55 Bng 3.5: nh hng ca t l nguyờn liu n chuyn húa v chn lc sn phm .59 Bng 3.6: nh hng ca t l xỳc tỏc n chuyn húa v chn lc sn phm 61 Bng 3.7: nh hng ca thi gian n chuyn húa v chn lc sn phm .64 Trang DANH MC HèNH Hỡnh 1.1: Phn ng tng hp GTBE t glycerol v iso-butylen Hỡnh 1.2: Phõn t Glycerol 15 Hỡnh 1.3: Phõn t TBA .20 Hỡnh 1.4: BET ca xỳc tỏc Zeolit H thng mi .22 Hỡnh 1.5: nh hng ca hm lng xỳc tỏc n chuyn húa glycerol, xỳc tỏc A15, ỏp sut 0,1 MPa, TBA/Gly = 4, thi gian 6h [11] .26 Hỡnh 1.6: nh hng ca thi gian phn ng n chuyn húa glycerol, xỳc tỏc A15, P=0,1MPa, TBA/Gly=4, thi gian 6h [11] 27 Hỡnh 1.7: chuyn húa theo glycerol ph thuc t l nguyờn liu, xỳc tỏc A15, nhit 80oC [10] 28 Hỡnh 1.8: nh hng ca nhit n chuyn húa Glycerol, xỳc tỏc A15, TBA/Gly=4/1, thi gian phn ng 6h [10] 28 Hỡnh 1.9: S phõn b sn phm ca quỏ trỡnh tng hp GTBE trờn xỳc tỏc A15, P = 0,1MPa, TBA/Gly =4, thi gian 6h [9] 29 Hỡnh 1.10: chuyn húa v chn lc sn phm cỏc nhit khỏc nhau, xỳc tỏc A15, nhit 70oC, tc khuy 1200 rpm [11] 30 Hỡnh 1.11: th biu th quan h gia nhit v ỏp sut hi TBA [14] 30 Hỡnh 2.1: S quy trỡnh tng hp GTBE [23] 33 Hỡnh 2.2: S h thng phn ng .34 Hỡnh 2.3: ng chun nng ca ME 39 Hỡnh 3.1: th biu din nh hng ca hm lng xỳc tỏc n phn ng tng hp GTBE .42 Hỡnh 3.2: Sc ký ca sn phm GTBE thu c sau hũa tan dung mụi ng vi hm lng xỳc tỏc 2,5% 43 Hỡnh 3: Sc ký ca sn phm GTBE thu c sau hũa tan dung mụi ng vi hm lng xỳc tỏc 5% 44 Hỡnh 3.4: Sc ký ca sn phm GTBE thu c sau hũa tan dung mụi ng vi hm lng xỳc tỏc 7,5% 44 Hỡnh 3.5: th biu din nh hng ca thi gian phn ng n quỏ trỡnh tng hp GTBE 45 Hỡnh 3.6: Sc ký ca sn phm GTBE thu c sau hũa tan dung mụi ng vi thi gian phn ng l 2h 46 Hỡnh 3.7: Sc ký ca sn phm GTBE thu c sau hũa tan dung mụi ng vi thi gian phn ng l 4h 46 Hỡnh 3.8: Sc ký ca sn phm GTBE thu c sau hũa tan dung mụi ng vi thi gian phn ng l 6h 47 Hỡnh 3.9: th biu din nh hng ca t l nguyờn liu .48 Hỡnh 3.10: Sc ký ca sn phm GTBE thu c sau hũa tan dung mụi ng vi t l nguyờn liu TBA/Gly l 2/1 49 Hỡnh 3.11: Sc ký ca sn phm GTBE thu c sau hũa tan dung mụi ng vi t l nguyờn liu TBA/Gly l 4/1 49 Trang Hỡnh 3.12: Sc ký ca sn phm GTBE thu c sau hũa tan dung mụi ng vi t l nguyờn liu TBA/Gly l 5/1 50 Hỡnh 3.13: Sc ký ca sn phm GTBE thu c sau hũa tan dung mụi ng vi t l nguyờn liu TBA/Gly l 6/1 50 Hỡnh 3.14: th biu din nh hng ca nhit n phn ng tng hp GTBE 52 Hỡnh 3.15: Sc ký ca sn phm GTBE thu