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

doi:10.11949/0438-1157.20200653

摘要/Abstract

摘要：

铁基催化剂CO₂加氢直接合成烯烃是实现CO₂减排及CO₂转化与利用的最佳途径之一。目前铁基催化剂的CO₂加氢活性及反应过程中铁基催化剂结构强度仍然较低，成为CO₂加氢制烯烃产业化生产的重要挑战。通过浸渍法制备一系列负载型铁基催化剂，研究载体材料性质对铁基催化剂结构及CO₂加氢直接合成烯烃的影响特性。研究发现，载体可诱导铁基催化剂在CO₂加氢反应过程中形成的铁物种，同时影响铁基催化剂表面碳物种的有序度，调变对CO₂吸附及活化能力；研究结果表明ZrO₂负载的Fe催化剂展现出最佳的CO₂加氢合成烯烃催化性能，在温度320℃和反应压力2.0 MPa时，CO₂转化率>30%，C₂~C₇烃类产物中烯烃选择性高达85%以上，烯烷比为8.2，且CO选择性较低为17.1%。

关键词: 二氧化碳, 加氢, 催化剂, 载体, 烯烃, 铁物种, 碱金属, 钠, 表面碳物种

Abstract:

The direct synthesis of olefins by CO₂ hydrogenation with iron-based catalysts is one of the best ways to achieve CO₂ emission reduction and CO₂ conversion and utilization. At present, the CO₂ hydrogenation activity and structural strength of the iron-based catalysts are still relatively low during CO₂ hydrogenation process, which has become an important challenge for the industrialization of CO₂ hydrogenation to olefins. In this work, a series of the supported iron-based catalyst was prepared by the impregnation method to study the influence of the properties of support materials on the structure of iron-based catalysts and the reactivities of the direct synthesis of olefins from CO₂ hydrogenation. This work found that the support induced the iron species formed during the process of CO₂ hydrogenation, simultaneously affected the order degree of carbon species on the surface of iron-based catalyst, and tuned the capability of CO₂ adsorption and the activities of CO₂ activation. The results shown that the Fe-based catalyst supported on ZrO₂ exhibited the best catalytic performance for CO₂ hydrogenation to olefins at 320℃ and 2.0 MPa. The CO₂ conversion (>30%) and the selectivity of olefins in C₂—C₇ hydrocarbon products were as high as over 85%, the ratio of olefins to paraffins was 8.2, and the CO selectivity was 17.1%.

Key words: carbon dioxide, hydrogenation, catalyst, support, olefins, iron species, alkali metal, Na, surface carbon species

中图分类号:

O 643.3

刘洋洋, 孙超, Malhi Haripal Singh, 位重洋, 张振洲, 涂维峰. 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.

Yangyang LIU, Chao SUN, Malhi Haripal Singh, Chongyang WEI, Zhenzhou ZHANG, Weifeng TU. 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.

图/表 8

图1 不同载体材料负载的Fe基催化剂CO2加氢反应性能[反应条件：320℃、2.0 MPa、CO2/H2/Ar=1/3/3和空速9000 ml/(g·h)]

Fig.1 Catalytic performance of the Fe based catalysts supported on different supports for CO2 hydrogenation [reaction conditions：320℃, 2.0 MPa, CO2/H2/Ar =1/3/3 and GHSV=9000 ml/(g·h)]

表1 负载型Fe基催化剂CO2加氢性能

Table 1 Performance of supported Fe catalysts for CO2 hydrogenation

催化剂	CO₂转化率 /%	含碳产物的选择性/C%			C₂~C₇烷烃和烯烃的选择性/C%		C₂~C₇烃类 O/P比	C₂~C₇⁼ 时空产率/(g/(kg·h))
催化剂	CO₂转化率 /%	CO	CH₄	C₂~C₇	C₂~C₇^o	C₂~C₇⁼	C₂~C₇烃类 O/P比	C₂~C₇⁼ 时空产率/(g/(kg·h))
FeNa/SiO₂	18.9	68.3	27.9	4.8	50.4	49.6	1.0	3.0
FeNa/Al₂O₃	38.4	10.0	34.4	55.6	50.1	49.9	1.0	67.8
FeNa/ZrO₂	32.6	17.1	20.2	62.7	10.8	89.2	8.2	111.4

