氟修饰的含Ni类水滑石在甲烷部分氧化制合成气中的应用研究

张军; 王秀芝; 赵宁; 肖福魁; 魏伟; 孙予罕

氟修饰的含Ni类水滑石在甲烷部分氧化制合成气中的应用研究

张军^1,2,
王秀芝¹,
赵宁¹,
肖福魁¹,
魏伟^1,,
孙予罕^1,2

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.
中国科学院上海高等研究院低碳能源转化中心, 上海 201203

详细信息

通讯作者:
魏伟, Tel: +86 351 4049612. E-mail: weiwei@sxicc.ac.cn。

中图分类号: TQ21
计量
- 文章访问数: 1250
- HTML全文浏览量: 9
- PDF下载量: 806
- 被引次数: 0
出版历程
- 收稿日期: 2011-05-11
- 修回日期: 2011-08-03
- 刊出日期: 2012-04-30

Application of fluorine-modified Ni-Mg-Al hydrotalcite catalyst in the partial oxidation of methane to syngas

1.
State Key Laboratory of Coal Conversion, Institute of Coal Chemistry, Chinese Academy of Sciences, Taiyuan 030001, China;
2.
Low Carbon Energy Conversion Center, Shanghai Advanced Research Institute, Chinese Academy of Sciences, Shanghai 201203, China

摘要

摘要: 通过共沉淀法合成了含Ni/Mg/Al的类水滑石,并利用水滑石的"重构性能"将F^-引入到水滑石层间。焙烧该类水滑石后得到Ni/Mg/Al/O-F催化剂,采用XRD、SEM、CO₂-TPD、H₂-TPR、N₂吸附-脱附等手段对其结构进行了表征。结果表明,焙烧后的催化剂为方镁石结构,并具有丰富的介孔,Ni/Mg/Al/O-F较之不含F^-的复合氧化物Ni/Mg/AlO具有更小的比表面积、颗粒粒径和结晶度,但是碱密度明显增大,并且在甲烷部分氧化(POM)反应中表现出更高的活性和稳定性,反应120h后,活性没有下降。这是因为F^-的引入提高了催化剂碱性和活性组分Ni的分散,从而改善了催化剂的抗积炭和烧结能力。
- 类水滑石 /
- POM /
- 复合氧化物 /
- F^-
Abstract: Fluorine-modified Ni-Mg-Al mixed oxides (Ni/Mg/Al/O-F) prepared from thermal decomposition of hydrotalcite-type (HT) precursor was characterized by XRD, SEM, CO₂-TPD, H₂-TPR, and N₂ sorption and used as catalyst in partial oxidation of methane (POM) to syngas. The results indicated that Ni/Mg/Al/O-F catalyst after calcination takes the mesoporous structure of periclase. Compared with the non-modified Ni-Mg-Al mixed oxides (Ni/Mg/Al/O), Ni/Mg/Al/O-F exhibits lower surface area, lower crystallinity and smaller particle size, but higher basicity of moderate and strong intensity. Ni/Mg/Al/O-F exhibits high activity and stability in POM; the activity at 1053K retains without deactivation even after 120h on stream. The presence of the F-anions can enhance the dispersion of active nickel species and their resistance to coking, which may contribute to the high performance of Ni/Mg/Al/O-F catalyst.
- hydrotalcite /
- partial oxidation of methane /
- fluorine modification /
- Ni-Mg-Al mixed oxides

HTML全文

参考文献(26)

CAVANI F, TRIFIRÒ F, VACCARI A. Hydrotalcite-type anionic clays: Preparation, properties and applications[J]. Catal Today, 1991, 11(2): 173-301.

申延明, 王蕾 ,李悦, 吴静, 张振祥, 刘长厚. MgAl-PdCl₄水滑石的合成与表征[J]. 燃料化学学报, 2007, 35(6): 711-715. (SHEN Yan-ming, WANG Lei, LI Yue, WU Jing, ZHANG Zhen-xiang, LIU Chang-hou. Preparation and characterization of MgAl-PdCl₄hydrotalcite[J]. Journal of Fuel Chemistry and Technology, 2007, 35(6): 711-715.)

CHRISTENSEN K O, CHEN D, LØDENG R, HOLMEN A. Effect of supports and Ni crystal size on carbon formation and sintering during steam methane reforming[J]. Appl Catal A, 2006, 314(1): 9-22.

MELONI D, MONACI R, SOLINAS V, AUROUX A, DUMITRIU E. Characterisation of the active sites in mixed oxides derived from LDH precursors by physico-chemical and catalytic techniques[J]. Appl Catal A, 2008, 350(1): 86-95.

HOLGADO M J, RIVES V, SAN ROMÁN M S. Characterization of Ni-Mg-Al mixed oxides and their catalytic activity in oxidative dehydrogenation of n-butane and propene[J]. Appl Catal A, 2001, 214(2): 219-228.

郭翠梨. 甲烷部分氧化制合成气La-Ni-O系催化剂性能的研究. 天津: 天津大学, 2006. (GUO Cui-li. Study on the catalytic performance of La-Ni-O catalysts for partial oxidation of methane. Tianjing: Tianjing University, 2006.)

