载体效应对Ru催化剂F-T反应性能的影响

程春园; 刘粟侥; 吴宝山

载体效应对Ru催化剂F-T反应性能的影响

程春园^{1, 2},
刘粟侥^{3, 4},
吴宝山^{1, 3, 4, ,}

1.
中国科学院山西煤炭化学研究所煤转化国家重点实验室, 山西太原 030001
2.
中国科学院大学, 北京 100049
3.
煤炭间接液化国家工程实验室, 北京 101407
4.
中科合成油技术有限公司, 北京 101407

基金项目:

国家自然科学基金 21473229

详细信息

通讯作者:
吴宝山, Tel: 0086-010-69667779, E-mail: wbs@sxicc.ac.cn

中图分类号: O643.36
计量
- 文章访问数: 109
- HTML全文浏览量: 26
- PDF下载量: 8
- 被引次数: 0
出版历程
- 收稿日期: 2017-01-16
- 修回日期: 2017-03-14
- 网络出版日期: 2021-01-23
- 刊出日期: 2017-05-10

Support effects on ruthenium catalyst for the Fischer-Tropsch synthesis

CHENG Chun-yuan^{1, 2},
LIU Su-yao^{3, 4},
WU Bao-shan^{1, 3, 4
, ,}

1.
State Key Laboratory of Coal Conversion, Institute of Coal Chemistry, Chinese Academy of Sciences, Taiyuan 030001, China
2.
University of Chinese Academy of Sciences, Beijing 100049, China
3.
National Engineering Laboratory for Indirect Coal Liquefaction, Beijing 101407, China
4.
Synfuels China Technology CO. LTD., Beijing 101407, China

Funds:

National Natural Science Foundation of China 21473229

摘要

摘要: 采用浸渍法将Ru负载于SiO₂、Al₂O₃和Beta分子筛制备了不同载体的Ru基F-T合成催化剂。通过N₂-物理吸附、XRD、NH₃-TPD、H₂-TPR、H₂-TPD、XPS和CO-DRIFTS等表征方法对不同催化剂的织构、物相、酸性、还原性质、吸附性能和电子状态信息进行了考察，并对不同载体催化剂的F-T反应性能及产物分布进行了研究。结果表明，不同载体Ru基催化剂在金属分散度、还原性质、对氢气吸附性能和电子状态等方面均存在较大差异。其中，酸性较弱的Ru/SiO₂催化剂具有较弱的金属载体相互作用、较小的颗粒粒径和较高的电子密度，同时该催化剂的Ru金属平台位点较多，导致其在F-T反应过程中表现较好的反应稳定性，其产物以重质烃为主，CH₄和轻质烃选择性较低。
- 金属-载体相互作用 /
- 钌催化剂 /
- F-T合成
Abstract: Series of Ru-based F-T synthesis catalysts, respectively with different supports of SiO₂, Al₂O₃ and Beta zeolite, were prepared by impregnation method. Characterization techniques such as N₂-adsorption, XRD, NH₃-TPD, H₂-TPR, H₂-TPD, XPS and CO-DRIFTS were used to study the textural structure, phase, acidity, reduction behavior, chemical adsorption and electron properties of the catalysts. F-T synthesis performances of the catalysts were investigated as well. The results indicated that the supports imposed obvious effects on the reduction and dispersion of Ru, therefore led to the differences in acidity and surface properties of the catalysts. F-T reaction performance showed that the relatively stable Ru/SiO₂ catalyst exhibited high selectivity to heavy hydrocarbons, ascribing to its less acidity, weaker metal-support interaction, and better Ru particle dispersion.
- metal-support interaction /
- ruthenium catalyst /
- F-T synthesis

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图 1 不同载体和还原前后催化剂的XRD谱图

Figure 1 XRD patterns of different support (a) and (un) reduced ((b), (c)) catalysts

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图 2 不同催化剂的NH₃-TPD谱图

Figure 2 NH₃-TPD profiles of the catalysts with different supports

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图 3 不同催化剂的H₂-TPR谱图

Figure 3 H₂-TPR profiles of the catalysts with different supports

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图 4 不同催化剂的H₂-TPD谱图

Figure 4 H₂-TPD profiles of the catalysts with different supports

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图 5 不同催化剂的TEM照片

Figure 5 TEM images of the catalysts

(a): Ru/Beta; (b): Ru/Al; (c): Ru/Si

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图 6 不同催化剂还原后的XPS谱图

Figure 6 XPS spectra of the reduced catalysts with different supports

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图 7 不同催化剂的CO-DRIFTS谱图

Figure 7 CO-DRIFTS spectra of different catalysts

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图 8 不同催化剂上TOF随反应时间的变化

Figure 8 Evolution of TOF with time on steam of different catalysts

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表 1 不同载体及其相应催化剂的理化性质

Table 1 Physicochemical properties of the support and Ru-loading catalysts

Catalyst	Metal content^a w/%	BET surface area A/(m²·g^-1)	Pore volume v/(cm³·g^-1)	H₂ pulse
Catalyst	Metal content^a w/%	BET surface area A/(m²·g^-1)	Pore volume v/(cm³·g^-1)	dispersion/%	particle size d/ nm
Ru/Beta	0.97	398(402^b)	0.34(0.37)	10.5	12.8
Ru/Al	0.98	162(166)	0.47(0.47)	11.8	11.4
Ru/Si	1.03	218(222)	0.70(0.74)	17.8	7.6
^a: Ru content was determined by ICP-OES
^b: physicochemical properties of different supports

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表 2 Ru负载催化剂在相同TOF下的选择性

Table 2 Selectivity of the supported Ru catalysts at the same TOF

Catalyst	TOF^a/h^-1	CO conversion x%	CO₂ selectivity s_mol/%	HC selectivity s/%
Catalyst	TOF^a/h^-1	CO conversion x%	CO₂ selectivity s_mol/%	C₁	C_2-2	C_5-11	C₁₂₊
Ru/Beta	239.5	9.0	1.4	13.1	22.5	38.6	25.8
Ru/Al	236.4	11.3	0.9	9.0	13.4	31.2	46.4
Ru/Si	242.7	13.8	6.4	7.8	12.9	27.5	51.8
^a: based on H₂ chemisorption result

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