合成气制低碳烯烃铁催化剂活性相的研究进展

doi:10.16085/j.issn.1000-6613.2019-0254

摘要/Abstract

摘要：

近年来，合成气制低碳烯烃铁基催化剂的研究备受广大研究者关注，但催化剂的活性相备受争议。大多数研究者认为碳化铁是合成气制低碳烯烃的活性相。本文归纳总结了近些年研究者对活性相碳化铁的研究，重点阐述了催化剂及其活性相的制备方法、还原气体、渗碳温度等因素对形成碳化铁的影响以及活性相碳化铁及暴露于催化剂表面的碳化铁晶面对合成气制低碳烯烃催化性能及产物分布的影响。今后工作的重点是进一步制备和研究不同结构的碳化铁活性相对目标产物的调控。此外，碳化铁的晶面对产物分布的影响也是未来的研究方向。

关键词: 合成气, 催化剂, 碳化铁, 活性相, 低碳烯烃

Abstract:

Recently, the research of iron-based catalysts for synthesis of light olefins from syngas has attracted much attention, but the active phase of the catalysts is controversial. However, it is generally accepted by many researchers that iron carbide is the active phase in Fischer-Tropsch to olefins (FTO). In the paper, the recent research on active phase iron carbide is summarized, and the effect preparation methods, reduction gas, carburizing temperature on iron carbide are emphatically described. In addition, this work elaborates the effect of iron carbide and the crystal facets exposed on the catalyst surface on the catalytic performance and product distribution in FTO process. Therefore, the key point of the future work will focus on further preparation and research the regulation of iron carbide with different structures to the target products. In addition, the research of the effect of iron carbide crystals on the distribution of products is also an important problem to be solved by researchers in the future.

Key words: syngas, catalysts, iron carbide, active phase, light olefins

中图分类号:

O643.36

王玲玉,韩文锋,刘化章,杨霞珍. 合成气制低碳烯烃铁催化剂活性相的研究进展[J]. 化工进展, 2019, 38(11): 4949-4955.

Lingyu WANG,Wenfeng HAN,Huazhang LIU,Xiazhen YANG. Research progress on active phase of iron-based catalysts for light olefins synthesis from syngas[J]. Chemical Industry and Engineering Progress, 2019, 38(11): 4949-4955.

