Formation of surface chlorine species by low temperature reaction of HCl with metal-doped carbon
Formation of surface chlorine species by low temperature reaction of HCl with metal-doped carbon
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DOI：
10.1016/j.fuel.2019.02.084
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发表时间：
2019-06
期刊：
影响因子：
7.4
通讯作者：
N. Tsubouchi;Y. Mochizuki;Yuji Shinohara;A. Kawashima;Y. Ohtsuka
中科院分区：
文献类型：
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作者：
N. Tsubouchi;Y. Mochizuki;Yuji Shinohara;A. Kawashima;Y. Ohtsuka
用酚醛树脂制备的模型碳被O2活化，然后用钙、铜或锌浸渍，以阐明氯在煤炭利用中的行为。在100~300 °C范围内，盐酸与碳材料之间的相互作用更加容易。盐酸与钙、铜、锌反应的浓度较高。用X射线光电子能谱(XPS)和程序升温脱附(TPD)技术研究了碳载体与HCl反应生成的表面氯物种。XPS测试表明，与HCl反应后，存在无机氯和有机氯物种。当碳样在HCl反应后洗涤时，大部分HCl被洗脱。TPD测量也检测到了化学吸附的HCl物种；指示了无机氯、有机氯和化学吸附的HCl物种的存在。在100 °C时，有机氯物种的生成量与活性碳位的数量之间没有相关性，但在300 °C时，有机氯的生成量随碳中心的数量而增加，表面官能团是C-氯键的生成中心。讨论了氯化氢与金属掺杂(钙、铜、锌)碳在低温下反应生成有机氯物种的可能方案。
A model carbon prepared from phenolic resin was O2-activated and then impregnated with Ca, Cu or Zn to clarify chlorine behavior in coal utilization. Ease of interaction between HCl and the carbon material was enhanced at 100–300 °C. The concentration at which HCl reacted with Ca, Cu and Zn was high. The surface chloric species that were generated by reaction of the carbon substrate with HCl were studied using X-ray photoelectron spectroscopy (XPS) and temperature programmed desorption (TPD). XPS measurements suggested the presence of inorganic chloride and organic chlorine species after reaction with HCl. When the carbon samples were washed after the HCl reaction, most of the HCl was eluted. Chemically adsorbed HCl species were also detected by TPD measurement; the presence of inorganic chloride, organic chlorine and chemically adsorbed HCl species were indicated. No correlation was determined between the amount of organic chlorine species generated and the number of activated carbon sites at 100 °C. However, the amount of organic chlorine at 300 °C indicated a tendency to increase with the number of carbon sites, and the surface functional oxygen groups acted as sites for the generation of C-Cl bonds. As a result, possible scheme for the generation of organic chlorine species at low temperature by reaction between HCl and the metal-doped (Ca, Cu or Zn) carbon is discussed.