王爱菊, 钟顺和. La₂O₃助剂对CH₄部分氧化制氢Ni-Cu/ZrSiO催化剂的影响[J]. 燃料化学学报, 2004, 32(1): 73-77. (WANG Ai-ju, ZHONG Shun-he. Effect of La₂O₃ on Ni-Cu/ZrSiO catalyst for partial oxidation of methane to produce hydrogen [J]. Journal of Fuel Chemistry and Technology, 2004, 32(1): 73-77. )

王越, 叶季蕾, 段华超, 刘源. 钡改性的Ni/γ-Al₂O₃催化剂用于甲烷部分氧化的研究[J]. 燃料化学学报, 2005, 33(6): 750-754. (WANG Yue, YE Ji-le,i DUAN Hua-chao, LIU Yuan. Study on partial oxidation of methane over Ba modified Ni/γ-Al₂O₃ catalyst[J]. Journal of Fuel Chemistry and Technology, 2005, 33(6): 750-754. )

谢春英, 龚茂初, 章洁, 陈耀强, 郑林, 李孝维, 许清淮. 镍基镧钡改性氧化铝催化剂性能研究[J]. 天然气化工, 2002, 27(2): 8-11. (XIE Chun-ying, GONG Mao-chu, ZHANG Jie, CHEN Yao-qiang, Zheng Lin, LI Xiao-wei, XU Qing-huai. Study on the properties of catalysts supported on La, Ba modified alumina containing nickel[J]. Natural Gas Chemical Industry, 2002, 27(2): 8-11.)

WU G, WANG X, CHEN B, LI J, ZHAO N, WEI W, SUN Y. Fluorine-modified mesoporous Mg-Al mixed oxides: Mild and stable base catalysts for O-methylation of phenol with dimethyl carbonate[J]. Appl Catal A, 2007, 329: 106-111.

ZHANG J, WEI W, SUN Y. Fluorine-modified mesoporous Ni-Mg-Al mixed oxides for partial oxidation of methane[J]. Catal Lett, 2010, 135(3/4): 321-329.

BÎRJEGA R, PAVEL O D, COSTENTIN G, CHE M, ANGELESCU E. Rare-earth elements modified hydrotalcites and corresponding mesoporous mixed oxides as basic solid catalysts[J]. Appl Catal A, 2005, 288(1/2): 185-193.

DAZA C E, GALLEGO J, MORENO S, MOLINA R. CO₂ reforming of methane over Ni/Mg/Al/Ce mixed oxides[J]. Catal Today, 2008, 133-135(4/5): 357-366.

LUCRÉDIO A F, JERKIEWICKZ G, ASSAF E M. Nickel catalysts promoted with cerium and lanthanum to reduce carbon formation in partial oxidation of methane reactions[J]. Appl Catal A, 2007, 333(1): 90-95.

GARCÍA-GARCÍA J M, PÉREZ-BERNAL M E, RUANO-CASERO R J, RIVES V. Chromium and yttrium-doped magnesium aluminum oxides prepared from layered double hydroxides[J]. Solid State Sci, 2007, 9(12): 1115-1125.

BENGAARD H S, NØRSKOV J K, SEHESTED J, CLAUSEN B S, NIELSEN L P, MOLENBROEK A M, ROSTRUP-NIELSEN J R. Steam reforming and graphite formation on Ni catalysts[J]. J Catal, 2002, 209(2): 365-384.

COSTANTINO U, CURINI M, MONTANARI F, NOCCHETTI M, ROSATI O. Hydrotalcite-like compounds as heterogeneous catalysts in liquid phase organic synthesis: II Preparation of 4H-chromenes promoted by hydrotalcite doped with hydrous tin(IV) oxide[J]. Microporous Mesoporous Mater, 2008, 107(1/2): 16-22.

PEREZ-LOPEZ O W, SENGER A, MARCILIO N R, LANSARIN M A. Effect of composition and thermal pretreatment on properties of Ni-Mg-Al catalysts for CO₂ reforming of methane[J]. Appl Catal A, 2006, 303(2): 234-244.

PESIC L, SALIPENOVIC S, MARKOVIC V, VUCELIC D, KAGUNYA W, JONES W. Thermal characteristics of a synthetic hydrotalcite-like material[J]. J Mater Chem, 1992, 2(10): 1069-1072.

PRESCOTT H A, LI Z J, KEMNITZ E, TRUNSCHKE A, DEUTSCH J, LIESKE H, AUROUX A. Application of calcined Mg-Al hydrotalcites for Michael additions: An investigation of catalytic activity and acid-base properties[J]. J Catal, 2005, 234(1): 119-130.

Di COSIMO J I, DÍEZ V K, XU M, IGLESIA E, APESTEGUI C R. Structure and surface and catalytic properties of Mg-Al basic oxides[J]. J Catal, 1998, 178(2): 499-510.

ZHANG W, WANG H, LI Q, DONG Q, ZHAO N, WEI W, SUN Y. The mechanism for the synthesis of 1-methoxy-2-propanol from methanol and propylene oxide over magnesium oxide[J]. Appl Catal A, 2005, 294(2): 188-196.

MOLINA R, PONCELET G. α-Alumina-supported nickel catalysts prepared from nickel acetylacetonate: A TPR study[J]. J Catal, 1998, 173(2): 257-262.

BASILE F, FORNASARI G, TRIFIRÒ F, VACCARI A. Partial oxidation of methane: Effect of reaction parameters and catalyst composition on the thermal profile and heat distribution[J]. Catal Today, 2001, 64(1/2): 21-30.

LIU S G, GUAN L X, LI J P, ZHAO N, WEI W, SUN Y H. CO₂ reforming of CH₄ over stabilized mesoporous Ni-CaO-ZrO₂ composites[J]. Fuel, 2008, 87(12): 2477-2481.

LUCRÉDIO A F, JERKIEWICKZ G, ASSAF E M. Cobalt catalysts promoted with cerium and lanthanum applied to partial oxidation of methane reactions[J]. Appl Catal B, 2008, 84(1/2): 106-111.

施引文献

资源附件(0)

访问统计