Ni/ZrO2催化剂的制备及甲烷分步水蒸气重整反应性能

doi:10.16085/j.issn.1000-6613.2017-0790

摘要/Abstract

摘要： 采用沉淀法制备了ZrO₂载体，进一步采用浸渍法制备了不同Ni负载量的Ni/ZrO₂催化剂。通过XRD、N₂物理吸附、H₂-TPR和H₂-TPD等表征手段对Ni/ZrO₂催化剂的物理结构和化学特性进行了研究，探讨了活性金属Ni物种的状态，并计算了Ni粒子的大小。随着Ni负载量的增加，Ni/ZrO₂催化剂的比表面积逐渐减小，金属Ni的分散度逐渐减小，Ni粒子尺寸逐渐增大，低温H₂脱附峰所占比例逐渐增大。当Ni负载量为10.2%（质量分数）时，Ni/ZrO₂催化剂上ZrO₂晶粒的平均尺寸和Ni粒子的尺寸大小均接近30nm。进一步考察了Ni/ZrO₂催化剂在甲烷分步水蒸气重整反应中的催化性能。结果表明，Ni负载量在一定范围内的Ni/ZrO₂催化剂对于甲烷分步水蒸气重整反应具有良好的催化性能，Ni负载量过高或过低均不利于甲烷的转化。当Ni负载量为10.2%时，载体ZrO₂粒子和金属Ni粒子尺寸匹配，Ni/ZrO₂催化剂表现出最佳的甲烷转化活性和稳定性。

关键词: Ni/ZrO₂, 甲烷, 重整, 表征

Abstract: A series of Ni/ZrO₂ catalysts with different amount of nickel loadings were prepared via impregnation method using zirconium dioxide as the carrier, while zirconium dioxide was firstly obtained through precipitation from zirconium salts and calcination treatment. X-ray diffraction (XRD), nitrogen physical adsorption, hydrogen temperature programmed reduction (H₂-TPR), and hydrogen temperature programmed desorption (H₂-TPD)techniques were utilized to analyze the physical and chemical properties of the prepared catalysts. The possible status of the active nickel species were investigated and the diameters of nickel and nickel oxide aggregates were calculated. With the increase of the loading amount of nickel, both the BET area of the Ni/ZrO₂ catalysts and the dispersion degree of nickel decreased, while the diameter of the nickel aggregates and the portion of the desorption area in the H₂-TPD curves increased. When the loading amount of nickel was around 10.2%, the diameter of the nickel aggregates and that of zirconia dioxide crystals were close to 30nm. The performance of Ni/ZrO₂ catalysts was further investigated based on the reaction of stepwise steam reforming of methane. The results indicated that the Ni/ZrO₂ catalysts could exhibit excellent performance only when the amount of nickel loading was in some range. Both insufficient and excess amount of nickel loadings would lower the catalytic conversion of methane. When the loading amount of nickel was around 10.2%, the catalyst showed the best performance in that the zirconium dioxide particles had similar size to that of the nickel species.

Key words: Ni/ZrO₂, methane, reforming, characterization

中图分类号:

TQ426.8

姜健准, 刘红梅, 张明森. Ni/ZrO₂催化剂的制备及甲烷分步水蒸气重整反应性能[J]. 化工进展, 2018, 37(01): 112-118.

JIANG Jianzhun, LIU Hongmei, ZHANG Mingsen. Preparation of Ni/ZrO₂ catalyst and its performance in the reaction of stepwise steam reforming of methane[J]. Chemical Industry and Engineering Progress, 2018, 37(01): 112-118.

