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 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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