Synthesis and catalytic performance of bimetallic NiMo-and NiW-ZSM-5/MCM-41 composites for production of liquid biofuels
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Abstract: This work presents a synthesis of bimetallic NiMo and NiW modified ZSM-5/MCM-41 composites and their heterogeneous catalytic conversion of crude palm oil (CPO) to biofuels. The ZSM-5/MCM-41 composites were synthesized through a self-assembly of cetyltrimethylammonium bromide (CTAB) surfactant with silica-alumina from ZSM-5 zeolite, prepared from natural kaolin by the hydrothermal technique. Subsequently, the synthesized composites were deposited with bimetallic NiMo and NiW by impregnation method. The obtained catalysts presented a micro-mesoporous structure, confirmed by XRD, SEM, TEM, EDX, NH3-TPD, XRF and N2 adsorption-desorption measurements. The results of CPO conversion demonstrate that the catalytic activity of the synthesized catalysts decreases in the series of NiMo-ZSM-5/MCM-41 > NiW-ZSM-5/MCM-41 > Ni-ZSM-5/MCM-41 > Mo-ZSM-5/MCM-41 > W-ZSM-5/MCM-41 > NiMo-ZSM-5 > NiW-ZSM-5 > ZSM-5/MCM-41 > ZSM-5 > MCM-41. It was found that the bimetallic NiMo-and NiW-ZSM-5/MCM-41 catalysts give higher yields of liquid hydrocarbons than other catalysts at a given conversion. Types of hydrocarbon in liquid products, identified by simulated distillation gas chromatography-flame ionization detector (SimDis GC-FID), are gasoline (150-200 ℃; C5-12), kerosene (250-300 ℃; C5-20) and diesel (350 ℃; C7-20). Moreover, the conversion of CPO to biofuel products using the NiMo-and NiW-ZSM-5/MCM-41 catalysts offers no statistically significant difference (P > 0.05) at 95% confidence level, evaluated by SPSS analysis.
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Figure 1 XRD patterns at (a) high diffraction angle and (b) low diffraction angle of ZSM-5/MCM-41 composite prepared at pH value 9.5 with different crystallization times
a: 12 h; b: 24 h; c: 48 h; d: 72 h
Figure 2 XRD patterns at (a) high diffraction angle and (b) low diffraction angle of ZSM-5/MCM-41 composite prepared with crystallization time of 48 h at different pH
a: 8.5; b: 9.5; c: 10.5; d: 11.5
Figure 3 XRD patterns of catalysts
a: ZSM-5; b: ZSM-5/MCM-41; c: NiMo-ZSM-5/ MCM-41; d: NiW-ZSM-5/MCM-41
Figure 4 SEM images of catalysts
(a): ZSM-5; (b): NiMo-ZSM-5; (c): NiW-ZSM-5; (d): ZSM-5/MCM-41; (e): NiMo-ZSM-5/MCM-41; (f): NiW-ZSM-5/MCM-41
Figure 5 TEM images and EDX spectra of catalysts
(a): ZSM-5/MCM-41; (b): NiMo-ZSM-5/MCM-41; (c): NiW-ZSM-5/MCM-41
Figure 6 N2 adsorption-desorption isotherms of catalysts
(a): MCM-41; (b): ZSM-5; (c): ZSM-5/MCM-41; (d): NiMo-ZSM-5/MCM-41; (e): NiW-ZSM-5/MCM-41
Figure 7 NH3-TPD profiles of catalysts
a: MCM-41; b: ZSM-5; c: ZSM-5/MCM-41; d: NiMo-ZSM-5/MCM-41; e: NiW-ZSM-5/MCM-41
Figure 8 Comparison on effect of different catalysts used on the production of liquid fuels
Figure 9 SimDis GC-FID chromatograms of products obtained after distillation in the conversion of CPO by using catalysts
(a): NiMo-ZSM-5/MCM-41 (gasoline); (b): NiW-ZSM-5/MCM-41 (gasoline); (c): NiMo-ZSM-5/MCM-41 (kerosene); (d): NiW-ZSM-5/MCM-41 (kerosene); (e): NiMo-ZSM-5/MCM-41 (diesel); (f): NiW-ZSM-5/MCM-41 (diesel)
Figure 10 Percentage area of carbon numbers of liquid products after distillation identified by SimDis GC-FID using various catalysts
a: NiMo-ZSM/MCM-41 (gasoline); b: NiW-ZSM-5/MCM-41 (gasoline); c: NiMo-ZSM-5/MCM-41 (kerosene); d: NiW-ZSM-5/MCM-41 (kerosene); e: NiMo-ZSM-5/MCM-41 (diesel); f: NiW-ZSM-5/MCM-41(diesel)