c sau hũa tan dung mụi ng vi iu kin nhit 50oC 52 Hỡnh 3.16: Sc ký ca sn phm GTBE thu c sau hũa tan dung mụi ng vi iu kin nhit 60oC 53 Hỡnh 3.17: Sc ký ca sn phm GTBE thu c sau hũa tan dung mụi ng vi iu kin nhit 70oC 53 Hỡnh 3.18: Sc ký ca sn phm GTBE thu c sau hũa tan dung mụi ng vi iu kin nhit 75oC 54 Hỡnh 3.19: Sc ký ca sn phm GTBE thu c sau hũa tan dung mụi ng vi iu kin nhit 80oC 54 Hỡnh 3.20: th biu din nh hng ca nhit n chuyn húa glycerol 56 Hỡnh 3.21: Sc ký ca sn phm GTBE thu c sau phn ng ó hũa tan dung mụi ng vi nhit phn ng 60oC 56 Hỡnh 3.22: Sc ký ca sn phm GTBE thu c sau phn ng ó hũa tan dung mụi ng vi nhit phn ng 75oC 57 Hỡnh 3.23: Sc ký ca sn phm GTBE thu c sau phn ng ó hũa tan dung mụi ng vi nhit phn ng 90oC 57 Hỡnh 3.24: Sc ký ca sn phm GTBE thu c sau phn ng ó hũa tan dung mụi ng vi nhit phn ng 105oC .58 Hỡnh 3.25: Sc ký ca sn phm GTBE thu c sau phn ng ó hũa tan dung mụi ng vi nhit phn ng 120oC .58 Hỡnh 3.26: th biu din nh hng ca t l nguyờn liu n chuyn húa Glycerol trờn xỳc tỏc Zeolit beta 60 Hỡnh 3.27: Sc ký ca sn phm GTBE thu c sau phn ng ó hũa tan dung mụi ng vi t l nguyờn liu 3/1 60 Hỡnh 3.28: Sc ký ca sn phm GTBE thu c sau phn ng ó hũa tan dung mụi ng vi t l nguyờn liu 4/1 61 Hỡnh 3.29: th biu din nh hng ca t l xỳc tỏc n chuyn húa glycerol trờn xỳc tỏc zeolit beta 62 Hỡnh 3.30 Sc ký ca sn phm thu GTBE c sau phm ng ó hũa tan dung mụi ng vi t l 5% xỳc tỏc .63 Hỡnh 3.31 Sc ký ca sn phm GTBE thu c sau phm ng ó hũa tan dung mụi ng vi t l 7,5% xỳc tỏc 64 Hỡnh 3.32: th biu din nh hng ca thi gian n chuyn húa glycerol trờn xỳc tỏc zeolit beta 65 Hỡnh 3.33: Sc ký ca sn phm GTBE thu c sau phn ng ó hũa tan dung mụi ng vi thi gian phn ng 4h 66 Hỡnh 3.34: Sc ký ca sn phm GTBE thu c sau phn ng ó hũa tan dung mụi ng vi thi gian phn ng 6h 66 Trang LI M U Hin nhu cu s dng cỏc loi nhiờn liu ngy cng nhiu, kộo theo ú l cỏc v mụi trng v phỏt thi t ng c Khi ng c hot ng, nhiờn liu c t chỏy s thi mt lng ln cỏc cht c hi nh hng n sc khe ngi v c mụi trng sinh thỏi Vỡ vy, cỏc loi nhiờn liu khụng nhng phi m bo c cỏc yờu cu liờn quan n quỏ trỡnh chỏy ng c, m cũn phi m bo cỏc yờu cu nghiờm ngt v mụi trng ỏp ng nhu cu nõng cao cht lng nhiờn liu, mt nhng bin phỏp l s dng ph gia cha oxy, ú cú glyxerin tert-butyl ete (glycerol tert-butyl ether, GTBE) Khi pha GTBE vo nhiờn liu s thỳc y quỏ trỡnh chỏy tt hn, hon ton hn, ci thin c s phỏt thi cng nh hiu