液相中镍催化剂催化合成气甲烷化的初步研究

黄国宝; 王志青; 李庆峰; 黄戒介; 房倚天

液相中镍催化剂催化合成气甲烷化的初步研究

1.
中国科学院山西煤炭化学研究所煤转化国家重点实验室, 山西太原 030001;
2.
中国科学院大学, 北京 100049

基金项目: 国家自然科学基金青年科学基金（21106173）；中国科学院战略性先导科技专项（XDA07050100）；山西省青年科技研究基金（2013021007-2）；中国科学院山西煤炭化学研究所青年人才项目（2011SQNRC01）。

详细信息

通讯作者:
李庆峰，Tel/Fax：0351-2021137，E-mail：lqf@sxicc.ac.cn。

中图分类号: TQ032
计量
- 文章访问数: 660
- HTML全文浏览量: 22
- PDF下载量: 557
- 被引次数: 0
出版历程
- 收稿日期: 2014-02-18
- 修回日期: 2014-03-29
- 刊出日期: 2014-08-30

Syngas methanation over nickel catalyst in liquid-phase

1.
State Key Laboratory of Coal Conversion, Institute of Coal Chemistry, Chinese Academy of Sciences, Taiyuan 030001, China;
2.
University of Chinese Academy of Sciences, Beijing 100049, China

摘要

摘要: 采用液相还原法制备非负载型镍催化剂，将非负载型镍催化剂分散在液相供氢溶剂十氢萘中，催化合成气甲烷化反应。在高压反应釜内，考察了反应温度、物质的量比等操作条件下，镍催化剂催化合成气甲烷化反应的反应活性。并对催化剂进行XRD、SEM、H₂-TPR表征分析。研究结果表明，在330 ℃、催化剂用量为2%时，产品气中甲烷含量可达89.39%，CO和H₂的转化率分别为94.56%和92.60%；催化剂用量为4%时，产品气中甲烷含量可高达94.26%，CO的转化率可达到99%以上。合成气甲烷化反应的最佳操作温度为330 ℃，H₂/CO物质的量比最佳为2.20~2.67。
- 合成气甲烷化 /
- 十氢萘 /
- 供氢溶剂 /
- 镍催化剂
Abstract: Unsupported metal nickel catalysts were prepared by liquid phase reduction method. The catalytic performance of the catalysts for syngas methanation were conducted in an autoclave using decalin as the hydrogen donor solvent at different operation conditions, such as temperature, mol ratio of H₂/CO in feed gas. And the catalyst characterizations were conducted by means of XRD, SEM, H₂-TPR.The results showed that the content of CH₄ in the product gas was 89.39% when 2% catalyst was used at 330 ℃, and the corresponding conversions of CO and H₂ were 94.56% and 92.60%, respectively. When 4% catalyst was used, the CO conversion was further improved to more than 99% while the content of CH₄ in the product gas exceeded 94.26%. The best operation temperature of syngas methanation in liquid phase was 330 ℃and the optimum range of H₂/CO mol ratio in feed was 2.20~2.67.
- syngas methanation reaction /
- decalin /
- hydrogen donation solvent /
- nickel catalyst

HTML全文

参考文献(21)

杨伯伦, 李星星, 伊春海, 蒋雪冬, 张勇, 周晓奇. 合成天然气技术进展[J]. 化工进展, 2011, 30(1): 110-116. (YANG Bo-lun, LI Xing-xing, YI Chun-hai, JIANG Xue-dong, ZHANG Yong, ZHOU Xiao-qi.Technological progress of synthetic natural gas[J]. Chemical Industry and Engingeering Progress, 2011, 30(1): 110-116.)

张小卫, 张俊圆. 我国煤制天然气现状及"十二五"发展趋势分析[J]. 化学工程与装备, 2011, 7: 151-152. (ZHANG Xiao-wei, ZHANG Jun-yuan. Present situation of coal-to-nature gas and the development trend analysis of "twelfth five-year" in our country[J]. Chemical Engingeering&Euipment, 2011, 7: 151-152.)

CAECILIA R V, MARTIN J, KRZYSZTOF J P. Exergy analysis of biomass-to-synthetic natural gas(SNG) process via indirect gasification of various biomass feedstock[J]. Energy, 2011, 36(6): 3825-3837.

SAKAE T, TORU S, KIYOSHI O. Complete removal of carbon monoxide in hydrogen-rich gas stream through methanation over supported metal catalysts[J]. Int J Hydrogen Energy, 2004, 29(10): 1065-1073.

SHI P, LIU C J. Characterization of silica supported nickel catalyst for methanation with improved activity by room temperature plasma treatment[J]. Catal Lett, 2009, 133(1/2): 112-118.

URASAKI K, ENDO K I, TAKAHIRO T, KIKUCHI R, KOJIMA T, SATOKAWA S. Effect of support materials on the selective methanation of CO over Ru catalysts[J]. Top Catal, 2010, 53(7/10): 707-711.

LIU Q H, DONG X F, MO X M, LIN W M. Selective catalytic methanation of CO in hydrogen rich gases over NiZrO₂ catalyst[J]. J Nat Gas Chem, 2008, 17(3): 268-272.

