原位XRD反应装置下H2O对Fe5C2的物相及F-T反应性能影响的研究

郭天雨; 刘粟侥; 青明; 冯景丽; 吕振刚; 王洪; 杨勇

原位XRD反应装置下H₂O对Fe₅C₂的物相及F-T反应性能影响的研究

郭天雨^{1, 2},
刘粟侥³,
青明³,
冯景丽³,
吕振刚³,
王洪³,
杨勇^{1, 3, ,}

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.
中科合成油技术有限公司国家能源煤基液体燃料研发中心, 北京 101407

详细信息

中图分类号: O643
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出版历程
- 收稿日期: 2019-09-27
- 修回日期: 2019-10-22
- 网络出版日期: 2021-01-23
- 刊出日期: 2020-01-10

In situ XRD study of the effect of H₂O on Fe₅C₂ phase and Fischer-Tropsch performance

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 Energy Center for Coal to Liquids, Synfuels China Co. Ltd, Beijing 101407, China

More Information

Corresponding author: YANG Yong, Tel: +86 69667699, E-mail: yyong@sxicc.ac.cn

摘要

摘要: 将原位XRD反应装置与在线气相色谱技术结合，研究了不同H₂O含量（4.36%、1.68%、0.56%）条件下单一相Fe₅C₂的氧化速率，并考察了不同Fe₅C₂氧化程度（0、25%、55%、68%）和氧化次数对其费托合成（F-T）反应性能的影响。研究结果表明，Fe₅C₂物相的氧化速率随H₂O含量的提高而逐渐增加，同时H₂O氧化使Fe₅C₂颗粒粒径减小，暴露出更多活性位点，造成F-T反应活性提高，且氧化程度越大，活性提高越明显；随着氧化次数的增加，F-T反应活性逐渐提高，但CH₄选择性增加，C₅₊选择性逐渐降低。
- Fe₅C₂ /
- 水汽氧化 /
- 原位XRD /
- 费托合成
Abstract: In situ XRD reaction device combined with the online gas chromatography was used to study the oxidation behavior of the effect of H₂O content (4.36%, 1.68%, 0.56%) on the phase and Fischer-Tropsch synthesis (FTS) performance of the single phase Fe₅C₂. The results show that the oxidation rate of the Fe₅C₂ phase increases with the increase of the content of injected H₂O. Meanwhile, the particle size of Fe₅C₂ phase decreases and more active sites exposes during the H₂O oxidation, resulting in the increase of the FTS activity. Furthermore, the FTS activity increases with the increase of the oxidation times, but the selectivity of CH₄ increases and the C₅₊ selectivity decreases gradually.
- Fe₅C₂ /
- H₂O oxidation /
- in situ XRD /
- Fischer-Tropsch synthesis

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图 1 原位XRD反应装置示意图

Figure 1 Schematic diagram of the in situ XRD reactor

1: normal gas cylinder; 2: needle valve; 3: pressure reducing valve; 4: mass flow controller; 5: check valve; 6: bubbler; 7: in situ capillary reactor setup (a: thermocouple, b: silica capillary, c: catalyst sample, d: silica wool); 8: back pressure valve; 9: gas chromatography (agilent 6890 N)

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图 2 不同水含量0.56%(a)、1.68%(b)、4.36%(c)条件下Fe₅C₂催化剂的XRD谱图

Figure 2 XRD patterns of Fe₅C₂ catalysts under different H₂O contents 0.56%(a), 1.68%(b), 4.36%(c)

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图 3 Fe₅C₂的相对含量(a)及氧化速率(b)

Figure 3 Relative contents of Fe₅C₂ catalysts (a) and oxidation rate (b)

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图 4 不同水含量条件下样品中Fe₅C₂ (a)与Fe₃O₄ (b)的晶粒粒径变化

Figure 4 Particle size of Fe₅C₂ (a) and Fe₃O₄ (b) under different H₂O contents

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图 5 不同反应时间Fe₅C₂相对含量以及CO转化率

Figure 5 Relative contents of Fe₅C₂ and CO conversion in different times

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图 6 FTS与WGS的CO转化率

Figure 6 CO conversion in FTS and WGS

(x(WGS) = x_CO * sCO₂, x(FTS) =1-x(WGS))

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图 7 不同反应时间Fe₅C₂、Fe₃O₄的晶粒粒径

Figure 7 Particle size of Fe₅C₂ and Fe₃O₄ under different reaction time

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图 8 不同反应时间Fe₅C₂和Fe₃O₄的XRD谱图

Figure 8 XRD patterns of the samples prepared at different reaction times

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图 9 不同氧化程度Fe₅C₂催化剂上CO转化率(a)物相相对含量(b)

Figure 9 CO conversion (a) and relative abundance (b) of Fe₅C₂ under different oxidation degrees

(0, 25%, 55%, 68%)

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图 10 不同氧化程度Fe₅C₂催化剂上FTS反应的CO转化率

Figure 10 CO conversion in FTS of Fe₅C₂ under different oxidation degrees

(0, 25%, 55%, 68%)

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图 11 不同氧化程度反应中Fe₅C₂的晶粒粒径

Figure 11 Particle size of Fe₅C₂ catalyst under different oxidation degrees

(0, 25%, 55%, 68%)

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图 12 反复氧化三次的反应中CO转化率(a)和Fe₅C₂相的相对含量(b)

Figure 12 CO conversion (a) and relative content of Fe₅C₂ (b) in the oxidation condition for three times

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图 13 反复氧化三次的反应中FTS反应的CO转化率

Figure 13 CO conversion in FTS in the oxidation condition for three times

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图 14 三次反应中产物的选择性

Figure 14 Products selectivity after three oxidation times

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