图/表 5

参考文献 41

1	GALVIS H M T , BITTER J H , KHARE C B , et al . Supported iron nanoparticles as catalysts for sustainable production of lower olefins[J]. Science, 2012, 335(6070): 835-838.
2	CORMA A , MELO F V , SAUVANAUD L , et al . Light cracked naphtha processing: controlling chemistry for maximum propylene production[J]. Catalysis Today, 2005, 107/108: 699-706.
3	CHENG K , VIRGINIE M , ORDOMSKYO V V , et al . Pore size effects in high-temperature Fischer-Tropsch synthesis over supported iron catalysts[J]. Journal of Catalysis, 2015, 328: 139-150.
4	董丽, 杨学萍 . 合成气直接制低碳烯烃技术发展前景[J]. 石油化工, 2012, 41(10): 1201-1206.
	DONG L , YANG X P . New advances in direct production of light olefins from syngas[J]. Petrochemical Technology, 2012, 41(10): 1201-1206.
5	郭海军, 张海荣, 王璨, 等 . 合成气一步法直接转化制备低碳烯烃催化剂研究进展[J]. 新能源进展, 2017, 5(5): 358-364.
	GUO H J , ZHANG H R , WANG C , et al . Advances in catalysts for one-step direct conversion of syngas to light olefins[J]. Advances in New and Renewable Energy, 2017, 5(5): 358-364.
6	DE SMIT E , WECKHUYSEN B M . The renaissance of iron-based Fischer-Tropsch synthesis: on the multifaceted catalyst deactivation behaviour[J]. Chemical Society Reviews, 2008, 37(12): 2758-2781.
7	LIU Y , CHEN J F , ZHANG Y . Effects of pretreatment on iron-based catalysts for forming light olefins via Fischer-Tropsch synthesis[J]. Reaction Kinetics, Mechanisms and Catalysis, 2015, 114(2): 433-449.
8	LIU Y , CHEN J F , BAO J , et al . Manganese-modified Fe₃O₄ microsphere catalyst with effective active phase of forming light olefins from syngas[J]. ACS Catalysis, 2015, 5(6): 3905-3909.
9	蔡丽萍 . 助催化剂及工艺参数对Fe_(1- _x ₎O催化剂费-托合成性能的影响[D].杭州: 浙江工业大学,2006.
	CAI L P . Effect of promoters and reaction conditions on Fe_1- _x O-based iron catalysts for Fischer-Tropsch synthesis[D]. Hangzhou: Zhejiang University of Technology, 2006.
10	LI T Z , WANG H L , YANG Y , et al . Effect of manganese on the catalytic performance of an iron-manganese bimetallic catalyst for light olefin synthesis[J]. Journal of Energy Chemistry, 2013, 22(4): 624-632.
11	ZHAO M , CUI Y , SUN J C , et al . Modified iron catalyst for direct synthesis of light olefin from syngas[J]. Catalysis Today, 2018, 316: 142-148.
12	GAO X H , ZHANG J l , CHEN N , et al . Effects of zinc on Fe-based catalysts during the synthesis of light olefins from the Fischer-Tropsch process[J]. Chinese Journal of Catalysis, 2016, 37 (4): 510-516.
13	WANG G C , ZHANG K , LIU P , et al . Synthesis of light olefins from syngas over Fe-Mn-V-K catalysts in the slurry phase[J]. Journal of Industrial and Engineering Chemistry, 2013, 19 (3): 961-965.
14	GALVIS H M T , DE JONG K P . Catalysts for production of lower olefins from synthesis gas: a review[J]. ACS Catalysis, 2013, 3(9): 2130-2149.
15	夏航, 杨霞珍, 霍超, 等 . 合成气一步制取低碳烯烃铁基催化剂的研究进展[J]. 现代化工, 2016,36(8):19-23.
	XIA H , YANG X Z , HUO C , et al . Research progress of iron-based catalyst for direct conversion of synthesis gas to light olefins[J]. Modern Chemical Industry, 2016, 36(8): 19-23.
16	SAGE V , BURKE N . Use of probe molecules for Fischer-Tropsch mechanistic investigations: a short review[J]. Catalysis Today, 2011, 178(1): 137-141.
17	GU B , ORDOMSKY V V , BAHRI M , et al . Effects of the promotion with bismuth and lead on direct synthesis of light olefins from syngas over carbon nanotube supported iron catalysts[J]. Applied Catalysis B: Environmental, 2018, 234: 153-166.
18	JIAO F , LI J J , PAN X L , et al . Selective conversion of syngas to light olefins[J]. Science, 2016, 351(6277): 1065-1068.
19	CHANG Q , ZHANG C H , LIU C W , et al . Relationship between iron carbide phases (ε-Fe₂C, Fe₇C₃, and χ˗Fe₅C₂) and catalytic performances of Fe/SiO₂ Fischer-Tropsch catalysts[J]. ACS Catalysis, 2018, 8(4): 3304-3316.
20	PARK B J , JANG S H , LEE J H, et al . Hyperactive iron carbide@N-doped reduced graphene oxide/carbon nanotube hybrid architecture for rapid CO hydrogenation[J]. Journal of Materials Chemistry A, 2018, 6(24): 11134-11139.