表2 载体和负载型Fe催化剂的物理化学性质

Table 2 Physicochemical properties of supports and supported Fe catalysts

催化剂	BET / (m²/g)^①	总孔容v/ (cm³/g)^②	平均孔径d /nm^②	Fe₂O₃尺寸/nm^③
SiO₂	311.66	1.09	10.96	—
Al₂O₃	150.44	0.57	11.98	—
ZrO₂	4.39	0.04	25.87	—
FeNa/SiO₂	167.43	0.51	9.30	16.7
FeNa/Al₂O₃	140.31	0.38	8.30	15.9
FeNa/ZrO₂	14.20	0.08	18.82	19.0

图2 不同载体负载的Fe基催化剂前体的CO程序升温还原（CO-TPR）曲线

Fig.2 CO-TPR profiles of Fe-based catalyst precursor on different supports

图3 不同载体负载Fe基催化剂的XRD谱图[反应条件：320℃、2 MPa、CO2/H2/Ar=1/3/3和空速9000 ml/(g·h)]

Fig.3 XRD patterns of Fe-based catalyst on different supports [reaction conditions：320℃, 2 MPa, CO2/H2/Ar =1/3/3 and GHSV=9000 ml/(g·h)]

图4 不同载体负载的Fe基催化剂的拉曼光谱图[反应条件：320℃、2 MPa、CO2/H2/Ar=1/3/3和空速9000 ml/(g·h)]

Fig.4 Raman spectra of Fe-based catalyst on different supports [reaction conditions：320℃, 2 MPa, CO2/H2/Ar =1/3/3 and GHSV=9000 ml/(g·h)]

图5 H2预处理的载体和催化剂在50℃、Ar流中CO2吸附稳定后的红外光谱图

Fig.5 FTIR spectra of H2 pretreated supports and catalysts after CO2 adsorption and stabilization in Ar flow at 50℃

图6 载体对铁物种演化的影响及由此调节CO2加氢制烯烃的示意图

Fig.6 Schematic diagram of the effect of supports on the evolution of iron species and consequent tuning the hydrogenation of CO2 to olefins

