二氧化碳加氢合成低碳烯烃的研究进展

doi:10.16085/j.issn.1000-6613.2015.10.035

摘要/Abstract

摘要： 大气中逐年升高的二氧化碳浓度对全球环境产生了严重的影响。通过可再生能源得到的H₂与CO₂反应生成低碳烯烃,不但可以使CO₂得到资源化利用,还能减少低碳烯烃的生产对于石油资源的依赖。该技术还有望实现从海水中得到燃油。本文主要对CO₂加氢合成低碳烯烃的热力学、反应机理和催化剂研究进行了综述。目前,该反应中使用的催化剂以Fe系为主。文中简要介绍了直接转化催化剂中的载体、助剂和双金属活性组分对反应性能的影响以及经甲醇路线制低碳烯烃的双功能催化剂在该反应中的应用。高性能催化剂的设计以及反应机理的探索是CO₂加氢合成低碳烯烃未来的发展方向。

关键词: 二氧化碳, 加氢, 低碳烯烃, 催化剂

Abstract: Year by year, the accelerated accumulation of greenhouse gas, CO₂, in the atmosphere, has a serious impact on the global environment. The clean hydrogen resource, obtained from renewable energy, opens up an attractive route for simultaneous conversion of CO₂ into light olefins, which is regarded as a promising process for CO₂ utilization. This process also reduces the light olefins production dependence on petroleum consumption, and makes the achievement of fuel from seawater available. In this paper, the thermodynamics, the reaction mechanism and catalysts of carbon dioxide hydrogenation to light olefins were reviewed. At present, Fe-based catalysts are mainly studied in this reaction. Therefore, the influence of the catalyst supports, promoters and bimetallic active components on the performance of direct conversion of CO₂ into light olefins, as well as the utilization of bi-functional catalysts via the synthesis of methanol intermediates in this reaction, were briefly introduced. In the future, it shall be focused on the design of high performance catalyst and clarifying the reaction mechanism.

Key words: carbon dioxide, hydrogenation, light olefins, catalyst

中图分类号:

TQ032.4

梁兵连, 段洪敏, 侯宝林, 苏雄, 黄延强, 王爱琴, 王晓东, 张涛. 二氧化碳加氢合成低碳烯烃的研究进展[J]. 化工进展, 2015, 34(10): 3746-3754.

LIANG Binglian, DUAN Hongmin, HOU Baolin, SU Xiong, HUANG Yanqiang, WANG Aiqin, WANG Xiaodong, ZHANG Tao. Progress in the catalytic hydrogenation of carbon dioxide to light olefins[J]. Chemical Industry and Engineering Progree, 2015, 34(10): 3746-3754.

参考文献

[1] Wang W,Wang S,Ma X,et al. Recent advances in catalytic hydrogenation of carbon dioxide[J]. Chemical Society Reviews,2011,40(7):3703-3727.

[2] 李静,邓廷云,杨林,等. CO₂ 吸附活化及催化加氢制低碳烯烃的研究进展[J]. 化工进展,2013,32(2):340-345.

[3] Rodemerck U,Holeňa M,Wagner E,et al. Catalyst development for CO₂ hydrogenation to fuels[J]. Chem. Cat. Chem.,2013,5(7):1948-1955.

[4] Dorner R W,Hardy D R,Williams F W,et al. Heterogeneous catalytic CO₂ conversion to value-added hydrocarbons[J]. Energy & Environmental Science,2010,3(7):884-890.

[5] Kondratenko E V,Mul G,Baltrusaitis J,et al. Status and perspectives of CO₂ conversion into fuels and chemicals by catalytic,photocatalytic and electrocatalytic processes[J]. Energy & Environmental Science,2013,6(11):3112-3135.

[6] Centi G,Quadrelli E A,Perathoner S. Catalysis for CO₂ conversion:A key technology for rapid introduction of renewable energy in the value chain of chemical industries[J]. Energy & Environmental Science,2013,6(6):1711-1731.

[7] 许文娟,马丽萍,黄彬,等. CO₂ 催化加氢研究进展[J]. 化工进展,2009,28(s1):284-289.

[8] Saeidi S,Amin N A S,Rahimpour M R. Hydrogenation of CO₂ to value-added products——A review and potential future developments[J]. Journal of CO₂ Utilization,2014,5:66-81.

