Preparation of Fe-Mn catalyst by hydrothermal method and its catalytic activity for the synthesis of light olefins from CO hydrogenation
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摘要: 以水热合成法制备了K原位改性的Fe-Mn催化剂,考察了其CO加氢合成低碳烯烃催化活性。采用SEM、TEM、XRD、H2-TPR和FT-IR等手段对催化剂进行了表征。结果表明,制备的催化剂前驱体呈50~70 nm的球形颗粒,表面富含羰基和羟基,物相组成以Fe3O4为主,用于反应后有Fe5C2和MnCO3相生成。与共沉淀法制备催化剂相比,在设定的反应条件下,不同K含量改性的催化剂均具有较高的活性,以原料配比Fe:Mn:C6:K=3:1:5:0.10的催化剂性能最佳,CO转化率达95.02%,总低碳烯烃收率为62.86 g/m3(H2+CO),CH4和CO2选择性分别为13.88%和13.98%。Abstract: A series of potassium modified Fe-Mn catalysts were prepared by hydrothermal method and applied to the catalytic synthesis of light olefins from CO hydrogenation. The catalyst samples were characterized by SEM, TEM, XRD, H2-TPR and FT-IR techniques. Results showed that the prepared sample particles were spherical with 50~70 nm size and the carbonyl and hydroxy groups were observed on their surfaces. The bulk composition was mainly Fe3O4 before the reaction. Fe5C2 and MnCO3 were formed after the reaction. The prepared samples showed high activity and olefin selectivity under the given reaction conditions. Using the sample S3 (Fe:Mn:C6:K=3:1:5:0.10), the CO conversion and the olefin productivity reached 95.02% and 62.86 g/m3 (H2+CO), respectively. Compared with the catalyst prepared with co-precipitation method, the S3 catalyst had lower CH4 selectivity(13.88%) and CO2 selectivity(13.98%).
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Key words:
- Fe-Mn catalyst /
- hydrothermal method /
- CO hydrogenation /
- light olefins
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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, 4(10): 1201-1206. (DONG Li, YANG Xue-ping. New advances in direct production of light olefins from syngas[J]. Petrochemical Technology, 2012, 4(10): 1201-1206.) ZHANG Q H, KANG J C, WANG Y. Development of novel catalysts for Fischer-Tropsch synthesis: Tuning the product selectivity[J]. ChemCatChem, 2010, 2(9): 1030-1058. RAJE A P, DAVIS B H. Fischer-Tropsch synthesis over iron-based catalysts in a slurry reactor reaction rates, selectivities and implications for improving hydrocarbon productivity[J]. Catal Today, 1997, 36(6): 335-345. YANG Y, XIANG H W, ZHANG Y L. A highly active and stable Fe-Mn catalyst for slurry Fischer-Tropsch synthesis[J]. Catal Today, 2005, 106(12): 170-175. ZHOU J, CHU W, ZHANG H, XU H, ZHANG T. Effect of Fe content on FeMn catalysts for light alkenes synthesis[J]. Nat Gas Chem Ind, 2008, 2(3): 315-318. YANG Y, XIANG H W, XU Y Y, LI Y W. Effect of potassium promoter on precipitated iron-manganese catalyst for Fischer-Tropsch synthesis[J]. Appl Catal A: Gen, 2004, 266(2): 181-194. NING W S, KOIZUMI N, YAMADA M. Improvement of promoters on the Fischer Tropsch activity of mechanically mixed Fe catalysts[J]. Catal Commun, 2007, 8(3): 275-278. 张敬畅, 曹维良, 单伟力, 李梦波. 激光热解法制备铁基超微粒子催化剂及催化性能评价[J]. 催化学报, 1998, 19(1): 63-66. (ZHANG Jing-chang, CAO Wei-liang, SHAN Wei-li, LI Meng-bo. Preparation and characterization of Fe/ AC catalysts for synthesis of light olefins via carbon monoxide hydrogenation[J]. Chinese Journal of Catalysis, 1998, 19(1): 63-66.) GALVIS H M T, BITTER J H, KHARE C B, RUITENBEEK M, DUGULAN A L, JONG K P. Supported iron nanoparticles as catalysts for sustainable production of lower olefins[J]. Science, 2012, 335(2): 835-838. 禹国宾. 新型催化材料的制备及其在费托合成中的应用[D]. 复旦大学, 2009. (Yu Guo-bin. The preparation of a new catalytic material applying for F-T Synthesis[D]. Fudan University, 2009.) XU L, DU J, LI P, QIAN Y. In situ synthesis, magnetic property, and formation mechanism of Fe3O4 particles encapsulated in ID Bamboo-Shaped carbon microtubes[J]. J Phys Chem B, 2006, 110(5): 3871-3875. 付伯承. 碳包覆纳米四氧化三铁颗粒的合成与结构研究[D]. 北京化工大学, 2010. (FU Bo-cheng. Preparation and structure of carbon-encapsulated Fe3O4 nanoparticles[D]. Beijing University of Chemical Technology, 2010.) SUN X M, LIU J F, LI Y D. Use of carbonaceous polysaccharide microspheres as templates for fabricating metal oxide hollow spheres[J]. Chem Eur J, 2006, 12(7): 2039-2047. BUKUR D B, LANG X S, DING Y J. Pretreatment effect studies with a precipitated iron Fischer-Tropsch catalyst in a slurry reactor[J]. Appl Catal A: Gen, 1999, 186(1/2): 255-275. 李先国, 王琴, 钟炳, 彭少逸, 马玉刚, 吴东. 铁基超细粒子催化剂的F-T反应性能研究I. Fe-Mn催化剂的反应性能、活性相结构及锰的作用[J]. 燃料化学学报, 1993, 21(4): 344-349. (LI Xian-guo, WANG Qin, ZHONG Bing, PENG Shao-yi, MA Yu-gang, WU Dong. Studies on the F-T performance of iron based ultrafing catalysts I: Performance of Fe-Mn catalyst, active phases and role of Mn[J]. Journal of Fuel Chemistry and Technology, 1993, 21(4): 344-349.) LEITH I R, HOWDEN M G. Temperature-programmed reduction of mixed iron-manganese oxide catalysts in hydrogen and carbon monoxide[J]. Appl Catal, 1988, 27(2): 75-92.
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