卢红选, 秦榜辉, 孙鲲鹏, 肖利华, 徐贤伦. 预处理及反应条件对负载型钌催化剂甲烷化性能的影响[J]. 天然气化工, 2004, 29(4): 1-4. (LU Hong-xuan, QIN Bang-hui, SUN Kun-peng, XIAO Li-hua, XU Xian-lun. Effect of pretreatment on catalytic performance of Ru/Al₂O₃ for methanation[J]. Natural Gas Chemical Industry, 2004, 29(4): 1-4.)

张成. CO与CO₂甲烷化反应研究进展[J]. 化工进展, 2007, 26(9): 1269-1273. (ZHANG Cheng. Research progress of methanation of carbon monoxide and carbon dioxide[J]. Chemical Industry and Engingeering Progress, 2007, 26(9): 1269-1273.)

KOU Y, WANG H L, NIU J Z, JI W J. Surface coordinate geometry of iron catalysts distinctive behaviors of in CO hydrogenation[J]. J Phys Chem, 1996, 100(6): 2330-2333.

ALFRED P W, MARTIN S, CHRISTOPH T, GERHARD K. Aerosol catalysis on nickel nanoparticles[J]. J Nanopart Res, 1999, 1(2): 253-265.

HIPPE C, LAMBER R, SCHULZ G, SCHUBER U. Influence of the strong metal support interaction on the CO chemisorption at a Pt/SiO₂ catalyst[J]. Catal Lett, 1997, 43(3/4): 195-199.

CZEKAJ I, LOVIAT F, RAIMONDI F, WAMBACH J, BIOLLAZ S, WOKAUN A. Characterization of surface processes at the Ni-based catalyst during the methanation of biomass-derived synthesis gas: X-ray photoelectron spectroscopy(XPS)[J]. Appl Catal A: Gen, 2007, 329: 68-78.

路霞, 陈世恒, 王万丽, 马紫峰. CO甲烷化Ni基催化剂的研究进展[J]. 石油化工, 2010, 39(3): 340-354. (LU Xia, CHEN Shi-heng, WANG Wan-li, MA Zi-feng. Progress in Ni based catalysts for CO methanation[J]. Petrochemical Technology, 2010, 39(3): 340-354.)

崔晓曦, 张庆庚, 李忠, 牛凤芹, 范辉, 郑华艳, 闫少伟. 一种焦炉煤气进行甲烷化合成天然气的工艺: 中国, 101979475A[P]. 2011-02-23. (CUI Xiao-xi, ZHANG Qing-geng, LI zhong, NIU feng-qin, FAN hui, ZHENG hua-yan, YAN shao-wei. Process of coke-oven gas methanation produce synthetic nature gas: CN, 101979475A[P]. 2011-02-23.)

张庆庚, 李忠, 闫少伟, 崔晓曦, 范辉, 何忠, 郑华艳, 曹会博. 一种煤制合成气进行甲烷化合成天然气的工艺: 中国, 101979476B. 2013-05-29. (ZHANG Qing-geng, Li Zhong, YAN Shao-wei, CUI Xiao-xi, FAN Hui, HE Zhong, ZHENG Hua-yan, CAO Hui-bo. Process of coal-to-syngas methanation produce synthetic nature gas: CN, 101979476B. 2013-05-29.)

薛永兵, 凌开成, 邹刚明. 煤直接液化中溶剂的作用和种类[J]. 煤炭转化, 1999, 22(4): 1-4. (XUE Yong-bing, LING Kang-cheng, ZOU Gang-ming. Functions and kinds of solvents in coal direct liquefaction[J]. Coal Coversion, 1999, 22(4): 1-4.)

ATSUSHI I, SHINJI M, TOSHIAKI K. Elucidation of hydrogen transfer mechanisms in coal liquefaction using a tritium tracer method: Effects of solvents on hydrogen exchange reactions of coals with tritiated molecular hydrogen[J]. Fuel, 1995, 74(1): 63-70.

李军, 张秀成, 姚铁军, 霍尚义. 抗水合氧化铝载体研究进展[J]. 工业催化, 2003, 11(8): 48-52. (LI Jun, ZHANG Xiu-cheng, YAO Tie-jun, HUO Shang-yi. Developments preperation of hydration-tolerant catalysts supports[J]. Industrial Cataltsis, 2003, 11(8): 48-52.)

ANDREW D S, GRAINNE B, SONG C S. Shape-selective hydrogenation of naphthalene over zeolite-supported Pt and Pd catalysts[J]. Catal Today, 1996, 31(1/2): 45-56.

徐超, 王兴军, 胡贤辉, 陈雪莉, 王辅臣. 镍基催化剂在甲烷化过程中积碳的研究[J]. 化学世界, 2010: 98-99. (XU Chao, WANG Xing-jun, HU Xiao-hui, CHEN Xue-li, WANG Fu-chen. Research of carbon deposition in the methanation over nickel-based catalysts[J]. Chemical Word, 2010: 98-99.)

施引文献

资源附件(0)

访问统计