qu lm vic ca nhiờn liu Bờn cnh ú, mt nhng ngun nguyờn liu tng hp GTBE, ú l glycerol, ph phm ca quỏ trỡnh sn xut biodiesel Trong thi gian ti, Vit Nam, nhiờn liu khoỏng cn kit dn v vic s dng biodiesel c ng dng rng rói thc t, vic tn thu ngun glycerol ph phm ny sn xut cỏc sn phm hu ớch phc v cuc sng s tr nờn rt cn thit, lm tng hiu qu kinh t quỏ trỡnh sn xut biodiesel Quỏ trỡnh tng hp GTBE da trờn c s phn ng ete húa gia glycerol vi tert-butyl ancol (TBA) hoc iso-butylen (IB), c xỳc tin bi cỏc xỳc tỏc axit Sn phm to thnh l hn hp cỏc ng phõn mono-, di-, tri-GTBE Mi loi ng phõn li cú giỏ tr ng dng lm ph gia cho cỏc loi nhiờn liu khỏc Do ú, mc tiờu ca lun ny l nghiờn cu cỏc yu t nh hng v tỡm iu kin thớch hp cho quỏ trỡnh tng hp glycerol tert-butyl ether vi s cú mt ca xỳc tỏc Zeolit beta v Amberlyst, hng ti phỏt trin ng dng ca glycerol, ph phm ca sn xut biodiesel ch to cỏc sn phm cú giỏ tr nh ph gia nhiờn liu xng, diesel hay biodiesel Trang CHNG TNG QUAN V GTBE 1.1 GII THIU Glycerol tert-butyl ete (GTBE) l hn hp ca cỏc ete mono-tert-butyl ete (ME), di-tert-butyl ete (DE) v tri-tert-butyl ete (TE) Theo bỏo cỏo ca Malinavskii v Vedenskii cho bit, GTBE ó c tng hp c vo nm 1953 [1] bng cỏch gia nhit hn hp glycerol v TBA vi s cú mt ca 1% H2SO4 Trong bng sỏng ch s 5.476.971 ca M, GTBE c sn xut bi mt phn ng hai giai on ca glycerol v isobutylen vi s cú mt ca cht xỳc tỏc axit [2] Cỏc nghiờn cu trờn th gii ó cho thy GTBE cú th c s dng lm ph gia cho diesel v xng nhiờn liu Hỡnh 1.1: Phn ng tng hp GTBE t glycerol v iso-butylen 1.2 TNH CHT VT Lí V HểA HC CA GTBE 1.2.1 TNH CHT VT Lí GTBE l cht lng khụng mu, cú kh nng hũa tan tt nht cỏc dung mụi hu c, nhit chp chỏy cao, ỏi lc thp vi nc, tr s Octan >110 Do vy, trn vo nhiờn liu thỡ GTBE lm tng tr s Octan cho nhiờn liu xng, nõng cao kh nng chỏy sch ca nhiờn liu, ng thi GTBE cũn rt d phõn hy sinh hc nu b phỏt tỏn mụi trng Trong ba ng phõn thỡ ME cú kh nng hũa tan nc thp nht Trang Bng 1.1: Tớnh cht ca cỏc ng phõn GTBE [2, 3, 4] Tớnh cht ME DE TE Nhit sụi (oC) 256,61 240,6 248,5 Khi lng phõn t (g/mol) 148,2 204 260 Khi lng riờng (g/ml) 1,0a a Ti 20oC (ngun: MSDS-433845, Sigmaaldrich.com) Cha cú s liu 1.2.2 TNH CHT HểA HC GTBE khỏ n nh di iu kin axit yu, mụi trng kim hoc trung tớnh Do cỏc nguyờn t oxy cỏc phn t GTBE cú mt cp in t khụng chia v cỏc nguyờn t gc C(CH3)3 cú hiu ng cm ng dng (+I) ó to cho GTBE (ete) mang