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

参考文献 33

1	巩金龙. CO₂化学转化研究进展概述[J]. 化工学报, 2017, 68(4): 1282-1285.
	Gong J L. A brief overview on recent progress on chemical conversion of CO₂[J]. CIESC Journal, 2017, 68(4): 1282-1285.
2	Liu X, Wang M, Zhou C, et al. Selective transformation of carbon dioxide into lower olefins with a bifunctional catalyst composed of ZnGa₂O₄ and SAPO-34[J]. Chem. Commun. (Camb.), 2018, 54(2): 140-143.
3	Zhou W, Cheng K, Kang J C, et al. New horizon in C1 chemistry: breaking the selectivity limitation in transformation of syngas and hydrogenation of CO₂ into hydrocarbon chemicals and fuels[J]. Chemical Society Reviews, 2019, 48(12): 3193-3228.
4	Saeidi S, Najari S, Fazlollahi F, et al. Mechanisms and kinetics of CO₂ hydrogenation to value-added products: a detailed review on current status and future trends[J]. Renewable and Sustainable Energy Reviews, 2017, 80: 1292-1311.
5	Muleja A A, Gorimbo J, Masuku C M. Effect of co-feeding inorganic and organic molecules in the Fe and Co catalyzed Fischer–Tropsch synthesis: a review[J]. Catalysts, 2019, 9(9): 746.
6	Yang X Z, Zhang H, Liu Y X, et al. Preparation of iron carbides formed by iron oxalate carburization for Fischer–Tropsch synthesis[J]. Catalysts, 2019, 9(4): 347.
7	Puga A V. On the nature of active phases and sites in CO and CO₂ hydrogenation catalysts[J]. Catalysis Science & Technology, 2018, 8(22): 5681-5707.
8	Liu M, Yi Y H, Wang L, et al. Hydrogenation of carbon dioxide to value-added chemicals by heterogeneous catalysis and plasma catalysis[J]. Catalysts, 2019, 9(3): 275.
9	张玉龙, 邵光印, 张征湃, 等. 活化气氛对CO₂加氢制取低碳烯烃Fe-K催化剂构-效关系[J]. 化工学报, 2018, 69(2): 690-698.
	Zhang Y L, Shao G Y, Zhang Z P, et al. Activation atmospheres on structure-performance relationship of K-promoted Fe catalysts for lower olefin synthesis from CO₂ hydrogenation[J]. CIESC Journal, 2018, 69(2): 690-698.
10	Liang B L, Duan H M, Sun T, et al. Effect of Na promoter on Fe-based catalyst for CO₂ hydrogenation to alkenes[J]. ACS Sustainable Chemistry & Engineering, 2019, 7(1): 925-932.
11	Yang H Y, Zhang C, Gao P, et al. A review of the catalytic hydrogenation of carbon dioxide into value-added hydrocarbons[J]. Catalysis Science & Technology, 2017, 7(20): 4580-4598.
12	Dorner R W, Hardy D R, Williams F W, et al. K and Mn doped iron-based CO₂ hydrogenation catalysts: detection of KAlH₄ as part of the catalyst's active phase[J]. Applied Catalysis A: General, 2010, 373(1/2): 112-121.
13	Ando H. Selective alkene production by the hydrogenation of carbon dioxide over Fe-Cu catalyst[J]. Energy Procedia, 2016, 89: 421-427.
14	Wang X, Zhang J L, Chen J Y, et al. Effect of preparation methods on the structure and catalytic performance of Fe-Zn/K catalysts for CO₂ hydrogenation to light olefins[J]. Chinese Journal of Chemical Engineering, 2018, 26(4): 761-767.
15	Satthawong R, Koizumi N, Song C S, et al. Bimetallic Fe-Co catalysts for CO₂ hydrogenation to higher hydrocarbons[J]. Journal of CO₂ Utilization, 2013, 3/4: 102-106.
16	Li S W, Xu Y, Chen Y F, et al. Tuning the selectivity of catalytic carbon dioxide hydrogenation over iridium/cerium oxide catalysts with a strong metal-support interaction[J]. Angewandte Chemie International Edition, 2017, 56(36): 10761-10765.
17	Yoon S, Oh K, Liu F D, et al. Specific metal–support interactions between nanoparticle layers for catalysts with enhanced methanol oxidation activity[J]. ACS Catalysis, 2018, 8(6): 5391-5398.