21	OBRIEN R J , XU L G , SPICER R L , et al . Activation study of precipitated iron Fischer-Tropsch catalysts[J]. Energy & Fuels, 1996, 10(4): 921-926.
22	TONG A , DAN D, YI C . Effect of reduction and carburization pretreatment on iron catalyst for synthesis of light olefins from CO hydrogenation[J]. Chemical Research in Chinese Universities, 2017, 33(4): 672-677.
23	LIU X W , ZHAO S , MENG Y , et al . Mössbauer spectroscopy of iron carbides: from prediction to experimental confirmation[J]. Scientific Reports, 2016, 6: 26184.
24	DING M Y , YANG Y , XU J , et al . Effect of reduction pressure on precipitated potassium promoted iron-manganese catalyst for Fischer-Tropsch synthesis[J]. Applied Catalysis A: General, 2008, 345(2): 176-184.
25	WANG X B , CHEN X D , DING H , et al . Synthesis and magnetic properties of Fe₃C doped with Mn or Ni for applications as adsorbents[J]. Dyes and Pigments, 2017, 144: 76-79.
26	YANG C , ZHAO H B , HOU Y L , et al . Fe₅C₂ Nanoparticles: a facile bromide-induced synthesis and as an active phase for Fischer-Tropsch synthesis[J]. Journal of the American Chemical Society, 2012, 134(38): 15814-15821.
27	WANG P , CHEN W , CHIANG F K , et al . Synthesis of stable and low-CO₂ selective ε-iron carbide Fischer-Tropsch catalysts[J]. Science Advances, 2018, 4(10): 2947.
28	PHAM T H , DUAN X Z , QIAN G , et al . CO activation pathways of Fischer-Tropsch synthesis on χ-Fe₅C₂ (510): direct versus hydrogen-assisted CO dissociation[J]. Journal of Physical Chemistry C, 2014, 118(19): 10170-10176.
29	WANG D , CHEN B X , DUAN X Z , et al . Iron-based Fischer-Tropsch synthesis of lower olefins: the nature of χ-Fe₅C₂, catalyst and why and how to introduce promoters[J]. Journal of Energy Chemistry, 2016, 25(6): 911-916.
30	KANG S W , KIM K , CHUN D H , et al . High-performance Fe₅C₂@CMK-3 nanocatalyst for selective and high-yield production of gasoline-range hydrocarbons[J]. Journal of Catalysis, 2017, 349: 66-74.
31	HU E L , YU X Y , CHEN F , et al . Graphene layers-wrapped Fe/Fe₅C₂ nanoparticles supported on N-doped graphene nanosheets for highly efficient oxygen reduction[J]. Advanced Energy Materials, 2017, 8(9): 1702476.
32	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.
33	XIANG M L , ZOU J , LI Q H , et al . Catalytic performance of iron carbide for carbon monoxide hydrogenation[J]. Journal of Natural Gas Chemistry, 2010, 19(5): 468-470.
34	HERRANZ T , ROJAS S , PEREZ-ALONSO F J , et al . Genesis of iron carbides and their role in the synthesis of hydrocarbons from synthesis gas[J]. Journal of Catalysis, 2006, 243(1): 199-211.
35	DE SMIT E , BEALE A M , NIKITENKO S , et al . Local and long range order in promoted iron-based Fischer-Tropsch catalysts: a combined in situ X-ray absorption spectroscopy/wide angle X-ray scattering study[J]. Journal of Catalysis, 2009, 262(2): 244-256.
36	CAER G L , DUBOIS J M , PIJOLAT M , et al . Characterization by Mössbauer spectroscopy of iron carbides formed by Fischer-Tropsch synthesis[J]. Journal of Physical Chemistry, 1982, 86(24): 4799-4808.
37	XU K , SUN B , LIN J , et al . ε-Iron carbide as a low-temperature Fischer-Tropsch synthesis catalyst[J]. Nature Communications, 2014, 5: 5783.
38	LIU X W , ZHAO S , MENG Y , et al . Mössbauer spectroscopy of iron carbides: from prediction to experimental confirmation[J]. Scientific Reports, 2016, 6: 26184.
39	ZHAO S , LIU X W , HUO C F , et al . Potassium promotion on CO hydrogenation on the χ-Fe₅C₂(111) surface with carbon vacancy[J]. Applied Catalysis A: General, 2017, 534: 22-29.
40	GALVIS H M T , BITTER J H , DAVIDIAN T , et al . Iron particle size effects for direct production of lower olefins from synthesis gas[J]. Journal of the American Chemical Society, 2012, 134(39): 16207-16215.
41	ZHAO S , LIU X W , HUO C F , et al . The role of potassium promoter in surface carbon hydrogenation on Hägg carbide surfaces[J]. Applied Catalysis A: General, 2015, 493: 68-76.