tớnh cht c trng ca mt baz Ngoi ra, cỏc phõn t cũn nhúm (OH) cha phn ng ht nờn cỏc phõn t ny cũn mang y tớnh cht ca mt ancol n chc v a chc [5] - Tỏc dng vi cỏc axit vụ c mnh nh HCl, H2SO4 Sn phm ca phn ng l to mui (hp cht oxoni) Hp cht Oxoni + H2O GTBE + HO-SO3H - Phn ng vi HI: GTBE phn ng c vi HI to cỏc sn phm khỏc ph thuc vo nhit tin hnh phn ng - Phn ng vi oxy: nhit thp phn ng to cỏc hp cht peroxyt khụng bn, d gõy chỏy n; iu kin nhit cao GTBE chỏy oxy theo phn ng chỏy T thp hp cht peroxyt; GTBE + O2 GTBE + O2 CO2 + H2O; Trang - Phn ng halogen húa vi clo, brom: cỏc gc hydrocacbon H-C cũn cú kh nng tham gia phn ng halogen húa GTBE + Halogen (Cl2, Br2) - hp cht halogenua Ngoi ra, cỏc phõn t mono-tert-butyl ete v di-tert-butyl ete ca glycerol cũn cú cha nhúm OH cha phn ng ht nờn nú cú kh nng phn ng tip vi cỏc olefin hoc cỏc ancol to cỏc di-tert-butyl ete v tri-tert-butyl ete ca glycerol mono-ete + olefin (ancol) di-ete di-ete + olefin (ancol) tri-ete Quỏ trỡnh phn ng to hn hp sn phm GTBE din rt phc v khú kim soỏt thu c cỏc sn phm cú giỏ tr cng nh kh nng ng dng cao thỡ ũi hi cỏc nh cụng ngh phi tỡm cỏc gii phỏp v iu kin cụng ngh (nhit , ỏp sut) cng nh xỳc tỏc cú th thu c hiu sut sn phm tt nht 1.3 NG DNG CA GTBE Hin nay, du diesel sinh hc (biodiesel) c sn xut nh quỏ trỡnh trao i este ca triglyxerit vi ancol nh metanol hoc etanol l mt cụng ngh c la chn rt ph bin Quỏ trỡnh c s dng vi xỳc tỏc trờn c s l cỏc baz to thnh mt hn hp ca metyl este ca axit bộo v cú th s dng lm nhiờn liu ng c Quỏ trỡnh cũn to glycerol c coi nh l mt sn phm ph, vỡ glycerol khụng tng thớch vi nhiờn liu sinh hc hoc vi cỏc nhiờn liu khỏc vy nú phi c tỏch v s dng vi mc ớch khỏc V mt nhng hng mi cho glycerol l quỏ trỡnh sn xut GTBE tr li cho nhiờn liu di hỡnh thc l mt ete tng thớch hn glycerol, ú quỏ trỡnh ó b sung thờm mt lng nhiờn liu tỏi to cho nhiờn liu sinh hc [6, 7, 8] Cỏc ete truyn thng c thờm vo nhiờn liu ci thin quỏ trỡnh t chỏy nhiờn liu v gim thiu phỏt thi cỏc cht ụ nhim mụi trng khụng khớ, v ete Trang 10 Hỡnh 3.22: Sc ký ca sn phm GTBE thu c sau phn ng ó hũa tan dung mụi ng vi nhit phn ng 75oC Hỡnh 3.23: Sc ký ca sn phm GTBE thu c sau phn ng ó hũa tan dung mụi ng vi nhit phn ng 90oC Trang 57 Hỡnh 3.24: Sc ký ca sn phm GTBE thu c sau phn ng ó hũa tan dung mụi ng vi nhit phn ng 105oC Hỡnh 3.25: Sc ký ca sn phm GTBE thu c sau phn ng ó hũa tan dung mụi ng vi nhit