参考文献

[1] CHAN S H,STEMPIEN J P,DING O L,et al. Fuel cell and hydrogen technologies research,development and demonstration activities in Singapore-Au update[J]. Int. J. Hydogen Energ.,2016,41(32):13869-13878.
[2] YURDAKUL M,AYAS N,BIZKARRA K,et al. Preparation of Ni-based catalysts to produce hydrogen from glycerol by steam reforming process[sJ]. Int. J. Hydogen Energ.,2016,41(20):8084-8091.
[3] YOU Y W,MOON E H,HEO I,et al. Preparation and characterization of porous carbons from ion-exchange resins with different degree of cross-linking for hydrogen storage[J]. J. Ind. Eng. Chem.,2017,45:164-170.
[4] PENG W Q,LAN Z Q,WEI W L,et al. Investigation on preparation and hydrogen storage performance of Mg17Al12 alloy[J]. Int. J. Hydogen Energ.,2016,41(3):1759-1765.
[5] ALMASOUDI A,MOKAYA R. Preparation and hydrogen storage capacity of templated and activated carbons nanocast from commercially available zeolitic imidazolate framework[J]. J. Mater. Chem.,2012,22:146-152.
[6] DONG B X,TIAN H,WU Y C,et al. Improved electrolysis of liquid ammonia for hydrogen generation via ammonium salt electrolyte and Pt/Rh/Ir electrocatalysts[J]. Int. J. Hydogen Energ.,2016,41(33):14507-14518.
[7] 朱凌岳,王宝辉,吴红军. 电解水煤浆制氢技术研究进展[J]. 化工进展,2016,35(10):3129-3135. ZHU L Y,WANG B H,WU H J. Review on electrochemical splitting of coal water slurry for hydrogen[J]. Chemical Industry and Engineering Progress,2016,35(10):3129-3135.
[8] SELLAMI M H,LOUDIYI K. Electrolytes behavior during hydrogen production by solar energy[J]. Renew. Sust. Energ. Rev.,2017,70:1331-1335.
[9] 刘红梅,徐向亚,冯静,等. Ni/Al₂O₃催化剂上甲烷自热重整制合成气反应[J]. 石油化工,2016,45(2):149-155. LIU H M,XU X Y,FENG J,et al. Study on Ni/Al₂O₃ catalysts for methane autothermal reforming to syngas[J]. Petrochemical Technology,2016,45(2):149-155.
[10] 闫月君,刘启斌,隋军,等. 甲醇水蒸气催化重整制氢技术研究进展[J]. 化工进展,2012,31(7):1468-1476. YAN Y J,LIU Q B,SUI J,et al. Research progress of hydrogen production with methanol steam reforming[J]. Chemical Industry and Engineering Progress,2012,31(7):1468-1476.
[11] 李磊,郭瓦力,李俊磊,等. 丙三醇水蒸气重整制氢M/Al₂O₃催化剂[J]. 化工进展,2013,32(1):122-128. LI L,GUO W L,LI J L,et al. M/Al₂O₃ catalysts for hydrogen production via the steam reforming of glycerin[J]. Chemical Industry and Engineering Progress,2013,32(1):122-128.
[12] JUNG S H,CHOI B,PARK S,et al. Hydrogen production by compact combined dimethyl ether reformer/combustor for automotive applications[J]. Int. J. Hydrogen Energ.,2017,42(19):13463-13476.
[13] SONG C S,PAN W. Tri-reforming of methane:a novel concept for catalytic production of industrially useful synthesis gas with desired H₂/CO ratios[J]. Catal. Today,2004,98:463-484.
[14] CHOUDHARY T V,GOODMAN D W. CO-free production of hydrogen via stepwise steam reforming of methane[J]. J. Catal.,2000,192:316-321.
[15] CHOUDHARY T V,GOODMAN D W. Stepwise methane steam reforming:a route to CO-free hydrogen[J]. Catal. Lett.,1999,59:93-94.
[16] CHOUDHARY V R,BANERJEE S,RAJPUT A M. Hydrogen from step-wise steam reforming of methane over Ni/ZrO₂:factors affecting catalytic methane decomposition and gasification by steam of carbon formed on the catalyst[J]. Appl. Catal. A:Gen.,2002,234(1/2):259-270.
[17] CHOUDHARY V R,BANERJEE S,RAJPUT A M. Continuous production of H₂ at low temperature from methane decomposition over Ni-containing catalyst followed by gasification by steam of the carbon on the catalyst in two parallel reactors operated in cyclic manner[J]. J. Catal,2001,198(1):136-141.
[18] CHOUDHARY T V,SIVADINARAYANA C,CHUSUEI C,et al. Hydrogen production via catalytic decomposition of methane[J]. J. Catal.,2001,199(1):9-18.
[19] 郑文涛,李金刚,吴昊,等. 甲烷分步重整制氢催化剂研究进展[J]. 精细石油化工进展,2008,9(7):24-28. ZHENG W T,LI J G,WU H,et al. Research progress on catalysts for stepwise reforming of methane for hydrogen production[J]. Advances in Fine Petrochemicals,2008,9(7):24-28.
[20] 刘少文,李永丹. 甲烷重整制氢气的研究进展[J]. 武汉化工学院学报,2005,27(1):20-24. LIU S W,LI Y D. Research proceeding for methane reforming for hydrogen[J]. J. Wuhan Inst. Chem. Tech.,2005,27(1):20-24.
[21] LI Y D,CHEN J L,QIN Y N,et al. Simultaneous production of hydrogen and nanocarbon from decomposition of methane on a nickel-based catalyst[J]. Energ. Fuel.,2000,14(6):1188-1194.
[22] JAYAKUMAR S,ANANTHAPADMANABHAN P V,PERUMAL K,et al. Characterization of nano-crystalline ZrO₂ synthesized via reactive plasma processing[J]. Mater. Sci. Eng. B,2011,176:894-899.
[23] SU C L,LI J R,HE D H,et al. Synthesis of isobutene from synthesis gas over nanosize zirconia catalysts[J]. Appl. Catal. A,2000,202(1):81-89.
[24] 魏俊梅,徐柏庆,孙科强,等. CO₂重整CH₄纳米ZrO₂负载Ni催化剂的研究(Ⅱ)——催化剂组成与反应条件对催化剂性能的影响[J]. 高等学校化学学报,2002,23(11):2106-2111. WEI J M,XU B Q,SUN K Q,et al. CO₂ reforming of CH₄ over Ni supported on nano-ZrO₂ (Ⅱ)-effect of catalyst composition and reaction conditions on catalytic reactivity[J]. Chem. J. Chinese Univ.,2002,23(11):2106-2111.
[25] ROSSETTIA I,BIFFIA C,CLAUDIA L,et al. Ni/SiO₂ and Ni/ZrO₂ catalysts for the steam reforming of ethanol[J]. Appl. Catal. B:Environ.,2012,117/118:384-396.
[26] SONG Y Q,HE D H,XU B Q. Effects of preparation methods of ZrO₂ support on catalytic performances of Ni/ZrO₂ catalysts in methane partial oxidation to syngas[J]. Appl. Catal. A:Gen.,2008,337(1):19-28.

Ni/ZrO₂催化剂的制备及甲烷分步水蒸气重整反应性能

Preparation of Ni/ZrO₂ catalyst and its performance in the reaction of stepwise steam reforming of methane

PDF (PC)

可视化

摘要/Abstract

引用本文

使用本文

参考文献

相关文章 15

编辑推荐

Metrics

本文评价

[1]	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.
[2]	许家珩, 李永胜, 罗春欢, 苏庆泉. 甲醇水蒸气重整工艺的优化[J]. 化工进展, 2023, 42(S1): 41-46.
[3]	赖诗妮, 江丽霞, 李军, 黄宏宇, 小林敬幸. 含碳掺氨燃料的研究进展[J]. 化工进展, 2023, 42(9): 4603-4615.
[4]	黄玉飞, 李子怡, 黄杨强, 金波, 罗潇, 梁志武. 光催化CO₂和CH₄重整催化剂研究进展[J]. 化工进展, 2023, 42(8): 4247-4263.
[5]	奚永兰, 王成成, 叶小梅, 刘洋, 贾昭炎, 曹春晖, 韩挺, 张应鹏, 田雨. 微纳米气泡在厌氧消化中的应用研究进展[J]. 化工进展, 2023, 42(8): 4414-4423.
[6]	刘洋, 叶小梅, 苗晓, 王成成, 贾昭炎, 曹春晖, 奚永兰. 农村有机生活垃圾干发酵氨胁迫下中试工艺[J]. 化工进展, 2023, 42(7): 3847-3854.
[7]	张凯, 吕秋楠, 李刚, 李小森, 莫家媚. 南海海泥中甲烷水合物的形貌及赋存特性[J]. 化工进展, 2023, 42(7): 3865-3874.
[8]	鲁少杰, 刘佳, 冀芊竹, 李萍, 韩月阳, 陶敏, 梁文俊. 硅藻土基复合填料制备及滴滤塔去除二甲苯的性能[J]. 化工进展, 2023, 42(7): 3884-3892.
[9]	王俊杰, 潘艳秋, 牛亚宾, 俞路. 分子水平催化重整装置模型构建及应用[J]. 化工进展, 2023, 42(7): 3404-3412.
[10]	马源, 肖晴月, 岳君容, 崔彦斌, 刘姣, 许光文. CeO₂-Al₂O₃复合载体负载Ni基催化剂催化CO _x 共甲烷化性能[J]. 化工进展, 2023, 42(5): 2421-2428.
[11]	阮鹏, 杨润农, 林梓荣, 孙永明. 甲烷催化部分氧化制合成气催化剂的研究进展[J]. 化工进展, 2023, 42(4): 1832-1846.
[12]	龚陈俊, 梅道锋. 钨修饰对镍载氧体的沼气化学链重整制氢性能影响[J]. 化工进展, 2023, 42(4): 2130-2141.
[13]	张巍, 王锐, 缪平, 田戈. 全球可再生能源电转甲烷的应用[J]. 化工进展, 2023, 42(3): 1257-1269.
[14]	何阳东, 常宏岗, 王丹, 陈昌介, 李雅欣. 熔融金属法甲烷裂解制氢和碳材料研究进展[J]. 化工进展, 2023, 42(3): 1270-1280.
[15]	祝佳欣, 朱雯喆, 徐俊, 谢靖, 王文标, 谢丽. 基于导电材料强化抗生素胁迫厌氧消化的研究进展[J]. 化工进展, 2023, 42(2): 1008-1019.