Nghiên cứu tổng hợp xúc tác với pha hoạt tính chứa co, ni, mo trên chất mang al2o3 cho quá trình hydro deoxy hóa (HDO) guaiacol (2 methoxy phenol)

TR CAO MANG Al2O3 DEOXY (2-METHOXY PHENOL) CBHD : GS TSKH : : MSHV : 11406065 10/2013 I i h c n Ch bi n D ng d n khoa h c : mL c ch m nh ch m nh Lu c b o v t i h nH i m: cv c aH ng ch m b o v lu n c a Ch t ch H ng Khoa qu c s a ch a (n CH T CH H NG I H C QU C GIA TP.HCM IH C I CH c l p - T - H T NAM NHI M V LU H 26-11-1988 K thu u t ng h ch t mang Al2O3 methoxy phenol) MSHV: 11406065 TP.HCM : 605355 u i pha ho - NHI M V I DUNG: L m b o h th ng ph n PVPro (VPI) s d 50ml/m i di n cho bio-oil) u, t ng h ch u ki n ho p Kh n ng HDO guaiacol T chuy t o hydrocarbon t t t cao t i t -Al2O3, l a ch n l c MV : MV NG D N: ML C h Khoa TP.HCM NG D N CH NHI M B (H (H (H O L IC il ic c, t n ng d n, ch nh s Lu mL c sung nhi u ki n th t Nghi p c bi u sinh h c om u ki n thu n l t lu c bi t em xin g i l i c ,g n Th c t th thu th ab ch bi n d c bi ,t cho em su t th i gian th c hi n lu u ki n thu n l i Em xin g i l i c Nguy n th y d t c xin b o v lu em Xin g i l i c n c hi M l c vi n u, tham kh c nghi m, i nh ng thi cho em Cu il c kh nt tc H i h ch TP H 15 lu 10 ABSTRACT For the recent decades processes of biomass conversion into hydrocarbon fuels has been attracting much attention due to decreasing of crude-oil reserves, and increased environmental concerns Fast pyrolysis technology is commonly used for the biomass conversion into liquid products, referred to bio-oil The direct use of bio-oil without any additional treatments is complicated due to high content of oxygen Nowadays, the fast pyrolysis products are usually upgraded via their catalyst hydrotreatment, also known as Hydrodeoxygenation (HDO) Catalytic hydrotreatment of bio-oil and its model compounds was studied extensively over conventional sulfided Ni(Mo) and Co(Mo) hydrotreatment catalysts supported on -alumina In this way, if bio-oils are added to traditional fuels, the whole feed could be hydrotreated (HDO and HDS) in the same process to feed into conventional units, the RFCC unit for instant, in the oil refinery plant The purpose of this thesis is to investigate the influence of pretreatment activation process, catalyst composition, catalyst promoters to the HDO catalyst performance This would be the foundation of the bio-oil catalytic upgrading via HDO process with a deoxygenation degree suitable for certain application In this study, a series of MoO3 -Al2O3 catalysts promoted by Ni and Co have been prepared by the impregnation method and tested for the hydro deoxygenation of The aim of the catalyst reduction before reaction on the catalytic activity has been solidated The mechanism of the formation of the products will be proposed The promoting effect of Ni is found to be better than Co at low temperature The catalyst 6%NiO30%MoO3 -Al2O3 has been shown to be the most potential in GUA conversion and 8%NiO-40%MoO3 -Al2O3 is found to be the best catalyst with highest deoxygenation selectivity T T LU p k tr l u hydrocacbon us nhu c u s c gia b i s suy gi m tr ng d d d ch cs d nhi chuy n ph m l ng (bio-oil) Bio- s d ng tr c ti p n u ch t ng oxy cao Hi n ph m nhi th lo d (HDO) HDO bio- ut c th c hi n r CoMo, NiMo d ch c ph i tr n v -alumina u truy n