[9] Dorner R W,Hardy D R,Williams F W,et al. C₂-C₅+ olefin production from CO₂ hydrogenation using ceria modified Fe/Mn/K catalysts[J]. Catalysis Communications,2011,15(1):88-92.

[10] Dorner R W,Willauer H D,Hardy D R,et al. Effects of loading and doping on iron-based CO₂ hydrogenation catalysts[R]. NRL/MR/6180-09-9200. Washington,D C:Naval Research Laboratory. 2009.

[11] Willauer H D,Hardy D R,Schultz K R,et al. The feasibility and current estimated capital costs of producing jet fuel at sea using carbon dioxide and hydrogen[J]. Journal of Renewable and Sustainable Energy,2012,4(3):033111.

[12] Drab D M,Willauer H D,Olsen M T,et al. Hydrocarbon synthesis from carbon dioxide and hydrogen:A two-step process[J]. Energy & Fuels,2013,27(11):6348-6354.

[13] 刘业奎,王黎,侯栋,等.二氧化碳加氢合成低碳烯烃反应平衡体系热力学研究[J]. 催化学报,2004,25(3):210-218.

[14] Torrente-Murciano L,Mattia D,Jones M D,et al. Formation of hydrocarbons via CO₂ hydrogenation——A thermodynamic study[J]. Journal of CO₂ Utilization,2014,6:34-39.

[15] 徐龙伢,王清遐,梁东白,等. CO₂加氢制低碳烯烃的Fe/Silicalite-2催化剂研究[J]. 天然气化工,1995,20(5):6-10.

[16] Wang J J,You Z,Zhang Q,et al. Synthesis of lower olefins by hydrogenation of carbon dioxide over supported iron catalysts[J]. Catalysis Today,2013,215:186-193.

[17] Hu B,Frueh S,Garces H F,et al. Selective hydrogenation of CO₂ and CO to useful light olefins over octahedral molecular sieve manganese oxide supported iron catalysts[J]. Applied Catalysis B:Environmental,2013,132-133:54-61.

[18] Gupta N M,Kamble V S,Iyer R M. Effect of γ-irradiation on methanation of carbon dioxide over supported Ru catalysts[J]. Journal of Catalysis,1980,66(1):101-111.

[19] Gupta N,Kamble V,Rao K A,et al. On the mechanism of CO and CO₂ methanation over Ru/molecular-sieve catalyst[J]. Journal of Catalysis,1979,60(1):57-67.

[20] Willauer H D,Ananth R,Olsen M T,et al. Modeling and kinetic analysis of CO₂ hydrogenation using a Mn and K-promoted Fe catalyst in a fixed-bed reactor[J]. Journal of CO₂ Utilization,2013,3:56-64.

[21] Torres Galvis H M,de Jong K P. Catalysts for production of lower olefins from synthesis gas:A review[J]. ACS Catalysis,2013,3(9):2130-2149.

[22] Wang C,Xu L,Wang Q. Review of directly producing light olefins via CO hydrogenation[J]. Journal of Natural Gas Chemistry,2003,12(1):10-16.

[23] Zhang Q,Kang J,Wang Y. Development of novel catalysts for Fischer-Tropsch synthesis:Tuning the product selectivity[J]. Chem. Cat. Chem.,2010,2(9):1030-1058.

[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(6070):835-838.

[25] 李梦青,邓国才,陈荣悌,等. FeCoMnK/BeO催化剂上二氧化碳加氢合成低碳烯烃的反应性能和原位FT-IR研究[J]. 催化学报,2000,21(1):71-74.

[26] Riedel T,Schaub G,Jun K-W,et al. Kinetics of CO₂ hydrogenation on a K-promoted Fe catalyst[J]. Ind. Eng. Chem. Res.,2001,5(40):1355-1363.

[27] 郑斌,张安峰,刘民,等.纳米铁基催化剂在CO₂加氢制烃中的性能[J]. 物理化学学报,2012,28(8):1943-1950.

[28] 郑斌. 二氧化碳加氢制烃类铁基催化剂的制备及性能[D]. 大连:大连理工大学,2012.

[29] 卢振举,林培滋,徐长海,等. CO₂+H₂直接合成低碳烯烃的研究[J]. 天然气化工,1993,18(1):23-27.