参考文献 47

1	白雪楠, 白昕, 尤慧君. 中国碳交易市场发展现状及问题分析[J]. 中外企业家, 2020, 14: 100.
	Bai X N, Bai X, You H J. Development status and problems of carbon trading market in China [J]. Chinese and Foreign Entrepreneurs, 2020, 14: 100.
2	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.
3	靳治良, 钱玲, 吕功煊. 二氧化碳化学—现状及展望[J]. 化学进展, 2010, 22(6): 1102-1115.
	Jin Z L, Qian L, Lyu G X. CO₂ Chemistry—actuality and expectation[J]. Progress in Chemistry, 2010, 22(6): 1102-1115.
4	Wang S, Xi C. Recent advances in nucleophile-triggered CO₂-incorporated cyclization leading to heterocycles[J]. Chem. Soc. Rev., 2019, 48(1): 382-404.
5	成康, 张庆红, 康金灿, 等. 二氧化碳直接制备高值化学品中的接力催化方法[J]. 中国科学: 化学, 2020, 50(7): 743-755.
	Cheng K, Zhang Q H, Kang J C, et al. Relay catalysis in the direct conversion of carbon dioxide to high-value chemicals[J]. Sci. Sin. Chim., 2020, 50(7): 743-755.
6	陈倩倩, 顾宇, 唐志永, 等. 以二氧化碳规模化利用技术为核心的碳减排方案[J]. 中国科学院院刊, 2019, 34(4): 478-487.
	Chen Q Q, Gu Y, Tang Z Y, et al. Carbon dioxide sizable utilization technology based carbon reduction solutions[J]. Bulletin of the Chinese Academy of Sciences, 2019, 34(4): 478-487.
7	金涌, 周禹成, 胡山鹰. 低碳理念指导的煤化工产业发展探讨[J]. 化工学报, 2012, 63(1): 3-8.
	Jin Y, Zhou Y C, Hu S Y. Discussion on development of coal chemical industry using low-carbon concept[J]. CIESC Journal, 2012, 63(1): 3-8.
8	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.
9	高新华, 王康洲, 张建利, 等. CO/CO₂催化加氢双功能催化剂新进展[J]. 石油学报(石油加工), 2019, 35(6): 1228-1238.
	Gao X H, Wang K Z, Zhang J L, et al. Recent advances in bifunctional catalysts for hydrogenation of CO/CO₂[J]. Acta Petrolei Sinica(Petroleum Processing Section), 2019, 35(6): 1228-1238.
10	高鹏, 崔勖, 钟良枢, 等. CO/CO₂加氢高选择性合成化学品和液体燃料[J]. 化工进展, 2019, 38(1): 183-195.
	Gao P, Cui X, Zhang L S, et al. CO/CO₂ hydrogenation to chemicals and liquid fuels with high selectivity[J]. Chemical Industry and Engineering Progress, 2019, 38(1): 183-195.
11	Jiao F, Li J J, Pan X L, et al. Selective conversion of syngas to light olefins[J]. Science, 2016, 351: 1065-1068.
12	Wei C Y, Tu W F, Jia L Y, et al. The evolutions of carbon and iron species modified by Na and their tuning effect on the hydrogenation of CO₂ to olefins[J]. Applied Surface Science, 2020, DOI: 10.1016/j.apsusc.2020.146622. DOI
13	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.
14	Liang B L, Sun T, Ma J G, et al. Mn decorated Na/Fe catalysts for CO₂ hydrogenation to light olefins[J]. Catal. Sci. Technol., 2019, 9 (2): 456-464.
15	Zhang Z Z, Wei C Y, Jia L Y, et al. Insights into the regulation of FeNa catalysts modified by Mn promoter and their tuning effect on the hydrogenation of CO₂ to light olefins[J]. Journal of Catalysis, 2020, 390: 12-22.
16	Liu J H, Zhang A F, Jiang X, et al. Overcoating the surface of Fe-based catalyst with ZnO and nitrogen-doped carbon toward high selectivity of light olefins in CO₂ hydrogenation[J]. Ind. Eng. Chem. Res, 2019, 58 (10): 4017-4023.
17	Cheng K, Virginie M, Ordomsky 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.
18	Numpilai T, Chanlek N, Poo-Arporn Y, et al. Pore size effects on physicochemical properties of Fe-Co/K-Al₂O₃ catalysts and their catalytic activity in CO₂ hydrogenation to light olefins[J]. Applied Surface Science, 2019, 483: 581-592.
19	张俊, 张征湃, 苏俊杰, 等. 载体碱性对Fe基催化剂费-托合成反应的影响[J]. 化工学报, 2016, 67(2): 549-556.
	Zhang J, Zhang Z P, Su J J, et al. Effect of support basicity on iron based catalysts for Fischer-Tropsch synthesis[J]. CIESC Journal, 2016, 67(2): 549-556.
20	Wang J J, You Z Y, Zhang Q H, et al. Synthesis of lower olefins by hydrogenation of carbon dioxide over supported iron catalysts[J]. Catalysis Today, 2013, 215: 186-193.
21	Gu H, Ding J, Zhong Q, et al. Promotion of surface oxygen vacancies on the light olefins synthesis from catalytic CO₂ hydrogenation over Fe–K/ZrO₂ catalysts[J]. International Journal of Hydrogen Energy, 2019, 44(23): 11808-11816.
22	Lu J Z, Yang L J, Xu B L, et al. Promotion effects of nitrogen doping into carbon nanotubes on supported iron Fischer–Tropsch catalysts for lower olefins[J]. ACS Catalysis, 2014, 4(2): 613-621.
23	Su X J, Zhang J L, Fan S B, et al. Effect of preparation of Fe-Zr-K catalyst on the product distribution of CO₂ hydrogenation[J]. RSC Advances, 2015, 5(98): 80196-80202.
24	Torres Galvis H M, Bitter J H, Khare C B, et al. Supported iron nanoparticles as catalysts for sustainable production of lower olefins[J]. Science, 2012, 335: 835-838.
25	Park J Y, Lee Y J, Khanna P K, et al. Alumina-supported iron oxide nanoparticles as Fischer-Tropsch catalysts: effect of particle size of iron oxide[J]. Journal of Molecular Catalysis A: Chemical, 2010, 323(1/2): 84-90.
