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现代化工  2018, Vol. 38 Issue (3): 105-109    DOI: 10.16606/j.cnki.issn0253-4320.2018.03.023
  科研与开发 本期目录 | 过刊浏览 | 高级检索 |
氟化镁基催化剂催化2-氯-1,1,1,2-四氟丙烷气相脱卤化氢反应性能研究
贾兆华1,2, 毛伟1,2, 白彦波1,2, 吕剑1,2
1. 西安近代化学研究所, 陕西 西安 710065;
2. 氟氮化工资源高效开发与利用国家重点实验室, 陕西 西安 710065
Gas-phase dehydrohalogenation of 2-chloro-1,1,1,2-tetrafluoropropene over magnesium fluoride-based catalysts
JIA Zhao-hua1,2, MAO Wei1,2, BAI Yan-bo1,2, LV Jian1,2
1. Xi'an Modern Chemistry Research Institute, Xi'an 710065, China;
2. State Key Laboratory for Efficient Development and Utilization of Fluorine & Nitrogen Chemicals, Xi'an 710065, China
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摘要 采用等体积浸渍法制备了不同金属离子(Mn+)改性的系列氟化镁基催化剂(M/MgF2),考察了其在高温气相条件下催化转化2-氯-1,1,1,2-四氟丙烷(HCFC-244bb)合成新一代环保制冷剂2,3,3,3-四氟丙烯(HFO-1234yf)的反应性能。实验结果表明,单一氟化镁上同时存在脱HF、脱HCl 2种反应过程,但前者为主反应,脱HF生成副产物2-氯-3,3,3-三氟丙烯(HCFO-1233xf)的选择性达87.7%,目标脱HCl产物HFO-1234yf选择性不足10%。Al3+改性后,催化剂活性显著增加,但脱HF选择性也随之增大(约90%)。3% Fe/MgF2、3% Zr/MgF2催化剂上HFO-1234yf选择性有所提高,但不足20%。碱金属K+、Cs+的添加可大幅提高催化剂的脱HCl选择性,分别为76.4%和86.6%,但催化剂活性低于未改性MgF2催化剂。采用N2物理吸附、NH3-TPD等表征手段对催化剂结构、表面酸性进行表征,并将其与催化反应性能进行关联,结果表明,催化剂表面酸性的减弱有利于反应向选择性脱HCl方向移动。
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贾兆华
毛伟
白彦波
吕剑
关键词:  2-氯-1,1,1,2-四氟丙烷  2,3,3,3-四氟丙烯  脱卤化氢  镁基催化剂    
Abstract: A series of magnesium fluoride-based catalysts (M/MgF2) modified by different metal ions (Mn+) are prepared by equal volume impregnation method and their catalytic performances are investigated in the gas-phase catalytic dehydrochlorination of 1,1,1,2-tetrafluoro-2-chloropropane (HCFC-244bb) to make 2,3,3,3-tetrafluoropropylene (HFO-1234yf),a new generation of environment-friendly refrigerant.It is found that both dehydrofluorination and dehydrochlorination reactions occur on the pure MgF2 catalyst,with dehydrofluorination as the main reaction.More importantly,the dehydrochlorination selectivity to HFO-1234yf is only 8.8%,and the selectivity to 2-chloro-3,3,3-trifluropropylene (HCFO-1233xf) is as high as 87.7%.The catalyst modified by Al3+exhibits higher activity,however,the un-expected dehydrofluorination selectivity to HCFO-1233xf increases to around 90% over the catalyst modified by Al3+,although.The dehydrochlorination selectivity to HFO-1234yf over 3%Fe/MgF2 or 3%Zr/MgF2 catalysts increases,but still less than 20%.High dehydrochlorination selectivity can be achieved over the MgF2 catalysts modified by K or Cs halides,reaching 76.4% and 86.6% respectively,however,the activities of these catalysts are lower than the pure MgF2 catalyst.The structure and surface acidity of prepared catalysts are characterized by means of XRD,NH3-TPD and N2 physical adsorption measurements,which are then correlated with catalytic performance.The results show that decreasing the surface acidity of catalyst can benefit the dehydrochlorination of HCFC-244bb.
Key words:  2-chloro-1,1,1,2-tetrafluoropropene    2,3,3,3-tetrafluoropropylene    dehydrohalogenation    magnesium fluoride-based catalysts
收稿日期:  2017-10-21                出版日期:  2018-03-20
O623.2  
基金资助: 国家自然科学基金(21503161)
通讯作者:  吕剑(1963-),男,博士,研究员,博士生导师,研究方向为催化合成技术,通讯联系人,lujian204@gmail.com。    E-mail:  lujian204@gmail.com
作者简介:  贾兆华(1992-),男,硕士生,研究方向为含氟化学品合成,1542320290@qq.com
引用本文:    
贾兆华, 毛伟, 白彦波, 吕剑. 氟化镁基催化剂催化2-氯-1,1,1,2-四氟丙烷气相脱卤化氢反应性能研究[J]. 现代化工, 2018, 38(3): 105-109.
JIA Zhao-hua, MAO Wei, BAI Yan-bo, LV Jian. Gas-phase dehydrohalogenation of 2-chloro-1,1,1,2-tetrafluoropropene over magnesium fluoride-based catalysts. Modern Chemical Industry, 2018, 38(3): 105-109.
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http://www.xdhg.com.cn/CN/10.16606/j.cnki.issn0253-4320.2018.03.023  或          http://www.xdhg.com.cn/CN/Y2018/V38/I3/105
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