Table 1 Textural properties and metal content of catalysts
Table 2 NH3-TPD and activity parameters of catalysts
Table 3 Catalytic performance for the hydrocracking of CPO over different catalysts on simple distillation (n=3)
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[1] BOTAS J A, SERRANO D P, GARCIA A, VICENTE J, RAMOS R. Catalytic conversion of rapeseed oil into raw chemicals and fuels over Ni-and Mo-modified nanocrystalline ZSM-5 zeolite[J]. Catal Today, 2012, 195(1):59-70. doi: 10.1016/j.cattod.2012.04.061 [2] HANSHENG L, SHICHAO H, KE M, QIN W, QINGZE J, KENING S. Micro-mesoporous composite molecular sieves H-ZSM-5/MCM-41 for methanol dehydration to dimethyl ether:Effect of SiO2/Al2O3 ratio in H-ZSM-5[J]. Appl Catal A:Gen, 2013, 450(1):152-159. http://www.sciencedirect.com/science/article/pii/S0926860X1200662X [3] BOTAS J A, SERRANO D P, GARCIA A, RAMOS R. Catalytic conversion of rapeseed oil for the production of raw chemicals, fuels and carbon nanotubes over Ni-modified nanocrystalline and hierarchical ZSM-5[J]. Appl Catal B:Environ, 2014, 145(1):205-215. http://www.sciencedirect.com/science/article/pii/S0926337312005917 [4] HAN D, SUN N, LIU J, LI C, SHAN H, YANG C. Synergistic effect of W and P on ZSM-5 and its catalytic performance in the cracking of heavy oil[J]. J Energy Chem, 2014, 23(4):519-526. doi: 10.1016/S2095-4956(14)60180-7 [5] WANG X, GAO X, DONG M, ZHAO H, HUANG W. Production of gasoline range hydrocarbons from methanol on hierarchical ZSM-5 and Zn/ZSM-5 catalyst prepared with soft second template[J]. J Energy Chem, 2015, 24(4):490-496. doi: 10.1016/j.jechem.2015.06.009 [6] WU G, WU W, WANG X, ZAN W, WANG W, LI C. Nanosized ZSM-5 zeolites:Seed-induced synthesis and the relation between the physicochemical properties and the catalytic performance in the alkylation of naphthalene[J]. Microporous Mesoporous Mater, 2013, 180(1):187-195. http://www.sciencedirect.com/science/article/pii/S1387181112006609 [7] JINDAN N, CUOZHU L, TIANYOU Z, GUOCHANG D, SHENLIN H, LI W. Synthesis and catalytic performance of ZSM-5/MCM-41 zeolites with varying mesopore size by surfactant-directed recrystallization[J]. Catal Lett, 2013, 143(3):267-275. doi: 10.1007/s10562-013-0963-0 [8] QI J, ZHAO T, LI F, SUN G, XU X, MIAO C, WANG H, ZHANG X. Study of cracking of large molecules over a new type meso-ZSM-5 composite zeolite[J]. J Porous Mater, 2010, 17(2):177-184. doi: 10.1007/s10934-009-9278-3 [9] TAUFIQURRAHMI N, MOHAMED A R, BHATIA S. Deactivation and coke combustion studies of nanocrystalline zeolite beta in catalytic cracking of used palm oil[J]. Chem Eng J, 2010, 163(3):413-421. doi: 10.1016/j.cej.2010.07.049 [10] DAO K Y, MEI L F, YA H Y, YI B S, JIA Y C, YI W F. One-step synthesis of hierarchical-structured ZSM-5 zeolite[J]. J Fuel Chem Technol, 2016, 44(11):1363-1369. http://rlhxxb.sxicc.ac.cn/CN/abstract/abstract18933.shtml [11] NIKOORAZM M, CHOGHAMARANI A G, NOORI N. Preparation and characterization of functionalized Cu (Ⅱ) schiff base complex on mesoporous MCM-41 and its application as effective catalyst for the oxidation of sulfides and oxidative coupling of thiols[J]. J Porous Mater, 2015, 22(4):877-885. doi: 10.1007/s10934-015-9961-5 [12] OOI Y S, ZAKARIA R, MOHAMED A R, BHATIA S. Synthesis of composite material MCM-41/beta and its catalytic performance in waste used palm oil cracking[J]. Appl Catal A:Gen, 2004, 274(1/2):15-23. http://www.sciencedirect.com/science/article/pii/S0926860X04004454 [13] ZHANG H, LI Y. Preparation and characterization of Beta/MCM-41composite zeolite with a stepwise-distributed pore structure[J]. Powder Technol, 2008, 183(1):73-78. doi: 10.1016/j.powtec.2007.11.013 [14] GUO W, XIONG C, HUANG L, LI Q. Synthesis and characterization of composite molecular sieves comprising zeolite beta with MCM-41 structures[J]. J Mater Chem, 2001, 11(7):1886-1890. doi: 10.1039/b009903l [15] SONG C M, JIANG J, YAN Z. Synthesis and characterization of MCM-41-type composite materials prepared from ZSM-5 zeolite[J]. J Porous Mater, 2008, 15(2):205-211. doi: 10.1007/s10934-007-9121-7 [16] AHMAD M, FARHANA R, RAMAN A A A, BHARGAVA S K. Synthesis and activity evaluation of heterometallic nano oxides integrated ZSM-5 catalysts for palm oil cracking to produce biogasoline[J]. Energy Convers Manage, 2016, 119(1):352-360. http://www.sciencedirect.com/science/article/pii/S0196890416303193 [17] SANG Y, LIU H, HE S, LI H, JIAO Q, WU Q, SUN K. Catalytic performance of hierarchical H-ZSM-5/MCM-41 for methanol dehydration to dimethyl ether[J]. J Energy Chem, 2013, 22(5):769-777. doi: 10.1016/S2095-4956(13)60102-3 [18] CHANG N, GU Z, WANG Z, LIU Z, HOU X, WANG J. Study of Y zeolite catalysts for coal tar hydro-cracking in supercritical gasoline[J]. J Porous Mater, 2011, 18(5):589-596. doi: 10.1007/s10934-010-9413-1 [19] AKMAZ S, CAGLAYAN P A. Effect of catalyst, temperature, and hydrogen pressure on slurry hydrocracking reactions of naphthalene[J]. Chem Eng Technol, 2015, 38(5):917-930. doi: 10.1002/ceat.v38.5 [20] GUTIERREZ A, ARANDES J M, CASTANO P, OLAZAR M, BARONA A, BILBAO J. Effect of temperature in hydrocracking of light cycle oil on a noble metal-supported catalyst for fuel production[J]. Chem Eng Technol, 2012, 35(4):653-660. doi: 10.1002/ceat.201100382 [21] BENDEZU S, CID R, FIERRO J L G, LOPEZ AGUDO A. Thiophene hydrodesulfurization on sulfided Ni, W and NiW/USY zeolite catalysts:Effect of the preparation method[J]. Appl Catal A:Gen, 2000, 197(1):47-60. doi: 10.1016/S0926-860X(99)00532-3 [22] ZHAO Y, LIN X, LI D. Catalytic hydrocracking of a bitumen -derived asphaltene over NiMo/-Al2O3 at various temperatures[J]. Chem Eng Technol, 2015, 38(1):297-303. [23] ISHIHARA A, ITOH T, NASU H, HASHIMOTO T, DOIT. Hydrocracking of 1-methylnaphthalene/decahydronaphthalene mixture catalyzed by zeolite-alumina composite supported NiMo catalysts[J]. Fuel Process Technol, 2013, 116(1):222-227. http://www.sciencedirect.com/science/article/pii/S0378382013002324 [24] KUBICKA D, KALUZA L. Deoxygenation of vegetable oils over sulfided Ni, Mo and NiMo catalysts[J]. Appl Catal A:Gen, 2010, 372(2):199-208. doi: 10.1016/j.apcata.2009.10.034 [25] ISHIHARA A, FUKUI N, NASU H, HASHIMOTO T. Hydrocracking of soybean oil using zeolite-alumina composite supported NiMo catalysts[J]. Fuel, 2014, 134(1):611-617. http://www.sciencedirect.com/science/article/pii/S0016236114005602 [26] CHEN H, WANG Q, ZHANG X, WANG L. Effect of support on the NiMo phase and its catalytic hydrodeoxygenation of triglycerides[J]. Fuel, 2015, 159(1):430-435. http://www.sciencedirect.com/science/article/pii/S0016236115007012 [27] SUBSADSANA M, SANGDARA P, RUANGVIRIYACHAI C. Effect of bimetallic NiW modified crystalline ZSM-5 zeolite on catalytic conversion of crude palm oil and identification of biofuel products[J]. Asia-Pac J Chem Eng, 2017, 12(1):147-158. doi: 10.1002/apj.v12.1 -
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