新型FeCo双金属催化剂催化CO2加氢制低碳烯烃

doi:10.11949/0438-1157.20210076

摘要/Abstract

摘要：

CO₂加氢制备低碳烯烃是实现C1资源高值化利用的有效途径。为提高低碳烯烃选择性，以Fe-MOF为主体，对苯二甲酸为骨架配体，构建了金属比例可控的铁钴双金属催化剂（FeCo/MC），阐明了双金属的协同作用及金属比例对加氢性能的影响。发现Co的添加可以增加催化剂表面碱性位而显著地改善CO₂吸附，促进铁的碳化并通过费托反应的CO消耗促进逆水煤气反应。同时，适宜的铁钴比有助于改善金属间亲密度，从而通过合理串联活性位以获取最佳的低碳烯烃选择性和尽可能低的甲烷选择性，铁钴比为6时CO₂转化率为32.72%，低碳烯烃选择性最高达到37.14%。

关键词: 催化剂, 载体, 烯烃, 二氧化碳, 加氢, 铁物种

Abstract:

The hydrogenation of CO₂ on iron-based catalysts to produce light olefins is an effective way to realize the high-value utilization of C1 resources. To improve the selectivity of low-carbon olefins, Fe-MOF is used as the main body and terephthalic acid is used as the framework ligand to construct an iron-cobalt bimetallic catalyst (FeCo/MC) with a controllable metal ratio, which clarifies the synergistic effect of the bimetal and the effect of metal ratio on hydrogenation performance. It was found that the addition of Co can increase the basic sites on the catalyst surface to improve CO₂ adsorption significantly, while it promoted the carbonization of iron and benefited the positive progress of the reverse water gas shift reaction (RWGS) through the CO consumption of the Fischer-Tropsch reaction(FTS) route. In addition, a suitable iron to cobalt ratio helped to improve the intermetallic intimacy, which can connect active sites reasonably and obtain the best light olefin selectivity and the CH₄ selectivity as low as possible. The iron to cobalt ratio of 6 showed the highest light olefins selectivity (37.14%), and the CO₂ conversion rate was 32.72%.

Key words: catalyst, support, olefins, carbon dioxide, hydrogenation, iron species

中图分类号:

O 643.3

董子超, 吴玉, 张博风, 刘斯宝, 刘国柱, 赵杰. 新型FeCo双金属催化剂催化CO₂加氢制低碳烯烃[J]. 化工学报, 2021, 72(5): 2647-2656.

DONG Zichao, WU Yu, ZHANG Bofeng, LIU Sibao, LIU Guozhu, ZHAO Jie. Preparation and performances of FeCo/MC catalysts for CO₂ hydrogenation to light olefins[J]. CIESC Journal, 2021, 72(5): 2647-2656.

图/表 8

图1 催化剂热重和氮气-吸脱附表征

Fig.1 TG curves and N2 adsorption–desorption isotherms of catalysts

表1 FeCo(X∶1)/MC催化剂物理性质

Table 1 Specific surface area properties of FeCo(X∶1)/MC catalysts

X	Co^①/%(mass)	Fe^①/%(mass)	Fe/Co^②	S_BET/ (m²·g^-1)	S_micro/ (m²·g^-1)	S_meso/ (m²·g^-1)	V_micro/ (cm³·g^-1)	V_meso/ (cm³·g^-1)
3	9.1	26.5	3.1	152.9	43.5	109.4	0.02	0.31
4	6.6	26.0	4.1	133.3	14.6	118.7	0	0.32
6	4.6	25.5	5.8	118.2	6.6	111.6	0	0.27
9	3.9	34.0	9.1	171.1	54.9	116.2	0.02	0.42

图2 热解前[（a）~（d）]和热解后[（e）~（h）]催化剂的SEM图

Fig.2 SEM images of catalysts before [(a)—(d)] and after pyrolysis [(e)—(h)]

图3 FeCo/MC催化剂的HR-TEM图和粒径分布

Fig.3 HR-TEM images and particle size distribution of FeCo/MC catalysts

图4 催化剂性能表征

Fig.4 Characterization of catalysts

表2 FeCo/MC催化剂的CO2加氢性能

Table 2 CO2 hydrogenation performance of FeCo/MC catalysts

催化剂	CO₂ 吸附量^①/(mmol·g^-1)	CO₂ 转化率/%	产物选择性/%						O/P^②
催化剂	CO₂ 吸附量^①/(mmol·g^-1)	CO₂ 转化率/%	CO	CH₄	C₂~C₄	C₂=~C₄=	C₅+	alcohol	O/P^②
FeCo(3∶1)/MC	0.036	36.37	10.90	37.10	14.58	28.31	3.97	5.14	1.94
FeCo(4∶1)/MC	0.031	34.63	11.93	31.69	12.57	34.40	3.96	5.45	2.74
FeCo(6:∶1)/MC	0.026	32.72	13.48	27.30	10.59	37.14	5.49	6.00	3.51
FeCo(9∶1)/MC	0.022	29.17	16.19	26.33	10.70	35.60	5.03	6.15	3.32
Fe/MC	0.003	14.79	37.57	21.04	25.46	8.14	7.79	0	0.32

图5 反应后FeCo/MC催化剂的XRD图

Fig.5 XRD images of spent FeCo/MC catalysts

图6 不同Fe/Co比时的反应性能及反应过程示意图

Fig.6 Reaction performance with different Fe/Co ratio and schematic diagram of the reaction process

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新型FeCo双金属催化剂催化CO₂加氢制低碳烯烃

Preparation and performances of FeCo/MC catalysts for CO₂ hydrogenation to light olefins

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