phn ng 120oC Trang 58 3.2.2 NH HNG CA T L NGUYấN LIU nh hng ca t l nguyờn liu TBA/Gly n quỏ trỡnh ete húa glycerol c nghiờn cu di t 3/1 n 5/1 vi cỏc iu kin phn ng khỏc c trỡ : - Nhit : 120oC; - T l lng xỳc tỏc: 7,5 % wt theo glycerol; - Thi gian phn ng: 6h; - p sut: 10 atm; - Tc khuy: 1200 vũng/phỳt nh hng ca t l nguyờn liu TBA/Gly c nghiờn cu khong 3/1ữ5/1 Kt qu c a bng 3.5 Bng 3.5: nh hng ca t l nguyờn liu n chuyn húa v chn lc sn phm T l TBA/ chuyn húa chn lc sn phm (%) Gly theo glycerol (%) ME DE TE 3/1 42,66 33,82 22,98 4,38 4/1 56,12 30,53 23,20 4,50 5/1 61,58 27,96 21,40 4,05 T kt qu bng 3.5 cú th thy, tng t l TBA/Gly thỡ chuyn húa ca phn ng tng lờn, c th t l 3/1 chuyn húa t 42,66 (%); 4/1 t 56,12 (%) tng lờn 1,32 ln (13,46 (%)) so vi t l 3/1 Tip tc tng t l lờn 5/1 thỡ chuyn húa t 61,58 (%) ch tng 1,09 ln (5,46 (%)) so vi t l 4/1 ( th hỡnh 3.26) Trang 59 Hỡnh 3.26: th biu din nh hng ca t l nguyờn liu n chuyn húa Glycerol trờn xỳc tỏc Zeolit beta Nh vy, t l mol ca TBA/Gly cng ln thỡ chuyn húa ca phn ng cng ln Tuy nhiờn, s chờnh lch gia 4/1 v 5/1 khụng nhiu Do ú, m bo tớnh kinh t ca quỏ trỡnh, t l TBA/Gly =4/1 s c la chn cho cỏc nghiờn cu tip theo Sc ký sn phm thu c sau quỏ trỡnh phn ng cỏc t l nguyờn liu khỏc c a trờn cỏc hỡnh 3.27 v 3.28 Hỡnh 3.27: Sc ký ca sn phm GTBE thu c sau phn ng ó hũa tan dung mụi ng vi t l nguyờn liu 3/1 Trang 60 Hỡnh 3.28: Sc ký ca sn phm GTBE thu c sau phn ng ó hũa tan dung mụi ng vi t l nguyờn liu 4/1 3.2.3 NH HNG CA T L XC TC SO VI GLYCEROL nh hng ca t l xỳc tỏc so vi glycerol n quỏ trỡnh ete húa glycerol c nghiờn cu khong t 5-10%, vi cỏc iu kin phn ng khỏc c trỡ : - Nhit : 120oC; - T l nguyờn liu TBA/Gly (theo phn mol): 4/1; - Thi gian phn ng: 6h; - p sut: 10 atm; - Tc khuy: 1200 vũng/phỳt Bng 3.6: nh hng ca t l xỳc tỏc n chuyn húa v chn lc sn phm T l xỳc tỏc chuyn húa chn lc sn phm (%) theo Gly(% wt) theo glycerol (%) ME DE TE 5,0 46,66 34,16 24,62 4,71 7,5 56,12 30,53 23,20 4,50 10,0 54,84 29,86 22,38 4,32 Trang 61 T bng 3.6, cú th thy, s dng t l xỳc tỏc 7,5(%) wt (tớnh theo lng) so vi glycerol thỡ chuyn húa ca phn ng cao nht v t 56,12(%) t l xỳc tỏc 5,0(%) wt chuyn húa ca phn ng ch t 46,66(%) thp hn 9,46(%) so vi t l xỳc tỏc 7,5(%) wt; ng thi t l 10(%) wt thỡ chuyn húa ca phn ng gim xung cũn 54,84% (thp hn 1,28% so vi t l 7,5(%) wt) ( th hỡnh 3.29) Hỡnh 3.29: th biu din nh hng ca t l xỳc tỏc