Ce改性Ni/KIT-6催化剂上乙醇干气重整反应

摘要利用"一锅法"制备了Ce改性KIT-6载体，通过甲醇辅助浸渍法合成担载型Ni/Ce-KIT-6和Ni/KIT-6催化剂。利用BET、SEM、TEM、H₂-TPR、XRD和Raman等表征手段分别对催化剂物理化学性质进行分析。结果表明助剂Ce的掺杂可以抑制活性金属Ni在焙烧过程中的烧结，提高活性组分Ni的分散度以及金属-载体间的相互作用。进一步考察了Ce改性对Ni/KIT-6催化剂的乙醇干气重整反应性能的影响。测试结果表明，Ce添加有利于提高Ni基催化剂的活性和稳定性；Ni/Ce-KIT-6催化剂的乙醇和CO₂转化率均高于未掺杂的Ni/KIT-6催化剂，并且具有较高的H₂和CO选择性。60 h连续稳定性测试中Ni/Ce-KIT-6催化剂未失活，催化剂表面无明显积碳。Ce助剂的氧化还原能力（Redox）可以有效活化CO₂分子，提供活性氧原子，实现催化剂表面积碳的动态消除，提高催化剂稳定性。

	Service

	把本文推荐给朋友
	加入我的书架
	加入引用管理器
	Email Alert
	RSS
	作者相关文章
	隗义琛
	蔡伟杰
	谭凤芝
	刘宪云

关键词： Ni KIT-6 乙醇干气重整合成气

Abstract： The Ce modified KIT-6 carrier was prepared by "one-pot method", and the supported Ni/Ce-KIT-6 and Ni/KIT-6 catalysts were synthesized by methanol-assisted impregnation method. BET, SEM, TEM, H₂-TPR, XRD and Raman spectroscopy were performed to analyze the physical and chemical properties of the catalyst. The results show that the doping of the additive Ce can inhibit the sintering of the active metal Ni during the calcination process, but improve the dispersion of the active component Ni and the interaction between the metal and the carrier. The effect of doping of Ce on the performance of Ni/KIT-6 catalyst in ethanol dry gas reforming was further investigated. The results show that doping of Ce is beneficial to improve the activity and stability of the Ni-based catalyst; the conversions of ethanol and CO₂ catalyzed by Ni/Ce-KIT-6 catalyst are higher than that by the undoped Ni/KIT-6 catalyst, and the selectivity for hydrogen and CO are high. In the 60-hour continuous stability test, the Ni/Ce-KIT-6 catalyst was not deactivated, and there was no significant carbon deposition on the catalyst surface. The redox capability of Ce additives can effectively activate CO₂ molecules, provide active oxygen atoms, realize the dynamic elimination of carbon deposited on the catalyst surface, and improve the stability of the catalyst.

Keywords： Ni； KIT-6； ethanol； dry gas reforming； syngas

Received 2020-03-07;

Fund:辽宁省自然科学基金（20170540073）；大连市科技之星专项基金（2017RQ130）。

Corresponding Authors: 蔡伟杰,E-mail:caiweijie1978@163.com。 Email: caiweijie1978@163.com

About author: 隗义琛(1992-),男,硕士研究生,现从事CO₂催化转化方面的研究。

引用本文:

隗义琛, 蔡伟杰, 谭凤芝, 刘宪云.Ce改性Ni/KIT-6催化剂上乙醇干气重整反应[J]. 化学工业与工程, 2020,37(6): 10-17

Wei Yichen, Cai Weijie, Tan Fengzhi, Liu Xianyun.Ethanol Dry Reforming over Ce Modified Ni/KIT-6 Catalyst[J]. Chemcial Industry and Engineering, 2020,37(6): 10-17