18	刘洋洋, 孙超, Malhi Haripal Singh, 等. 载体对铁基催化剂结构及CO₂加氢制烯烃反应性能的影响特性[J]. 化工学报, 2020, 71(10): 4652-4662.
	Liu Y Y, Sun C, Singh M H, et al. Effects of identities of supports on Fe-based catalyst and their consequences on activities of CO₂ hydrogenation to olefins[J]. CIESC Journal, 2020, 71(10): 4652-4662.
19	Wan H J, Wu B S, Xiang H W, et al. Fischer–Tropsch synthesis: influence of support incorporation manner on metal dispersion, metal–support interaction, and activities of iron catalysts[J]. ACS Catalysis, 2012, 2(9): 1877-1883.
20	Wei J, Ge Q, Yao R, et al. Directly converting CO₂ into a gasoline fuel[J]. Nature Communications, 2017, 8: 15174.
21	Dokania A, Ramirez A, Bavykina A, et al. Heterogeneous catalysis for the valorization of CO₂: role of bifunctional processes in the production of chemicals[J]. ACS Energy Letters, 2019, 4(1): 167-176.
22	Cheng Y, Lin J, Wu T J, et al. Mg and K dual-decorated Fe-on-reduced graphene oxide for selective catalyzing CO hydrogenation to light olefins with mitigated CO₂ emission and enhanced activity[J]. Applied Catalysis B: Environmental, 2017, 204: 475-485.
23	Chew L M, Kangvansura P, Ruland H, et al. Effect of nitrogen doping on the reducibility, activity and selectivity of carbon nanotube-supported iron catalysts applied in CO₂ hydrogenation[J]. Applied Catalysis A: General, 2014, 482: 163-170.
24	Williamson D L, Herdes C, Torrente-Murciano L, et al. N-Doped Fe@CNT for combined RWGS/FT CO₂ hydrogenation[J]. ACS Sustainable Chemistry & Engineering, 2019, 7(7): 7395-7402.
25	Li Y H, Cai X H, Chen S J, et al. Highly dispersed metal carbide on ZIF-derived pyridinic-N-doped carbon for CO₂ enrichment and selective hydrogenation[J]. ChemSusChem, 2018, 11(6): 1040-1047.
26	Zheng Y L, Cheng P, Xu J S, et al. MOF-derived nitrogen-doped nanoporous carbon for electroreduction of CO₂ to CO: the calcining temperature effect and the mechanism[J]. Nanoscale, 2019, 11(11): 4911-4917.
27	Hu S, Liu M, Ding F S, et al. Hydrothermally stable MOFs for CO₂ hydrogenation over iron-based catalyst to light olefins[J]. Journal of CO₂ Utilization, 2016, 15: 89-95.
28	Ramirez A, Gevers L, Bavykina A, et al. Metal organic framework-derived iron catalysts for the direct hydrogenation of CO₂ to short chain olefins[J]. ACS Catalysis, 2018, 8(10): 9174-9182.
29	Dong Z C, Zhao J, Tian Y J, et al. Preparation and performances of ZIF-67-derived FeCo bimetallic catalysts for CO₂ hydrogenation to light olefins[J]. Catalysts, 2020, 10(4): 455.
30	Visconti C G, Martinelli M, Falbo L, et al. CO₂ hydrogenation to lower olefins on a high surface area K-promoted bulk Fe-catalyst[J]. Applied Catalysis B: Environmental, 2017, 200: 530-542.
31	de Smit E, Cinquini F, Beale A M, et al. Stability and reactivity of ϵ-χ-θ iron carbide catalyst phases in Fischer-Tropsch synthesis: controlling μ(C)[J]. Journal of the American Chemical Society, 2010, 132(42): 14928-14941.
32	Ding M Y, Yang Y, Wu B S, et al. Study on reduction and carburization behaviors of iron phases for iron-based Fischer-Tropsch synthesis catalyst[J]. Applied Energy, 2015, 160: 982-989.
33	Ishida T, Yanagihara T, Liu X H, et al. Synthesis of higher alcohols by Fischer-Tropsch synthesis over alkali metal-modified cobalt catalysts[J]. Applied Catalysis A: General, 2013, 458: 145-154.