th ng , bio-oil cx ng th l cd i ng c m RFCC M a lu ng c n t nx i v i ho n p bio- im kh oxy ng d 3/ t ng h p b -Al2O3 v i ch c m Ho n ng HDO v ph n ng o C gi T m quan tr ng vi c kh c tham gia ph n xu t Kh c kh n c a Ni t minh i v i ho nh n ph n s n ho c chuy c lo i oxy 8%NiO-40%MoO3 -Al2O3 c c ch ng -30%MoO3 -Al2O3 L uc ab uc aB n ch bi n d u nghi p l c c hi n, xu nhu c u th c t c u u sinh h c (bio-oil) s n xu t t n sinh kh i c bi p d u sinh h c Vi t Nam nh m ph i tr n v c nc ad RFCC c c d u (NMLD) Dung Qu t N i dung c a lu ng th c hi c nghi m c ut t ng h nghi oil, t g a bio-oil l nh c n ng hydro -methoxy phenol) v i n pha ho l a ch n ph ng th c lo p bio- , gi i quy t v cs khan hi m ngu ng d n khoa h c c a GS.TSKH u m L c t qu , s li u lu b n c th c hi n M t s k t qu lu c ch p p ph s th c Tp H 15 10 lu -1- M CL C M C L C M CL H DANH M C B NG DANH M C CH VI T T T U 1.1 tv 1.2 M u 11 1.3 1.3.1 1.3.2 Ph u 11 ng n u 11 u 12 1.4 u 12 1.5 c ti n 13 1.5.1 c ti n 13 1.5.2 c 13 NG QUAN 14 2.1 T ng quan v d u sinh kh i (bio-oil) 14 HVTH: 2.1.1 14 2.1.2 p bio-oil 16 GVHD: GS.TSKH mL c -2- 2.2 21 2.2.1 T 21 2.2.2 23 2.2.3 T ng h 2.2.4 c 28 u ki n ph n ng: 30 2.2.5 Thi t b ph n ng 32 2.3 p bio-oil b 33 2.3.1 c 33 2.3.2 c 35 C NGHI M 37 3.1 3.2 Thi t b 3.2.1 c nghi m chung 37 t s d ng 37 t: 37 3.2.2 Thi t b , d ng c 38 3.3 ng th c nghi m 38 3.3.1 i di n cho bio-oil 38 3.3.2 40 3.4 ng h 41 3.5 43 3.5.1 3.5.2 3.5.3 HVTH: 43 nh c c 45 45 GVHD: GS.TSKH mL c -3- 3.5.4 nh h 3.6 46 ch n l c c 47 3.7 H th ng thi t b ph n ng 48 3.7.1 C m thi t b c 48 3.7.2 Thi t b ph n ng 48 3.7.3 H th u ch t cho h ph n ng 49 3.7.4 h th ng ph n ng 50 3.7.5 nh c a h th ng ph n ng cao 52 3.8 c hi n vi c kh 3.8.1 Chu n b 54 54 3.8.2 Ho 3.9 ng h ) 54 c hi n ph n u Guaiacol 55 n ph t qu 55 3.10 3.10.1 Thu s n ph m 55 3.10.2 n ph m 56 3.10.3 t qu 56 T QU O LU N 58 4.1 58 4.1.1 K t qu 4.1.2 K t qu 4.1.3 K t qu 4.2 Ho HVTH: 58 nh c c c 60 64 68 GVHD: GS.TSKH mL c - 76 - K T LU N NGH 5.1 K t lu n c nghi t qu i di n cho biong pha ho 10 40%, m t s k t lu Vi c kh ho n thi vi c chuy n a ch n ng lo i oxy T 6Co30MoAl, vi c kh chuy ut l a ch n lo a Mo chuy n v s oxy c kh s nl oxy y MoO2 c bi i Ni cho kh i Oxy t nhi th p (300 oC) C chuy n a Ni cho m HDO hai c a pha ho y Oxy guaiacol t cho vi c kh MoO3 di n d tinh th nt v im c HDO c chuy x p i Oxy nh nh chuy n uc ns ng m t i Oxy cao c tinh th pha MoO2 cao HVTH: GVHD: GS.TSKH mL c - 77 c a ph n xu u s n ph m c a ph n henol n ph m trung gian c li u GUA n n xu a ng t o s n ph bi i Co t o ch y u t o m ng l s n ph m t Ni bi ng ph n c lo i b Oxy, n cl a Co ch Oxy t ng ph n ng t l ng c t o m ng n xu t 5.2 Ki n ngh Do gi i h n c b ph n u k c v th t v t ch t (thi t ki n ngh nh ng th c nghi m m i d k t qu Bi ch t mang: ch Al2O3 cs d - u, ch ng b o c c [4] y, vi c bi n b Zr) s c i thi i Ce ho c c hi u qu c Kh c bi 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GS.TSKH mL c -7- DANH M C CH VI T T T GUA: Guaiacol (2- methoxyphenol) DOD: Deoxygenation degree (M ) nh b ng hydro) HDN ng hydro) HDO: Hydrodeox i oxy b ng hydro) CV: Control Valve (van m t chi u)... 2.2 T ng quan m t s h cs d [4] Co MoS2 /Al2O3 Co MoS2/ Al2O3 Bio-oil Bio-oil 4 P (bar) 200 300 Ni MoS2/ Al2O3 Ni MoS2 /Al2O3 Pd/C Bio-oil Bio-oil Bio-oil Bio-oil Guaiacol 0.5 4 200 85 200 140 80