[30] Chew L M,Ruland H,Schulte H J,et al. CO₂ hydrogenation to hydrocarbons over iron nanoparticles supported on oxygen-functionalized carbon nanotubes[J]. Journal of Chemical Sciences,2014,126(2):481-486.

[31] Owen R E,O'Byrne J P,Mattia D,et al. Promoter effects on iron-silica Fischer-Tropsch nanocatalysts:Conversion of carbon dioxide to lower olefins and hydrocarbons at atmospheric pressure[J]. Chem. Plus. Chem.,2013,78(12):1536-1544.

[32] Ding F,Zhang A,Liu M,et al. Effect of SiO₂-coating of FeK/Al₂O₃ catalysts on their activity and selectivity for CO₂ hydrogenation to hydrocarbons[J]. RSC Advances,2014,4(17):8930.

[33] 王湘波. 二氧化碳加氢合成低碳烯烃催化剂的研究[D]. 长春:长春工业大学,2012.

[34] You Z Y,Deng W,Zhang Q,et al. Hydrogenation of carbon dioxide to light olefins over non-supported iron catalyst[J]. Chinese Journal of Catalysis,2013,34(5):956-963.

[35] 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.

[36] Dorner R W,Hardy D R,Williams F W,et al. Effects of ceria-doping on a CO₂ hydrogenation iron-manganese catalyst[J]. Catalysis Communications,2010,11(9):816-819.

[37] 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.

[38] Satthawong R,Koizumi N,Song C,et al. Comparative study on CO₂ hydrogenation to higher hydrocarbons over Fe-based bimetallic catalysts[J]. Topics in Catalysis,2014,(57):588-594.

[39] 刘歆颖,邓国才,郭先芝,等.铁镍双金属催化剂用于二氧化碳加氢合成低碳烯烃的研究[J]. 燃料化学学报,1999,27(5):447-450.

[40] 刘歆颖,邓国才,陈荣悌,等.铁钴双金属催化剂上二氧化碳加氢合成低碳烯烃[J]. 燃料化学学报,1999,27(2):145-149.

[41] Li B,Wang J,Yuan Y,et al. Carbon nanotube-supported rufe bimetallic nanoparticles as efficient and robust catalysts for aqueous-phase selective hydrogenolysis of glycerol to glycols[J]. ACS Catalysis,2011,1(11):1521-1528.

[42] Fujimoto K,Shikada T. Selective synthesis of C₂-C₅ hydrocarbons from carbon dioxide utilizing a hybrid catalyst composed of a methanol synthesis catalyst and zeolite[J]. Applied Catalysis,1987,31(1):13-23.

[43] Bai R X,Tan Y,Han Y. Study on the carbon dioxide hydrogenation to iso-alkanes over Fe-Zn-M/zeolite composite catalysts[J]. Fuel Processing Technology,2004,86(3):293-301.

[44] Inui T,Takeguchi T. Effective conversion of carbon dioxide and hydrogen to hydrocarbons[J]. Catalysis Today,1991,10(1):95-106.

[45] Fujiwara M,Sakurai H,Shiokawa K,et al. Synthesis of C₂₊ hydrocarbons by CO₂ hydrogenation over the composite catalyst of Cu-Zn-Al oxide and HB zeolite using two-stage reactor system under low pressure[J]. Catalysis Today,2015,242:255-260.

[46] 桂霞,王陈魏,云志,等.燃烧前CO₂捕集技术研究进展[J]. 化工进展,2014,33(7):1895-1901.

[47] Keith D W,Ha-duong M,Stolaroff J K. Climate strategy with CO₂ capture from the air[J]. Climatic Change,2006,74(1-3):2006.

[48] Sumida K,Rogow D L,Mason J A,et al. Carbon dioxide capture in metal-organic frameworks[J]. Chem. Rev.,2012,112(2):724-781.

[49] Furukawa H,Ko N,Go Y B,et al. Ultrahigh porosity in metal-organic frameworks[J]. Science,2010,329(5990):424-428.

[50] 郑修新,张晓云,余青霓,等. CO₂吸收材料的研究进展[J]. 化工进展,2012,31(2):360-366.

[51] 张立武,单春晖. 新型CO₂捕获材料研究进展[J]. 化工新型材料,2011,39(9):18-20.