Nghiên cứu xúc tác trên cơ sở h ZSM5 ứng dụng cho công nghệ sản xuất xăng có chỉ số octan cao từ nguồn nguyên liệu naphtha

I H C QU C GIA TP.HCM TR NG I H C BÁCH KHOA - V MÃO NGHIÊN C U XÚC TÁC TRÊN C S H-ZSM5 NG D NG CHO CÔNG NGH S N XU T X NG CÓ CH S OCTAN CAO T NGU N NGUYÊN LI U NAPHTHA CHUYÊN NGÀNH: K THU T HÓA D U MÃ NGÀNH : 60 53 55 LU N V N TH C S TP H CHÍ MINH, tháng 12 n m 2013 I IH I H C QU C GIA TP H ng d n khoa h c: PGS TS Hu nh Quy n h cv ch m nh PGS.TS Nguy cv ch m nh TS Nguy n H cv Lu cb ov t ih 2014 nH m: cv c aH ng ch m b o v lu m L c PGS.TS Nguy TS Nguy n H PGS.TS Hu nh Quy n n c a Ch t ch H lu c s a ch a (n IH C I CH cl p Ch t ch H T T NAM H B g NHI M V LU H am 27/07/1987 K thu u MSHV: 11400176 I H-ZSM5 ng d ng cho s RON cao t ngu n s n xu u Naphtha II NHI M V - I DUNG: u t ng quan v ng, ch bi condensate t i Vi t Nam - T ng h p l a ch - T ng h - Kh t mang zeolite H-ZSM5 v -hexane T t mang - Kh - Kh xu ng c a nhi ph n ng ph n Mo,Cr/H-ZSM5 - Kh ng c a kh Mo,Cr/H-ZSM5 III IV V MV NG D N: NG D N PGS.TS HU NH QUY N 24 06 MV 12 PGS.TS HU NH QUY N CH NHI M B L c hi ng t t c nh ng k t qu ng tham kh ng k t qu nt H LU December 12, 2013 L PGS.TS Hu nh Quy n Nguy n Tu n L i t u, nh ng c ti c hi n lu ng d t ng c h Th c S y thu t i h c Qu ng u H i ng d b cho em nh ng ki n th c v a qua L i k ti ib nhi ng tr em th c hi n lu H 12 H i c hi n lu LU December 12, 2013 T Vi n, s condensate c i Vi t Nam t g n 500,000 t u ch ch y u t ti n d c hi n t i c Nh m b o v n c m s n xu ng, m t l n ch th , th ul condensate v ng ch bi n Nh t i Vi t Nam bu c ph n xu t c m bi n m ti p t c c nh d ng Hydrogen MUP M a lu t vi c kh hi u qu c t ng h n u naphtha theo d ng Hydrogen MUP T zeolite H-ZSM5 Cr s ct ml t theo nh ng t l X XRD, BET, TEM, t H-ZSM5 b ng ng kim lo i t u n ph m s t c u, mt c hi n ph n u - u qu th c c K t qu cho th y, vi c t H-ZSM5 i nh di m ic ng ho nh zeolite HSZM-5 S n ph s , sau th c hi n ph n ng v s n ph t ch s ng c a nhi nc u H-ZSM5 77 T l , n aromatic s n ph n 18.73% (ch a 2% benzene) Euro2 Hi u su t thu h i l ng nv i cao, kho ng 57.5% uc a h n n hi u su t thu h i s n ph c kh ii K t qu cho th y nhi t s LU December 12, 2013 n ph ch h t ng nhi ng tr u qu n ph n K t qu u c a lu ngu y kh n li nh c d u ch bi n condensate c nh t i Vi t Nam iii u LU December 12, 2013 ABSTRACT Viet Nam stores a large amount of condensate, the total consumption of condensate, which is produced by condensate-treating factories, reached upto 500,000 ton in 2009[3] Although they distributed large amount of fuel to the domestic market, but current technology of these factories only produces gasoline A83 (gasoline has 83 RON number) To protect the enviroment, a journey which was set to lower and get to stop producing and using low RON gasoline, typical is A83, was approved by the Prime Minister and will be effected in 1/1/2014 Little and small condensate-treating factories in Viet Nam must look for new suitable technology to continue exist And the aimed technology is increasing RON number without using Hydrogen for naphtha by selective aromatization mechanism technology MUP The aim of this thesis is to focus on synthesizing, investigating the effects of catalyst through process of increasing RON number without using Hydrogen for naphtha by selective aromatization mechanism From first H-ZSM5 zeolite, we will soak Mo and Cr into it, follow exactly chosen ratio The catalyst