协同高效的铁催化剂构建及其在CO<sub>2</sub>加氢制高碳烃中的应用

纪学玮; 葛庆杰; 孙剑

协同高效的铁催化剂构建及其在CO₂加氢制高碳烃中的应用

纪学玮^{1, 2},
葛庆杰¹,
孙剑^1, ,

1.
中国科学院大连化学物理研究所洁净能源国家实验室, 辽宁大连 116023
2.
中国科学院大学, 北京 100049

基金项目:

国家自然科学基金 91745107

详细信息

中图分类号: O643
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- 被引次数: 0
出版历程
- 收稿日期: 2018-11-13
- 修回日期: 2019-02-16
- 网络出版日期: 2021-01-23
- 刊出日期: 2019-04-10

Construction of synergistic and efficient iron-based catalysts for hydrogenation of CO₂ to higher hydrocarbons

JI Xue-wei^{1, 2},
GE Qing-jie¹,
SUN Jian^{1
, ,}

1.
Dalian National Laboratory for Clean Energy, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian 116023, China
2.
University of Chinese Academy of Sciences, Beijing 100049, China

Funds:

National Natural Science Foundation of China 91745107

More Information

Corresponding author: SUN Jian, E-mail: sunj@dicp.ac.cn

摘要

摘要: 采用物理掺杂法制备了生物质灰分作为助剂的融铁催化剂，通过X射线衍射、透射电镜、穆斯堡尔谱等方法对催化剂进行了表征，并在固定床反应器中对其CO₂加氢制高碳烃的催化性能进行了评价。结果表明，与不含生物质灰分助剂的催化剂相比，添加助剂的融铁催化剂粒径较小且尺寸分布较窄，Fe₃O₄、Fe₅C₂、Fe₃C和α-Fe四相协同共存，进而促使逆水气变换反应与C-C偶联的串联反应高效进行，在有效抑制甲烷生成的同时，可明显提升高碳烃选择性。高碳烃产物以C_4-18的烃类为主，在300 ℃、1.0 MPa、4800 h^-1、H₂/CO₂=3.0、助剂添加量为5%（质量分数）的条件下，其在烃类产物中选择性最高可达73.9%。
- CO₂加氢 /
- 高碳烃 /
- Fe基催化剂 /
- 生物质 /
- 协同作用
Abstract: A series of fused iron (FI) catalysts promoted with biomass ash were prepared by physical mixing method and characterized by X-ray diffraction, transmission electron microscopy and Mossbauer spectroscopy. The catalytic performance of CO₂ hydrogenation to higher hydrocarbons was evaluated in a fixed bed reactor. The results show that compared with the catalyst without biomass ash (B-ash), the fused iron catalysts promoted with biomass ash have smaller particle size and narrower size distribution, and the four phases of Fe₃O₄, Fe₅C₂, Fe₃C as well as α-Fe coexist in synergy. Thus, the tandem reaction of reverse water gas shift (RWGS) and C-C coupling proceed efficiently, and the selectivity of higher hydrocarbons is significantly improved while methane formation is effectively suppressed. Among the products, C_4-18 hydrocarbons are dominant. The C_4-18 hydrocarbons' selectivity in all hydrocarbons reaches 73.9% at the conditions of 300℃, 1.0 MPa, 4800 h^-1, H₂/CO₂=3.0 as well as the additive amount of the promoter is 5% (mass ratio).
- CO₂ hydrogenation /
- high hydrocarbons /
- Fe-based catalyst /
- biomass /
- synergism

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图 1 不同催化剂的TEM照片及粒径分布

Figure 1 TEM images of different catalysts

(a)、(b): FI; (c)、(d): FI-B-ash

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图 2 不同催化剂的XRD谱图

Figure 2 XRD spectra of different catalysts

a: fresh FI; b: fresh FI-1B-ash; c: fresh FI-5B-ash; d: fresh FI-10B-ash; e: fresh FI-15B-ash; f: used FI; g: used FI-5B-ash

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图 3 反应后不同催化剂上的铁物种分布图

Figure 3 Iron species distribution in different catalysts after reaction

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图 4 不同催化剂的CO-TPD谱图

Figure 4 CO-TPD profiles of different catalysts

a: FI; b: FI-1B-ash; c: FI-5B-ash; d: FI-10B-ash; e: FI-15B-ash

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图 5 不同催化剂的CO₂-TPD谱图

Figure 5 CO₂-TPD profiles of different catalysts

a: fresh FI; b: fresh FI-B-ash

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图 6 助剂添加量对CO₂加氢性能的影响

Figure 6 Effect of additive amount on the performance of CO₂ hydrogenation

a: CO₂ conversion; b: CO selectivity; c: CH₄ selectivity in hydrocarbons; d: C₄₊ selectivity in hydrocarbons reaction conditions: H₂/CO₂ = 3.0, t=320 ℃, p=1.0 MPa, v=4800 h^-1

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表 1 B-ash元素组成及含量

Table 1 The elemental composition of calcined corncob

Material	Composition of element w/%
Material	O	K	Si	Ca	Cl	Al	Fe	Mg	P	Na	S	others
B-ash	26.9	22.8	21.8	7.2	6.8	5.6	3.2	2.1	1.0	0.9	0.8	0.9

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表 2 不同催化剂的比表面积

Table 2 Specific surface area of different catalysts

Catalyst	FI	FI-1-B-ash	FI-5-B-ash	FI-10-B-ash	FI-15-B-ash
Surface area A /(m²·g^-1)	4.3	1.7	1.7	1.0	1.4

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表 3 空速对CO₂加氢性能的影响

Table 3 Effect of velocity on the performance of CO₂ hydrogenation

Velocity /h^-1	CO₂ conv. x/%	CO sel. s/%	Hydrocarbons sel. s/%
Velocity /h^-1	CO₂ conv. x/%	CO sel. s/%	CH₄	C_{2, 3}	C₄₊
2400	44.4	11.86	9.9	19.1	71.0
4800	28.1	35.9	9.5	18.6	71.9
9600	29.8	28.0	10.6	19.4	70.0
reaction conditions: H₂/CO₂=3.0, t=320 ℃, p=1.0 MPa

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表 4 压力对CO₂加氢性能的影响

Table 4 Effect of pressure on the performance of CO₂ hydrogenation

Pressure p/MPa	CO₂ conv. x/%	CO sel. s/%	Hydrocarbons sel. s/%
Pressure p/MPa	CO₂ conv. x/%	CO sel. s/%	CH₄	C_{2, 3}	C₄₊
0.5	27.0	45.3	9.4	19.4	71.2
1.0	28.1	35.9	9.5	18.6	71.9
2.0	38.7	13.8	10.7	18.8	70.5
reaction conditions: H₂/CO₂=3.0, t=320 ℃, v=4800 h^-1

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表 5 温度对CO₂加氢性能的影响

Table 5 Effect of temperature on the performance of CO₂ hydrogenation

Temperature t/℃	CO₂ conv. x/%	CO sel. s/%	Hydrocarbons sel. s/%
Temperature t/℃	CO₂ conv. x/%	CO sel. s/%	CH₄	C_{2, 3}	C₄₊
280	21.0	34.4	9.9	17.1	73.0
300	23.8	37.8	8.1	18.0	73.9
320	28.1	35.9	9.5	18.6	71.9
340	32.8	31.6	12.6	21.0	66.4
reaction conditions: H₂/CO₂=3.0, p=1.0 MPa, v=4800 h^-1

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