n chuyn húa glycerol trờn xỳc tỏc zeolit beta iu ny cú th gii thớch nh sau: t l xỳc tỏc 5,0 (%) wt: Do lng TBA a vo phn ng gp ln glycerol (tớnh theo phn mol), nờn t l xỳc tỏc 5,0 (%) wt thỡ lng ion H+ cha phự hp tn cụng vo nhúm hydroxyl (OH) loi phõn t nc v hỡnh thnh lng cation carboni [(CH 3)3C+] nhiu nht dn n chuyn húa ca phn ng cha cao t l xỳc tỏc 10,0 (%) wt: Khi tng t l xỳc tỏc lờn 10,0 (%) wt thỡ chuyn húa gim l nu s dng lng xỳc tỏc quỏ nhiu thỡ H+ cũn xỳc tin cho quỏ trỡnh loi nc ca TBA hỡnh thnh nờn sn phm iso-butylene nh sau: Trang 62 Ngoi ra, phn ng thc hin nhit 120C, ỏp sut 10 atm, d dng thỳc y cho quỏ trỡnh oligome húa iso-butylene thnh C8 Chớnh sn phm oligome húa ny l tỏc nhõn lm th ng húa xỳc tỏc, tc l lm hot tớnh ca xỳc tỏc gim xung dn n chuyn húa ca phn ng gim xung [20] Do ú, t l xỳc tỏc zeolit beta/glycerol thớch hp cho quỏ trỡnh ete húa glycerol l 7,5 (%) wt iu kin ny s c s dng cho cỏc nghiờn cu tip theo Sc ký sn phm thu c sau quỏ trỡnh phn ng cỏc t l xỳc tỏc khỏc c a trờn cỏc hỡnh 3.30 v 3.31 Hỡnh 3.30 Sc ký ca sn phm thu GTBE c sau phm ng ó hũa tan dung mụi ng vi t l 5% xỳc tỏc Trang 63 Hỡnh 3.31 Sc ký ca sn phm GTBE thu c sau phm ng ó hũa tan dung mụi ng vi t l 7,5% xỳc tỏc 3.2.4 NH HNG CA THI GIAN PHN NG nh hng ca thi gian phn ng n quỏ trỡnh ete húa glycerol c nghiờn cu khong t n gi vi cỏc iu kin phn ng khỏc c trỡ : - Nhit : 120oC; - T l nguyờn liu TBA/Gly ( theo phn mol): 4/1; - T l lng xỳc tỏc: 7,5 % wt theo glycerol; - p sut: 10 atm; - Tc khuy: 1200 vũng/phỳt Bng 3.7: nh hng ca thi gian n chuyn húa v chn lc sn phm Thi gian chuyn húa theo phn ng (h) glycerol (%) chn lc sn phm (%) ME DE TE 53,62 29,67 22,29 4,33 56,12 30,53 23,20 4,50 55,19 29,57 22,06 4,28 Trang 64 T kt qu bng 3.7, cú th thy, tin hnh phn ng (h) thỡ chuyn húa t 53,62 (%); (h) chuyn húa tng lờn 56,12 (%) (tng 2,5 (%) so vi (h)); tip tc tng thi gian phn ng lờn 8(h) thỡ chuyn húa lỳc ny l 55,19 (%) (gim 0,93 (%) so vi 6(h)) Nh vy, chuyn húa ca phn ng thay i khụng ỏng k thi gian phn ng thay i ( th hỡnh 3.32) Hỡnh 3.32: th biu din nh hng ca thi gian n chuyn húa glycerol trờn xỳc tỏc zeolit beta Khi tin hnh phn ng (h) iu kin nhit 120C, ỏp sut 10 atm, chuyn húa gim l iu kin ny nu tng thi gian phn ng thỡ quỏ trỡnh loi nc TBA thnh iso-butylene v quỏ trỡnh polymer húa iso-butylene thnh polymer xy lm gim hot tớnh xỳc tỏc cho phn ng chớnh to GTBE Do ú, thi