华南理工大学学报(自然科学版) ›› 2004, Vol. 32 ›› Issue (1): 49-55,64.

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添加剂对共沉淀法制备的VPO催化剂的影响

叶代启1 付名利1 梁红2 程胜中1 荣铁志1 庞先燊1   

  1. 1.华南理工大学 环境科学与工程系‚广东 广州510640;2.广州大学 轻化工程系‚广东 广州510091
  • 收稿日期:2003-04-07 出版日期:2004-01-20 发布日期:2015-09-07
  • 通信作者: 叶代启(1965-)‚男‚副教授‚主要从事空气污染控制技术的研究. E-mail:cedqye@scut.edu.cn
  • 作者简介:叶代启(1965-)‚男‚副教授‚主要从事空气污染控制技术的研究.
  • 基金资助:
    国家自然科学基金资助项目(29100028);广东省自然科学基金资助项目(920111);广东省重大科技项目(2KB06601S)

Influence of Additives on Various VPO Catalysts Prepared by Coprecipitation Process

Ye Dai-qi1  FuMing-li1 Liang Hong2 Cheng Sheng-zhong1 Rong Tie-zhi1 Pang Xian-shen 1   

  1. 1.Dept.of Environmental Science and Engineering‚South China Univ.of Tech.‚Guangzhou510640‚Guangdong‚China;
    2.Dept.of Light Chemical Engineering‚Guangzhou Univ.‚Guangzhou510091‚Guangdong‚China
  • Received:2003-04-07 Online:2004-01-20 Published:2015-09-07
  • Contact: Ye Dai-qi(born in1965)‚male‚associate professor‚mainly researches on air pollution control technology. E-mail:cedqye@scut.edu.cn
  • About author:Ye Dai-qi(born in1965)‚male‚associate professor‚mainly researches on air pollution control technology.
  • Supported by:
     Supported by the National Natural Science Foundation of China (29100028)‚Guangdong Provincial Natural Science Foundation (920111) and Guangdong Provincial Key Scientific and Technological Project (2KB06601S)

摘要: 研究了添加剂对用于选择性氧化正丁烷为顺丁烯二酸酐的 VPO 催化剂的结构和性能的影响.催化剂采用共沉淀法制备‚添加元素为Zr‚Co‚Ce‚Zn‚Sn‚K‚Ba 和Bi 等.催化剂性能测试在固定床微反应器内于常压下进行.结果表明‚添加剂对催化剂性能有很大的影响.各种组分对正丁烷氧化的促活顺序为:VPO-Zr>VPO-Co>VPO-Zn>VPO-Sn>VPO-Bi>VPO-Ce>VPO-Ba>VPO-K>VPO‚而对正丁烷氧化为顺丁烯的选择性促活顺序为:VPO-Zr>VPO-Ce>VPO-Zn>VPO-Sn>VPO-Co>VPO-Bi>VPO>VPO-Ba>VPO-K.XRD‚FTIR 和 TGA/DTG 测试结果表明‚添加剂的加入并未使活化前后催化剂的本体结构发生明显改变.所有VPO 催化剂前体均主要含VOPO4.0.5H2O‚而活化后的催化剂主要含有(VO)2P2O7和少量α-VOPO4.XPS 测试证实催化剂表面有 P‚V 和 O 等元素富集的现象‚而且表面氧物种数与催化剂活性直接相关.

关键词: VPO 催化剂, 添加剂, 正丁烷, 顺丁烯二酸酐, 表面氧物种

Abstract: The effect of additives on the structures and properties of various VPO catalysts used for the select tive oxidation of n-butane to maleic anhydride was investigated.A series of VPO catalysts were prepared by coprecipitation process with the addition of Zr‚Co‚Ce‚Zn‚Sn‚K‚Ba and Bi as promoters.The catalytic performance test was conducted in a fixed-bed micro-reactor at atmospheric pressure.The results show that the catalytic behavior is affected remarkably by additives.For n-butane oxidation activity‚the effect of various elements follows the order of VPO-Zr>VPO-Co>VPO-Zn>VPO-Sn>VPO-Bi>VPO-Ce>VPO-Ba>VPO-K>VPO.For MA (Maleic Anhydride) selectivity‚the promoting effect is in the order of VPO-Zr>VPO-Ce>VPO-Zn>VPO-Sn>VPO-Co>VPO-Bi>VPO>VPO-Ba>VPO-K.Test results of catalysts including XRD‚FTIR and TGA/DTG indicate that no remarkable change occurs in the bulk structure due to the addition of elements‚both for precursor and final catalysts.All precursor catalysts are composed of VOPO4.0.5H2O‚while in the final samples‚(VO)2P2Ois formed accompanied by less amounts of α-VOPO4.XPS measurement suggests the enrichment of P‚V and O on the surface of catalysts‚and the amount of surface oxygen species is directly related to the catalyst activity.

Key words:  vanadyl pyrophosphate catalyst, additive, n-butane oxidation, maleic anhydride, surface oxygen species

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