[1]	张明焱, 刘燕, 张雪婷, 刘亚科, 李从举, 张秀玲. 非贵金属双功能催化剂在锌空气电池研究进展[J]. 化工进展, 2023, 42(S1): 276-286.
[2]	时永兴, 林刚, 孙晓航, 蒋韦庚, 乔大伟, 颜彬航. 二氧化碳加氢制甲醇过程中铜基催化剂活性位点研究进展[J]. 化工进展, 2023, 42(S1): 287-298.
[3]	谢璐垚, 陈崧哲, 王来军, 张平. 用于SO₂去极化电解制氢的铂基催化剂[J]. 化工进展, 2023, 42(S1): 299-309.
[4]	杨霞珍, 彭伊凡, 刘化章, 霍超. 熔铁催化剂活性相的调控及其费托反应性能[J]. 化工进展, 2023, 42(S1): 310-318.
[5]	王乐乐, 杨万荣, 姚燕, 刘涛, 何川, 刘逍, 苏胜, 孔凡海, 朱仓海, 向军. SCR脱硝催化剂掺废特性及性能影响[J]. 化工进展, 2023, 42(S1): 489-497.
[6]	邓丽萍, 时好雨, 刘霄龙, 陈瑶姬, 严晶颖. 非贵金属改性钒钛基催化剂NH₃-SCR脱硝协同控制VOCs[J]. 化工进展, 2023, 42(S1): 542-548.
[7]	程涛, 崔瑞利, 宋俊男, 张天琪, 张耘赫, 梁世杰, 朴实. 渣油加氢装置杂质沉积规律与压降升高机理分析[J]. 化工进展, 2023, 42(9): 4616-4627.
[8]	王鹏, 史会兵, 赵德明, 冯保林, 陈倩, 杨妲. 过渡金属催化氯代物的羰基化反应研究进展[J]. 化工进展, 2023, 42(9): 4649-4666.
[9]	张启, 赵红, 荣峻峰. 质子交换膜燃料电池中氧还原反应抗毒性电催化剂研究进展[J]. 化工进展, 2023, 42(9): 4677-4691.
[10]	王伟涛, 鲍婷玉, 姜旭禄, 何珍红, 王宽, 杨阳, 刘昭铁. 醛酮树脂基非金属催化剂催化氧气氧化苯制备苯酚[J]. 化工进展, 2023, 42(9): 4706-4715.
[11]	葛亚粉, 孙宇, 肖鹏, 刘琦, 刘波, 孙成蓥, 巩雁军. 分子筛去除VOCs的研究进展[J]. 化工进展, 2023, 42(9): 4716-4730.
[12]	吴海波, 王希仑, 方岩雄, 纪红兵. 3D打印催化材料开发与应用进展[J]. 化工进展, 2023, 42(8): 3956-3964.
[13]	向阳, 黄寻, 魏子栋. 电催化有机合成反应的活性和选择性调控研究进展[J]. 化工进展, 2023, 42(8): 4005-4014.
[14]	王耀刚, 韩子姗, 高嘉辰, 王新宇, 李思琪, 杨全红, 翁哲. 铜基催化剂电还原二氧化碳选择性的调控策略[J]. 化工进展, 2023, 42(8): 4043-4057.
[15]	刘毅, 房强, 钟达忠, 赵强, 李晋平. Ag/Cu耦合催化剂的Cu晶面调控用于电催化二氧化碳还原[J]. 化工进展, 2023, 42(8): 4136-4142.