will be sent for XRD, BET, TEM, testing to determine the best concentration of Mo and Cr for the reaction Final testing step is doing the reaction with raw material is naphtha, using the optimal catalyst above Both raw material and the outlet product will be sent for GC-MC testing to see the effects of catalyst We found that, soaking 10%Mo and 3%Cr is not harm the H-ZSM5 zeolite, in the other hand, it helps the zeolite become stable, more active and increase the surface area of H-ZSM5 zeolite Raw material only has RON number around 69, but after doing the reaction in hours, the outlet product has RON number is 77 Beside that, aromatic content has increased from 2.28% up to 18.73% (only 2% of benzene) in total component of outlet products It can satisfy the standard of Euro2 The liquid recovery is 57.5% The catalyst after reacted can be re-generated iv LU December 12, 2013 Effect of temperature to gasoline production yields and its composition has been investigated, the research results showed that the more temperature increases, the more aromatic content and gas will be produced The best temperature is 3800C This study is only the first step of catalytic synthesis for increasing RON number without using Hydrogen for naphtha by selective aromatization mechanism technology It will be the potential way to solve Viet Nam condensate- v LU December 12, 2013 DANH M BI : K ho : Bi n 2010 kh 2025 p kh t mang Zeolite H-ZSM5 23 h ph n ng 24 : H th ng ph n ng c u H- c t m 30 :Ph XRD c Di nh 25 31 m 32 : M u ch p TEM c a H- 10Mo/H-ZSM5 (b) 33 Gi TPD-NH3 c a m Bi chuy 34 u su t thu h i l ng theo th i gian 35 - a s n ph m v 36 : Ph XRD c : Di 39 m 40 :M u ch p TEM c a H: Gi -ZSM5 (b) 41 TPD-NH3 c a m 41 : Bi u su t thu h i l ng theo th i gian 43 : Bi u su t thu h i l ng theo th i gian 44 : -parafin c a s n ph m v o nh m : Bi : Bi C; Vp = 18ml/h; mxt = 2g) 45 n ph m ph n ng 47 nc ut n ph m 49 n s n ph n ph m 50 n ng 51 : Ph XRD c a x n ng 51 vi LU PH L C 2.5 DI December 12, 2013 M U 10Mo1Cr 79 LU PH L C 2.6 DI December 12, 2013 M U 10Mo3Cr 80 LU PH L C 2.7 DI December 12, 2013 M U 10Mo5Cr 81 LU December 12, 2013 PH L C 3: PH XRD C PH L C 3.1 PH XRD M U 5Mo 82 LU PH L C 3.2 PH December 12, 2013 XRD M U 10Mo 83 LU PH L C 3.3 PH December 12, 2013 XRD M U 15Mo 84 LU PH L C 3.4 PH December 12, 2013 XRD M U 10Mo1Cr 85 LU PH L C 3.5 PH December 12, 2013 XRD M U 10Mo3Cr 86 LU PH L C 3.6 PH December 12, 2013 XRD M U 10Mo5Cr 87 LU PH L C 4: K T QU PH L C 4.1 December 12, 2013 N U NAPHTHA 88 LU December 12, 2013 PH L C 4.2 S N PH M T I M U M380,2 89 LU December 12, 2013 PH L C 4.3 S N PH M T I M U M450,2 90 LU December 12, 2013 PH L C 4.4 S N PH M T I M U M500,2 91 LU December 12, 2013 PH L C 4.5 S N PH M T I M U M380,1 92 LU December 12, 2013 PH L C 4.6 S N PH M T I M U M380,3 93 ... ph i ph ch n th i [18] D c v nh zeolite H- ZSM5 [7-9], zeolite H- ZSM5 u n ch t mang o ph n ng th a v t li u g - t c ng nghi p [7] ho ng nghi p [9] cho th y, h ch n l i cao cho ph n ho c c methane... -ZSM gi -ZSM5 K t qu cho th y , ph n S n ph m c p ch H- ZSM5 [15] ti tr u m i quan h gi a chuy r H- ZSM5 t nt i th h MoO3 n ng dehydroaromatic H- ZSM5 v t qu u cho th i d ng [Mo5O12]6+ H- ZSM5 t n... ng h ng h p ch nhi c bi c ng d ng x n Trong nhi uv c bi c cho ph n ng c p cho nh ng chuy ch n l ng r l Si/Al l c bi acid -hexane, H- ZSM5 c c a h th ng mao qu n ch carbon t C4-C10 v n -ZSM5 p cho