编辑推荐 0

Metrics

阅读次数

全文

835

HTML			PDF

最新录用	在线预览	正式出版	最新录用	在线预览	正式出版
2	0	21	38	0	774

来源	本网站	其他网站

次数	336	499
比例	40%	60%

摘要

890

最新录用	在线预览	正式出版

38	0	852

来源	本网站	其他网站

次数	618	272
比例	69%	31%

[1]	张义飞, 刘舫辰, 张双星, 杜文静. 超临界二氧化碳用印刷电路板式换热器性能分析[J]. 化工学报, 2023, 74(S1): 183-190.
[2]	杨欣, 王文, 徐凯, 马凡华. 高压氢气加注过程中温度特征仿真分析[J]. 化工学报, 2023, 74(S1): 280-286.
[3]	吴曦, 区祖迪, 张鑫杰, 徐士鸣, 朱晓静. HFO-1243zf爆燃特性实验研究[J]. 化工学报, 2023, 74(S1): 346-352.
[4]	宋瑞涛, 王派, 王云鹏, 李敏霞, 党超镔, 陈振国, 童欢, 周佳琦. 二氧化碳直接蒸发冰场排管内流动沸腾换热数值模拟分析[J]. 化工学报, 2023, 74(S1): 96-103.
[5]	李艺彤, 郭航, 陈浩, 叶芳. 催化剂非均匀分布的质子交换膜燃料电池操作条件研究[J]. 化工学报, 2023, 74(9): 3831-3840.
[6]	程业品, 胡达清, 徐奕莎, 刘华彦, 卢晗锋, 崔国凯. 离子液体基低共熔溶剂在转化CO₂中的应用[J]. 化工学报, 2023, 74(9): 3640-3653.
[7]	陈杰, 林永胜, 肖恺, 杨臣, 邱挺. 胆碱基碱性离子液体催化合成仲丁醇性能研究[J]. 化工学报, 2023, 74(9): 3716-3730.
[8]	杨学金, 杨金涛, 宁平, 王访, 宋晓双, 贾丽娟, 冯嘉予. 剧毒气体PH₃的干法净化技术研究进展[J]. 化工学报, 2023, 74(9): 3742-3755.
[9]	曹跃, 余冲, 李智, 杨明磊. 工业数据驱动的加氢裂化装置多工况切换过渡状态检测[J]. 化工学报, 2023, 74(9): 3841-3854.
[10]	杨绍旗, 赵淑蘅, 陈伦刚, 王晨光, 胡建军, 周清, 马隆龙. Raney镍-质子型离子液体体系催化木质素平台分子加氢脱氧制备烷烃[J]. 化工学报, 2023, 74(9): 3697-3707.
[11]	杨菲菲, 赵世熙, 周维, 倪中海. Sn掺杂的In₂O₃催化CO₂选择性加氢制甲醇[J]. 化工学报, 2023, 74(8): 3366-3374.
[12]	洪瑞, 袁宝强, 杜文静. 垂直上升管内超临界二氧化碳传热恶化机理分析[J]. 化工学报, 2023, 74(8): 3309-3319.
[13]	李凯旋, 谭伟, 张曼玉, 徐志豪, 王旭裕, 纪红兵. 富含零价钴活性位点的钴氮碳/活性炭设计及甲醛催化氧化应用研究[J]. 化工学报, 2023, 74(8): 3342-3352.
[14]	杨欣, 彭啸, 薛凯茹, 苏梦威, 吴燕. 分子印迹-TiO₂光电催化降解增溶PHE废水性能研究[J]. 化工学报, 2023, 74(8): 3564-3571.
[15]	余娅洁, 李静茹, 周树锋, 李清彪, 詹国武. 基于天然生物模板构建纳米材料及集成催化剂研究进展[J]. 化工学报, 2023, 74(7): 2735-2752.

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

RichHTML

PDF (PC)

可视化

摘要/Abstract

引用本文

使用本文

图/表 8

参考文献 33

相关文章 15

编辑推荐 0

Metrics

本文评价