gian thớch hp tin hnh phn ng ether húa glycerol v TBA trờn xỳc tỏc zeolit beta l gi Sc ký sn phm thu c sau quỏ trỡnh phn ng sau cỏc thi gian phn ng khỏc c a trờn cỏc hỡnh 3.33 v 3.34 Trang 65 Hỡnh 3.33: Sc ký ca sn phm GTBE thu c sau phn ng ó hũa tan dung mụi ng vi thi gian phn ng 4h Hỡnh 3.34: Sc ký ca sn phm GTBE thu c sau phn ng ó hũa tan dung mụi ng vi thi gian phn ng 6h Trang 66 KT LUN ó xỏc nh c iu kin thớch hp cho quỏ trỡnh tng hp GTBE s dng xỳc tỏc Amberlyst 36 m l nhit 70oC, t l nguyờn liu TBA/glycerol bng 4/1, hm lng xỳc tỏc 7,5% lng glycerol v thi gian phn ng l 6h iu kin ny, chuyn húa glycerol cao nht l 50,76%, chn lc mono GTBE l 89,09%, t hiu sut tng hp ng phõn ME l 45,29% ó xỏc nh c iu kin thớch hp cho quỏ trỡnh tng hp GTBE s dng xỳc tỏc Zeolit beta l nhit 120oC, t l nguyờn liu TBA/glycerol bng 4/1, hm lng xỳc tỏc 7,5% lng glycerol v thi gian phn ng l 6h iu kin ny, chuyn húa ca glycerol t c l 56,12%, chn lc mono GTBE l 30,53%, t hiu sut tng hp ng phõn ME l 17,1% Gia hai loi xỳc tỏc, vic s dng Amberlyst 36 cho phộp tin hnh phn ng iu kin nhit thp hn (70C), so vi Zeolit beta (120C), ng thi hiu sut to sn phm ME cao hn nhiu Do vy, vi mc ớch ca quỏ trỡnh tng hp GTBE l sn xut ME lm ph gia cho xng thỡ s dng xỳc tỏc Amberlyst 36 s cho hiu qu tt hn Tuy nhiờn, cn cú cỏc nghiờn cu tip theo nõng cao hiu sut to ME trờn xỳc tỏc Amberlyst 36 Bờn cnh ú, nguyờn liu cha phn ng ht (vỡ dựng d tertbutyl ancol) cú th thu hi v tỏi s dng cho cỏc phn ng tip theo nh quỏ trỡnh chng ct phõn on iu kin chõn khụng Do ú, tng hiu qu kinh t ca quỏ trỡnh sn xut ph gia GTBE cho nhiờn liu, song hnh vi vic nghiờn cu tinh ch glycerol thi t quỏ 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Engineering Chemistry Research, April, 2015 Trang 71 ... tert- butyl ete ME Glycerol mono -tert- butyl ete DE Glycerol di -tert- butyl ete TE Glycerol tri -tert- butyl ete MTBE Methyl tert- butyl ete ETBE Ethyl tert- butyl ete TAME Tertiary amyl methyl ete TBA tert- butyl. .. CHƢƠNG TỔNG QUAN VỀ GTBE 1.1 GIỚI THIỆU Glycerol tert- butyl ete (GTBE) hỗn hợp ete mono -tert- butyl ete (ME), di -tert- butyl ete (DE) tri -tert- butyl ete (TE) Theo báo cáo Malinavskii Vedenskii cho. .. biến tính etanol 1.6 XÚC TÁC CHO TỔNG HỢP GTBE 1.6.1 CÁC LOẠI XÚC TÁC ĐƢỢC SỬ DỤNG GTBE sản phẩm trình ete hóa, xúc tác sử dụng cho phản ứng phải có tính axit Một số xúc tác axit kể đến nhƣ: