透氧膜反应器内NiO/MgO催化甲烷重整反应的途径

doi:10.3969/j.issn.1007-2861.2013.06.005

上海大学学报(自然科学版) ›› 2013, Vol. 19 ›› Issue (6): 572-578.doi: 10.3969/j.issn.1007-2861.2013.06.005

透氧膜反应器内NiO/MgO催化甲烷重整反应的途径

杨志彬1, 丁伟中2

1. 江苏科技大学张家港校区冶金与材料工程学院, 江苏张家港 215600; 2. 上海大学上海市现代冶金与材料制备重点实验室, 上海 200072

出版日期:2013-12-30 发布日期:2013-12-30
通讯作者: 杨志彬(1981—), 男, 博士, 研究方向为冶金环境保护和资源回收利用. E-mail:zhibinyang@shu.edu.cn
作者简介:杨志彬(1981—), 男, 博士, 研究方向为冶金环境保护和资源回收利用.
基金资助:
国家自然科学基金资助项目(51304082); 江苏省自然科学基金资助项目(BK20130462); 江苏省高校自然科学基金资助项目(12KJB450001); 江苏科技大学人才引进基金资助项目(35271103); 江苏科技大学青年教师科研基金资助项目(112110108)

Reaction Pathways of Reforming of Methane over NiO/MgO Catalyst in Oxygen Permeation Membrane Reactor

YANG Zhi-bin1, DING Wei-zhong2

1. School of Metallurgy and Materials Engineering, Zhangjiagang Campus, Jiangsu University of Science and Technology, Zhangjiagang 215600, Jiangsu, China; 2. Shanghai Key Laboratory of Modern Metallurgy and Material Processing, Shanghai University, Shanghai 200072, China

Online:2013-12-30 Published:2013-12-30

摘要/Abstract

摘要： 在透氧膜反应器内对比分析了不加催化剂和添加 1 g 9% Ni/γ -Al2O3 催化剂的甲烷重整反应实验. 结果表明, 不加催化剂时甲烷相对较惰性; 而在催化剂的作用下, 甲烷重整活性得到了较大提高, 但是催化剂易积碳. 推测甲烷重整反应路径如下: 甲烷在催化剂活性组分上发生裂解, 产生氢和碳; 生成的氢与膜表面的氧反应生成 H₂O,从而使得膜表面侧氧分压下降, 透氧量增大. 通过设计不同 Ni 含量 NiO/MgO 催化剂下的甲烷裂解和甲烷重整反应实验, 验证了以上的反应机理模型.

关键词: 反应途径, 甲烷, 透氧膜反应器, 重整反应

Abstract: Reforming reaction of methane was carried out in an oxygen permeation membrane reactor, and fed with methane and Ar. A comparative analysis of the oxygen permeation performance under the condition of CH₄ diluted by Ar with 1 g 9% Ni/γ -Al₂O₃ catalyst and without catalyst was performed to investigate the reaction pathways. According to the results, the reaction pathways are deduced. The dissociation of CH₄ on catalyst first formed surface C species and H₂. The producted H₂ is then reacted with oxygen diffused or spilt over catalyst from membrane to form H₂O, causing the oxygen partial pressure to decrease, and the flux of oxygen to increase. This paper further shows the pathways of CH4 dissociation and H₂ oxidation, through catalytic partial oxidation of methane over NiO/MgO catalysts with different Ni contents in an oxygen permeation membrane reactor.

Key words: methane, oxygen permeation membrane reactor, reaction pathway, reforming reaction

中图分类号:

TQ 031.2

杨志彬1, 丁伟中2. 透氧膜反应器内NiO/MgO催化甲烷重整反应的途径[J]. 上海大学学报(自然科学版), 2013, 19(6): 572-578.

YANG Zhi-bin1, DING Wei-zhong2. Reaction Pathways of Reforming of Methane over NiO/MgO Catalyst in Oxygen Permeation Membrane Reactor[J]. Journal of Shanghai University（Natural Science Edition）, 2013, 19(6): 572-578.

参考文献

[1] Dov ` ? V G, Friedler F, Huisingh D, et al. Cleaner energy for sustainable future [J]. J Cleaner Production, 2009, 17(10): 889-895.

[2] Hashemnejad S M, Parvari M. Deactivation and regeneration of nickel-based catalysts for steammethane reforming [J]. Chin J Catal, 2011, 32: 273-279.

[3] Fidalgo B, Menendez´ A J. Carbon materials as catalysts for decomposition and CO₂ reforming of methane: a review [J]. Chin J Catal, 2011, 32: 207-216.

[4] Daza C E, Moreno S, Molina R. Co-precipitated Ni-Mg-Al catalysts containing Ce for CO₂ reforming of methane [J]. Int J Hydrogen Energy, 2011, 36: 3886-3894.

[5] Dantas S C, Resende R L, Rossi R L, et al. Hydrogen production from oxidative reforming of methane on supported nickel catalysts: an experimental and modeling study [J]. Chem Engin J, 2012, 197: 407-413.

[6] Fan M S, Abdullah A Z, Bhatia S. Hydrogen production from carbon dioxide reforming of methane over Ni-Co/MgO-ZrO₂ catalyst: process optimization [J]. Int J Hydrogen Energy, 2011, 36: 4875-4886.

[7] 徐军科, 李兆静, 汪吉汇, 等. 甲烷干重整催化剂Ni/Al2O3 表面积炭表征与分析 [J]. 物理化学学报, 2009, 25: 253-260.

[8] Nakagawa K, Ikenalca N, Teng Y, et al. Transient response of catalyst bed temperature in the pulsed reaction of partial oxidation of methane to synthesis gas over supported rhodium and iridium catalysts [J]. J Catal, 1999, 186: 405.
[9] Ashcroft A T, Cheetham A K, Foord J S, et al. Selective oxidation of methane to synthesis gas using transition metal catalysts [J]. Nature, 1990, 344: 319-321.

[10] Hickman D A, Schmidt L D. Syngas formation by direct catalytic oxidation of methane [J]. Science, 1993, 259: 343-346.

[11] Hickman DA, Schmidt LD. Synthesis gas formation by direct oxidation of methane over Pt monoliths [J]. J Catal, 1992, 138: 267-274.

[12] Lapszewicz J A, Jiang X. Investigation of the mechanism of the partial oxidation of methane to synthesis gas [J]. J American Chemistry Society, 1992, 37(1): 252-260.

[13] Choudhary V R, Rajput A M, Mamman A S. NiOalkaline earth oxide catalysts for oxidative methaneto-syngas conversion: influence of alkaline earth oxide on the surface properties and temperature-programmed reduction/reaction by H2 and methane [J]. J Catal, 1998, 178(2): 576-585.

[14] Hofstad K H, Hoebink J H B J, Holmen A, et al. Partial oxidation of methane to synthesis gas over rhodium catalysts [J]. Catal Today, 1998, 40: 157-170.

[15] Ruckenstein E, Wang H Y. Partial oxidation of methane to synthesis gas over MgO-supported Rh catalysts: the effect of precursor of MgO [J]. Appl Catal A: Gen, 2000, 198: 33-41.

[16] Buyevskaya O V, Wolf D, Baerns M. Rhodiumcatalyzed partial oxidation of methane to CO and H₂ transient studies on its mechanism [J]. Catal Lett, 1994, 29: 249-260.

[17] Mallens E P J, Hoebink J H B J, Marin G B. An investigation on the reaction mechanism for the partial oxidation of methane to synthesis gas over platinum [J]. Catal Lett, 1995, 33: 291-304.

[18] Matsumura Y, Moffat J B. Oxidative methane conversion to carbon monoxide and hydrogen at low reactor wall temperatures over ruthenium supported on silica [J]. Catal Lett, 1994, 24: 59-65.

[19] Jin R C, Chen Y X, Li W Z, et al. Mechanism for catalytic partial oxidation of methane to syngas over a Ni/Al₂O₃ catalyst [J]. Appl Catal A: Gen, 2000, 201: 71-80.

[20] Shao Z P, Xiong G X, Dong H, et al. Synthesis, oxygen permeation study and membrane performance of a Ba_0.5Sr_0.5Co_0.8Fe_0.2O_3−δ oxygen-permeation dense ceramic reactor for partial oxidation of methane to syngas [J]. Separ Purif Technol, 2001, 25: 97-116.
[21] Ikeguchi M, Mimura T, Sekine Y, et al. Reaction and oxygen permeation studies in Sm_0.4Ba_0.6Fe_0.8Co_0.2O_3−δ membrane reactor for partial oxidation of methane to syngas [J]. Appl Catal A: Gen, 2005, 290: 212-220.

[22] Yang Z B, Zhang Y W, Zhang Y Y, et al. Hydrogen production from coke oven gas by reforming of methane: thermodynamic analyses and experiments [J]. Acta Phys Chim Sin, 2010, 26: 350.

[23] Zhang P, Chang X F, Wu Z T, et al. Effect of the packing amount of catalysts on the partial oxidation of methane reaction in a dense oxygen-permeable reactor [J]. Ind Eng Chem Res, 2005, 44: 1954-1959.

透氧膜反应器内NiO/MgO催化甲烷重整反应的途径

Reaction Pathways of Reforming of Methane over NiO/MgO Catalyst in Oxygen Permeation Membrane Reactor

PDF

可视化

摘要/Abstract

引用本文

使用本文

参考文献

相关文章 3

编辑推荐

Metrics

本文评价

[1]	杨志彬1, 丁伟中2. 钴镁固溶体催化剂在混合导体透氧膜反应器中的应用[J]. 上海大学学报(自然科学版), 2013, 13(5): 534-539.
[2]	丁伟中,沈培俊,杨志彬,郭曙强,张玉文,汪学广,吴成章,鲁雄刚. 焦炉煤气在透氧膜反应器中的重整机理[J]. 上海大学学报(自然科学版), 2011, 17(4): 529-534.
[3]	黄少卿，丁伟中，沈培俊，杨志彬，周宇鼎，张玉文. BaCo_0.7Fe_0.2Nb_0.1O_3-δ钙钛矿型混合导体透氧膜的性能[J]. 上海大学学报(自然科学版), 2010, 16(1): 43-47.