Hydrothermal reduction synthesis of K-Ni-Mo-based catalyst and its catalytic performance for higher alcohol synthesis from syngas
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摘要: 采用水热还原法制备出具有金属Ni和K2MoO4紧密接触的合成低碳醇用非硫化态K-Ni-Mo基催化剂。通过XRD、N2物理吸附-脱附、H2-TPR、HR-TEM、SEM-EDS、XPS、H2-TPD、CO-TPD和CO2-TPD等手段对所合成催化剂进行了分析表征。研究结果显示,向Ni-Mo基催化剂中引入K可产生K2MoO4相,同时伴随NiMoO4相含量的降低,显著提升了K-Ni-Mo基催化剂上CO非解离吸附活化能力,从而促进了CO转化和醇类产物的形成。此外,同时增加的催化剂表面碱性可提高催化剂上碱性羟基基团数量,进而有效降低烃类选择性,表现出优异的合成低碳醇性能。其中,K0.4-Ni-Mo基催化剂具有最优的催化性能,在5 MPa、240 ℃、空速5000 h−1的反应条件下,CO转化率达到19.6%,总醇选择性57.8%,其中,总醇中C2+醇选择性为66.5%。Abstract: A series of non-sulfurized K-Ni-Mo-based catalysts with close contact between Ni and K2MoO4 were prepared by hydrothermal reduction for higher alcohol synthesis from syngas. The as-prepared catalysts were characterized by XRD, N2 adsorption-desorption, H2-TPR, HR-TEM, SEM-EDS, XPS, H2-TPD, CO-TPD and CO2-TPD techniques. The results indicate that the introduction of K facilitates the formation of the K2MoO4 phase while brings about a decrease of NiMoO4. It can significantly assist the non-dissociative activation of CO for insertion and subsequently alcohol formation. Moreover, the addition of K increases the surface basicity, which leads to more amount of basic hydroxy groups on the catalytic surface. The catalytic basicity ameliorates the production of alcohols. In particular, the K0.4-Ni-Mo catalyst shows the best catalytic behavior with CO conversion of 19.6%, total alcohol selectivity of 57.8% and C2+ alcohol selectivity in the total alcohols of 66.5% at GHSV of 5000 h−1, 240 °C, and 5 MPa.
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图 1 合成气制低碳醇反应装置示意图
1:气瓶;2:系统前定压器;3:热电偶;4:加热炉;5:催化剂床层;6:反应器;7:热阱;8:冷阱;9:系统后定压器;10:气相色谱
Figure 1 Schematic diagram of reaction device for higher alcohols synthesis from syngas
1: Gas cylinder; 2: Pre-reaction pressure regulator; 3: Thermocouple; 4: Heating furnace; 5: Catalytic bed; 6: Reactor; 7: Hot trap; 8: Cold trap; 9: Back-pressure regulator; 10: Gas chromatography
表 1 不同K含量的K-Ni-Mo基催化剂的织构参数
Table 1 Texture parameters of the K-Ni-Mo-based catalysts
Catalyst SBET/(m2·g−1) vmic/(cm3·g−1) Dave/nm Ni-Mo 72.6 0.21 11.7 K0.1-Ni-Mo 65.9 0.15 9.3 K0.2-Ni-Mo 31.2 0.09 12.1 K0.3-Ni-Mo 24.5 0.10 16.8 K0.4-Ni-Mo 10.0 0.05 20.8 K0.5-Ni-Mo 9.3 0.05 22.4 SBET: BET surface area; vmic: pore volume; Dave: pore diameter 表 2 不同K含量的K-Ni-Mo基催化剂的Ni/K2MoO4比
Table 2 Ni/K2MoO4 ratios of the K-Ni-Mo-based catalysts
Catalyst Ni/K2MoO4 ratio a K0.1-Ni-Mo 0.43 K0.2-Ni-Mo 1.23 K0.3-Ni-Mo 1.46 K0.4-Ni-Mo 1.58 K0.5-Ni-Mo 0.89 a: by XPS 表 3 不同K-Ni-Mo基催化剂上低碳醇合成反应性能a
Table 3 Catalytic performances of the K-Ni-Mo-based catalystsa
Catalyst CO conversion/% STYROH
/(mg·g−1·h−1)Product selectivity w/%b Alcohol distribution C/% ROHc CHnd CH4 MeOH C2+OHe Ni-Mo 28.1 52 29.9 70.1 49.6 69.7 30.3 K0.1-Ni-Mo 25.4 38 38.9 61.1 59.4 46.7 53.3 K0.2-Ni-Mo 21.6 37 40.1 59.9 55.9 39.8 60.2 K0.3-Ni-Mo 20.5 31 43.2 56.8 57.5 37.6 62.4 K0.4-Ni-Mo 19.6 71 57.8 42.2 41.3 33.5 66.5 K0.5-Ni-Mo 19.7 69 53.6 46.4 57.8 36.7 63.3 a: Reaction conditions: t =240 °C, p=5 MPa, GHSV=5000 h−1, H2/CO=2; b: CO2 free; c: ROH=total alcohol; d: CHn=total hydrocarbon;
e: Alcohol with carbon numbers of 2–5 (mainly ethanol, 1-propanol, 1-butanol, 1-pentanol, and 2-propanol) -
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