Cu-Mo/C催化油酸甲酯选择性加氢脱氧制备生物柴油

doi:10.3969/j.issn.1673-5854.2023.02.006

Abstract

Abstract:

The Cu-Mo/C catalyst was prepared with ammonium molybdate tetrahydrate and copper nitrate trihydrate, and used for the selective hydrodeoxygenation reaction of methyl oleate. The catalysts were characterized by X-ray diffraction, X-ray diffraction photoelectron spectroscopy and electron paramagnetic resonance spectroscopy. The optimal process for the preparation of biodiesel from methyl oleate catalyzed by Cu-Mo/C and the catalytic performance of Cu-Mo/C were investigated. The results of the study showed that the addition of Cu promoted the formation of Mo/C catalyst and the Mo₂C and MoO₂ component in the catalyst worked together. The oxygen vacancies on the MoO₂ component could preferentially adsorb the C=O bond in the substrate and then Mo₂C component hydrodeoxygenated it, avoiding the hydrogenation of C=C bond. The excellent performance of catalyst and the selectivity of unsaturated hydrocarbons were achieved. The conversion rate of methyl oleate reached 98.8%, and the selectivity of unsaturated hydrocarbons was 40.2% at reaction temperature of 280 ℃, hydrogen pressure of 2.5 MPa and reaction time of 3 h. The catalytic activity of Cu-Mo₁₀/C was comparable to the noble metal Pd and commercial Mo/C catalysts, while the unsaturated hydrocarbon selectivity was higher as well as the good stability.

Key words: Cu-Mo/C, selective hydrodeoxygenation, oxygen vacancies, unsaturated hydrocarbons

CLC Number:

TQ35

Cong YU, Shitao YU, Lu LI. Preparation of Biodiesel by Selective Hydrodeoxygenation Methyl Oleate over Cu-Mo/C Catalyst[J]. Biomass Chemical Engineering, 2023, 57(2): 48-54.

Figures/Tables 8

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References 25

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催化剂 catalyst	Cu/%		Mo/%			O/%		C/%
催化剂 catalyst	Cu⁰	Cu²⁺	Mo²⁺	Mo⁴⁺	Mo⁶⁺	晶格氧 lattice oxygen	表面氧 surface oxide	C/%
Cu-Mo₂₀/C	0.67	0.44	2.26	11.69	13.67	28.45	27.24	15.46
Cu-Mo₁₅/C	2.13	0.69	4.30	9.98	11.96	21.92	21.41	27.32
Cu-Mo₁₀/C	4.03	0.34	7.86	8.34	7.45	15.31	19.54	36.37
Cu-Mo₅/C	9.77	1.23	9.06	4.33	6.21	13.92	12.15	42.51
Cu-Mo₁/C	13.38	1.30	11.12	1.85	4.54	8.59	9.19	49.06

催化剂 catalyst	转化率/% conversion	选择性 selectivity/%
催化剂 catalyst	转化率/% conversion	C₁₇^a	C₁₇^b	C₁₈^a	C₁₈^b	非烃类化合物 non-hydrocarbon compounds
Cu-Mo₂₀/C	49.5	4.8	3.9	22.7	53.3	15.3
Cu-Mo₁₅/C	76.4	3.4	3.1	40.2	43.7	9.6
Cu-Mo₁₀/C	98.8	2.1	1.8	54.6	38.4	3.1
Cu-Mo₅/C	99.2	1.5	1.3	84.5	10.6	2.1
Cu-Mo₁/C	99.5	0.7	0.4	96.4	1.9	0.6

催化剂 catalyst	转化率/% conversion	选择性 selectivity/%
催化剂 catalyst	转化率/% conversion	C₁₇^a	C₁₇^b	C₁₈^a	C₁₈^b	非烃类化合物 non-hydrocarbon compounds
Pd/C	99.1	70.8	0.2	16.6	1.5	10.9
Mo/C	98.6	3.6	2.7	79.3	9.8	4.6
Cu-Mo₁₀/C	98.8	2.1	1.8	54.6	38.4	3.1

样品 sample	含氧量/% oxygen content	氧化稳定性(110 ℃)/h oxidation stability	低位热值/(MJ·kg^-1) low calorific value
产物products	1.68	11.2	46.43
油酸甲酯methyl oleate	11.7	＜6.0	37.86
生物柴油^[17]biodiesel	―	≥6.0	≥42.78

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Preparation of Biodiesel by Selective Hydrodeoxygenation Methyl Oleate over Cu-Mo/C Catalyst

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