Preparation of KNiMo-based catalysts by using non-thermal plasma and their catalytic performance in the synthesis of higher alcohols from syngas
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摘要: 采用低温等离子体法在温和条件下制备了低碳醇合成（HAS）用的高性能KNiMo基催化剂，利用XRD、氮吸附、TEM、H2-TPD、CO-TPD和原位CO吸附DRIFTS等技术对其进行了表征。结果表明，与传统的热法制备相比，低温等离子体法不仅缩短了制备时间，而且得到的KNiMo基催化剂层数少、粒径小、分散度高，有利于形成更薄和更短的片层，并暴露大量位于边、角位的催化活性位，促进CO转化和醇的形成，表现出优异的低碳醇合成催化性能。其中，采用低温等离子体直接制备的KNiMo-DPS催化剂，在5 MPa、350℃、空速为5000 h-1的反应条件下，CO转化率达到32.3%，总醇选择性为75.1%，总醇中C2+醇的选择性为65.2%。Abstract: A series of KNiMo-based catalysts were prepared by using non-thermal plasma and characterized by XRD, nitrogen sorption, TEM, H2-TPD, CO-TPD, and in-situ CO adsorption DRIFTS; their catalytic performance in the higher alcohol synthesis (HAS) from syngas was investigated. The results indicate that in comparison with those prepared by the conventional thermal method, the KNiMo-based catalysts prepared by using non-thermal plasma display thinner and shorter MoS2 slabs and more highly dispersed and coordinatively unsaturated sites, which endow the KNiMo-based catalysts excellent performance in HAS. In particular, for the HAS over the KNiMo-DPS catalyst under 350 ℃, 5 MPa, and a gas hourly space velocity (GHSV) of 5000 h-1, the conversion of CO reaches 32.3%, with a selectivity of 75.1% to total alcohol and a C2+ alcohol selectivity of 65.2% in the total alcohols.
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Key words:
- higher alcohol synthesis /
- syngas conversion /
- KNiMo-based catalyst /
- non-thermal plasma
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图 1 (a) 硫化用介质阻挡放电(DBD)等离子体反应器结构示意和(b) DBD反应器放电时床层温度分布
Figure 1 (a) Configuration of the dielectric barrier discharge (DBD) plasma reactor; (b) Temperature distribution across the reaction bed under actual reaction conditions in plasma synthesis
图 2 不同方法合成的KNiMo基催化剂的XRD谱图
Figure 2 XRD patterns of the KNiMo-based catalysts synthesized by different methods
图 3 不同方法合成的KNiMo基催化剂的TEM照片
Figure 3 TEM images from KNiMo-CTS (a), KNiMo-CPS (b), KNiMo-DTS (c) and KNiMo-DPS (d)
图 4 KNiMo-DPS催化剂的HAADF-STEM-EDS照片
Figure 4 HAADF-STEM-EDS photographs of the KNiMo-DPS catalyst
图 5 不同方法所制备KNiMo基催化剂的H2-TPD谱图
Figure 5 H2-TPD profiles of the KNiMo-based catalysts synthesized by different methods
图 6 不同方法所合成KNiMo基催化剂的CO-TPD谱图
Figure 6 CO-TPD profiles of the KNiMo-based catalysts synthesized by different methods
图 7 KNiMo-DPS催化剂的原位CO吸附DRIFTS谱图
Figure 7 In-situ DRIFTS spectra of CO adsorption over the KNiMo-DPS catalyst
图 8 KNiMo-DPS催化剂的稳定性
Figure 8 Catalytic performance of KNiMo-DPS with the time on stream
图 9 KNiMo-DPS催化剂(a)和KNiMo-CTS催化剂(b)反应前后的XRD谱图
Figure 9 XRD patterns of the KNiMo-DPS (a) and KNiMo-CTS (b) catalysts, a comparison between the fresh ones and spent one after reaction tests
表 1 不同方法合成的KNiMo基催化剂的物化性质
Table 1 Physico-chemical characteristics of the KNiMo-based catalysts prepared by different methods
Catalyst Surface area
A/(m2·g-1)Particle size
d/nmCO adsorption amount
/(μmol·g-1)H2 adsorption amount
/(μmol·g-1)KNiMo-CTS 23 35.8 42 28 KNiMo-CPS 42 8.7 63 40 KNiMo-DTS 34 29.6 58 32 KNiMo-DPS 51 7.1 75 49 
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表 2 不同合成方法制备KNiMo基催化剂的HAS催化反应性能a
Table 2 Catalytic performance of the KNiMo-based catalysts synthesized by different methods toward HAS a
Catalyst CO
conversion x/%ROH STY/
(g·mL-1·h-1)Product selectivity w/%b Alcohol distribution w/% ROHc CHnd MeOH C2+OHe KNiMo-CTS 19.8 0.06 61.4 38.6 44.7 55.3 KNiMo-CPS 28.4 0.11 70.3 29.7 37.0 63.0 KNiMo-DTS 21.7 0.08 64.2 35.8 43.1 56.9 KNiMo-DPS 32.3 0.13 75.1 24.9 34.8 65.2 note: reactions were carried out at 350 ℃, 5.0 MPa, GHSV = 5000 h-1, H2/CO = 2. ROH means total alcohols and CHn is total hydrocarbons. STY is space-time yield and the product selectivity is CO2 free-based. Alcohols with carbon number of 2-5 (mainly ethanol, 1-propanol, 1-butanol, 1-pentanol and 2-propanol) were obtained in the product
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