[1] 杨东明, 梁相程. CO₂绿色利用技术[J]. 当代化工, 2019, 48(8):1838-1841 Yang Dongming, Liang Xiangcheng. Discussion on CO₂ green utilization technology[J]. Contemporary Chemical Industry, 2019, 48(8):1838-1841(in Chinese)
[2] Artz J, Mullr T E, Thenert J, et al. Sustainable conversion of carbon dioxide:An integrated review of catalysis and life cycle assessment[J]. Chem Rev, 2018, 118(2):434-450
[3] 范莎莎, 沈辉, 赵玉军, 等. 氧化钙吸附剂的制备及CO₂吸附性能[J]. 化学工业与工程, 2016, 33(4):7-10, 22 Fan Shasha, Shen Hui, Zhao Yujun, et al. Preparation and adsorption capacity of calcium-based sorbent[J]. Chemical Industry and Engineering, 2016, 33(4):7-10, 22(in Chinese)
[4] Abdulrasheed A, Jalil A A, Gambo Y, et al. A review on catalyst development for dry reforming of methane to syngas:Recent advances[J]. Renewable and Sustainable Energy Reviews, 2019, 108:175-193
[5] Li J, He Y L, Tan L, et al. Integrated tuneable synthesis of liquid fuels via Fischer-Tropsch technology[J]. Nature Catalysis, 2018, 1(10):787-793
[6] Bahari M B, Phuc N H H, Alenazey F, et al. Catalytic performance of La-Ni/Al₂O₃ catalyst for CO₂ reforming of ethanol[J]. Catalysis Today, 2017, 291:67-75
[7] Aramouni N A K, Touma J G, Tarboush B A, et al. Catalyst design for dry reforming of methane:Analysis review[J]. Renewable and Sustainable Energy Reviews, 2018, 82:2570-2585
[8] Qu F, Wei Y, Cai W, et al. Syngas production from carbon dioxide reforming of ethanol over Ir/Ce_0.75Zr_0.25O₂ catalyst:Effect of calcination temperatures[J]. Energy & Fuels, 2018, 32(2):2104-2116
[9] Zhao S, Cai W, Li Y, et al. Syngas production from ethanol dry reforming over Rh/CeO₂ catalyst[J]. J Saudi Chem Soc, 2018, 22(1):58-65
[10] 阮勇哲, 卢遥, 王胜平. 甲烷干重整Ni基催化剂失活及抑制失活研究进展[J]. 化工进展, 2018, 37(10):3850-3857 Ruan Yongzhe, Lu Yao, Wang Shengping. Progress in deactivation and anti-deactivation of nickel-based catalysts for methane dry reforming[J]. Chemical Industry and Engineering Progress, 2018, 37(10):3850-3857(in Chinese)
[11] 曹红霞, 张军, 郭成龙, 等. 三维介孔KIT-6上高分散Ni纳米粒子用于CO甲烷化:助剂对催化性能的影响[J]. 催化学报, 2017, 38(7):1127-1137 Cao Hongxia, Zhang Jun, Guo Chenglong, et al. Highly dispersed Ni nanoparticles on 3D-mesoporous KIT-6 for CO methanation:Effect of promoter species on catalytic performance[J]. Chinese Journal of Catalysis, 2017, 38(7):1127-1137(in Chinese)
[12] Li Z, Miao Z, Wang X, et al. One-Pot synthesis of ZrMo-KIT-6 solid acid catalyst for solvent-free conversion of glycerol to solketal[J]. Fuel, 2018, 233:377-387
[13] Han Y, Wen B, Zhu M, et al. Lanthanum incorporated in MCM-41 and its application as a support for a stable Ni-based methanation catalyst[J]. Journal of Rare Earths, 2018, 36(4):367-373
[14] Mousavi S M, Meshkani F, Rezaei M. Synthesis of nanocrystalline Ce_0.95Mn_0.05O₂ solid solution powders as support for nickel catalyst in dry reforming reaction[J]. Journal of Environmental Chemical Engineering, 2017, 5(6):5493-5500
[15] Zhi G, Guo X, Wang Y, et al. Effect of La₂O₃ modification on the catalytic performance of Ni/SiC for methanation of carbon dioxide[J]. Catalysis Communications, 2011, 16(1):56-59
[16] Li D, Zeng L, Li X, et al. Ceria-Promoted Ni/SBA-15 catalysts for ethanol steam reforming with enhanced activity and resistance to deactivation[J]. Applied Catalysis B:Environmental, 2015, 176/177:532-541
[17] Yan X, Hu T, Liu P, et al. Highly efficient and stable Ni/CeO₂-SiO₂ catalyst for dry reforming of methane:Effect of interfacial structure of Ni/CeO₂ on SiO₂[J]. Applied Catalysis B:Environmental, 2019, 246:221-231
[18] Li M S, van Veen A C. Tuning the catalytic performance of Ni-catalysed dry reforming of methane and carbon deposition via Ni-CeO_2-x interaction[J]. Applied Catalysis B:Environmental, 2018, 237:641-648
[19] Cao D, Zeng F, Zhao Z, et al. Cu based catalysts for syngas production from ethanol dry reforming:Effect of oxide supports[J]. Fuel, 2018, 219:406-416
[20] Jankhah S, Abatzoglou N, Gitzhofer F, et al. Catalytic properties of carbon nano-filaments produced by iron-catalysed reforming of ethanol[J]. Chemical Engineering Journal, 2008, 139(3):532-539
[21] Song H, Ozkan U S. Ethanol steam reforming over Co-based catalysts:Role of oxygen mobility[J]. Journal of Catalysis, 2009, 261(1):66-74