26	Lee Y H, Lee D W, Kim H, et al. Fe–Zn catalysts for the production of high-calorie synthetic natural gas[J]. Fuel, 2015, 159: 259-268.
27	Jin Y, Datye A K. Phase transformations in iron Fischer–Tropsch catalysts during temperature-programmed reduction[J]. Journal of Catalysis, 2000, 196(1): 8-17.
28	Li S Z, Li A W, Krishnamoorthy S, et al. Effects of Zn, Cu, and K promoters on the structure and on the reduction, carburization, and catalytic behavior of iron-based Fischer–Tropsch synthesis catalysts[J]. Catalysis Letters, 2001, 77(4): 197-205.
29	Zhang C H, Wan H J, Yang Y, et al. Study on the iron–silica interaction of a co-precipitated Fe/SiO₂ Fischer–Tropsch synthesis catalyst[J]. Catalysis Communications, 2006, 7(9): 733-738.
30	Yuen S, Kubsh J E, Dumesic J A, et al. Metal oxide-support interactions in silica-supported iron oxide catalysts probed by nitric oxide adsorption[J]. The Journal of Physical Chemistry, 1982, 86(15): 3022-3032.
31	Xie T Z, Wang J Y, Ding F S, et al. CO₂ hydrogenation to hydrocarbons over alumina-supported iron catalyst: effect of support pore size[J]. Journal of CO₂ Utilization, 2017, 19: 202-208.
32	Wu J H, Wang L C, Yang X, et al. Support effect of the Fe/BN catalyst on Fischer–Tropsch performances: role of the surface B-O defect[J]. Industrial & Engineering Chemistry Research, 2018, 57(8): 2805-2810.
33	Zhang Y L, Cao C X, Zhang C, et al. The study of structure-performance relationship of iron catalyst during a full life cycle for CO₂ hydrogenation[J]. Journal of Catalysis, 2019, 378: 51-62.
34	Pham T H, Qi Y Y, Yang J, et al. Insights into Hägg iron-carbide-catalyzed Fischer–Tropsch synthesis: suppression of CH₄ formation and enhancement of C–C coupling on χ-Fe₅C₂ (510)[J]. ACS Catalysis, 2015, 5(4): 2203-2208.
35	Moodley D J, van de loosdrecht J, Saib A M, et al. Carbon deposition as a deactivation mechanism of cobalt-based Fischer–Tropsch synthesis catalysts under realistic conditions[J]. Applied Catalysis A: General, 2009, 354(1/2): 102-110.
36	Zhang Y L, Fu D D, Liu X L, et al. Operando spectroscopic study of dynamic structure of iron oxide catalysts during CO₂ hydrogenation[J]. ChemCatChem, 2018, 10(6): 1272-1276.
37	Zhang Z P, Zhang J, Wang X, et al. Promotional effects of multiwalled carbon nanotubes on iron catalysts for Fischer-Tropsch to olefins[J]. Journal of Catalysis, 2018, 365: 71-85.
38	Thomsen C, Reich S. Double resonant Raman scattering in graphite[J]. Physical Review Letters, 2000, 85(24): 5214-5217.
39	Tuinstra F, Koenig J L. Raman spectrum of graphite[J]. The Journal of Chemical Physics, 1970, 53(3): 1126-1130.
40	Gruver V, Young R, Engman J, et al. The role of accumulated carbon in deactivating cobalt catalysts during FT synthesis in a slurry-bubble-column reactor[J]. American Chemical Society, Division of Petroleum Chemistry, Preprints, 2005, 50: 164-166.
41	Solis-Garcia A, Louvier-Hernandez J F, Almendarez-Camarillo A, et al. Participation of surface bicarbonate, formate and methoxy species in the carbon dioxide methanation catalyzed by ZrO₂-supported Ni[J]. Applied Catalysis B: Environmental, 2017, 218: 611-620.
42	Takano H, Kirihata Y, Izumiya K, et al. Highly active Ni/Y-doped ZrO₂ catalysts for CO₂ methanation[J]. Applied Surface Science, 2016, 388: 653-663.
43	Szamyi J, Kwak J H. Dissecting the steps of CO₂ reduction(1). The interaction of CO and CO₂ with γ-Al₂O₃: an in situ FTIR study[J]. Phys Chem Chem Phys, 2014, 16(29): 15117-15125.
44	Proano L, Tello E, Arellano-Trevino M A, et al. In-situ DRIFTS study of two-step CO₂ capture and catalytic methanation over Ru, "Na₂O"/Al₂O₃ dual functional material[J]. Applied Surface Science, 2019, 479: 25-30.
45	Szanyi J, Kwak J H. Dissecting the steps of CO₂ reduction(2). The interaction of CO and CO₂ with Pd/γ-Al₂O₃: an in situ FTIR study[J]. Phys. Chem. Chem. Phys., 2014, 16(29): 15126-15138.
46	Guo J Z, Hou Z Y, Gao J, et al. DRIFTS study on adsorption and activation of CH₄ and CO₂ over Ni/SiO₂ catalyst with various Ni particle sizes[J]. Chinese Journal of Catalysis, 2007, 28(1): 22-26.
47	Chang K, Ordomsky V V, Legras B, et al. Sodium-promoted iron catalysts prepared on different supports for high temperature Fischer-Tropsch synthesis[J]. Applied Catalysis A: General, 2015, 502: 204-214.

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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

Effects of identities of supports on Fe-based catalyst and their consequences on activities of CO₂ hydrogenation to olefins

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