The catalytic performance of some quaternary ammonium salts for the liquid phase reaction of butanol and hydrochloric acid at different conditions was studied experimentally and compared with the traditional catalyst ...The catalytic performance of some quaternary ammonium salts for the liquid phase reaction of butanol and hydrochloric acid at different conditions was studied experimentally and compared with the traditional catalyst （ZnCl2）. The organic ammonium catalysts investigated include ionic liquids N-butyl-N-methyl imidazolium fluoborate （[BMIM][BF4]） and N-butyl-N-methylimidazolium chloride （[BMIM]Cl） as well as hydrochloric salts of N-methylimidazol （[HMIM]Cl）, pyridine （[HPy]Cl） and triethylamine （[HEt3N]Cl）. It is shown that the intrinsic catalytic performance of all organic ammonium salts except [HEt3N]Cl is slightly superior to ZnCl2, while the selectivity of butyl chloride is nearly at the same level around 96%. The conversion of butanol increases slightly with temperature and the catalyst amount added while the variation of selectivity is not obvious. Based on the recycle experiments, the ionic liquids as catalyst for the reaction of butanol and hydrochloric acid can be used more than 5 times, which suggests great potential of using ionic liquids as novel catalyst for such reactions.展开更多
In this work, the synthesis of epichlorohydrin(ECH) from 1,3-dichloropropanol(DCP) by using solid sodium hydroxide(NaOH) is carefully investigated. Inert organic solvent, 1-octanol, is introduced to ensure reaction in...In this work, the synthesis of epichlorohydrin(ECH) from 1,3-dichloropropanol(DCP) by using solid sodium hydroxide(NaOH) is carefully investigated. Inert organic solvent, 1-octanol, is introduced to ensure reaction intensity under control. The reaction performances with respect to apparent kinetics and selectivity are determined to explore optimized reaction conditions and confirm potentials for enhancing productivity in one batch. The dissolution and liquid phase reaction mechanism and instant reaction assumption are proposed and verified through process analysis. A process design towards free additional water is schematically figured out to manipulate solid NaOH, by-product,and unreacted starting materials to realize a nearly closed circuit. This process allows high selectivity over 97% and complete DCP conversion at 323.2 K within a reaction time less than 20 min. Other advantages include near-zero wastewater emission, economically possible NaOH regeneration from NaCl, and robust operating condition window.展开更多
基金Supported by the National Natural Science Foundation of China （No.20376004）
文摘The catalytic performance of some quaternary ammonium salts for the liquid phase reaction of butanol and hydrochloric acid at different conditions was studied experimentally and compared with the traditional catalyst （ZnCl2）. The organic ammonium catalysts investigated include ionic liquids N-butyl-N-methyl imidazolium fluoborate （[BMIM][BF4]） and N-butyl-N-methylimidazolium chloride （[BMIM]Cl） as well as hydrochloric salts of N-methylimidazol （[HMIM]Cl）, pyridine （[HPy]Cl） and triethylamine （[HEt3N]Cl）. It is shown that the intrinsic catalytic performance of all organic ammonium salts except [HEt3N]Cl is slightly superior to ZnCl2, while the selectivity of butyl chloride is nearly at the same level around 96%. The conversion of butanol increases slightly with temperature and the catalyst amount added while the variation of selectivity is not obvious. Based on the recycle experiments, the ionic liquids as catalyst for the reaction of butanol and hydrochloric acid can be used more than 5 times, which suggests great potential of using ionic liquids as novel catalyst for such reactions.
基金Supported by the National Natural Science Foundation of China(21176136,21422603)the National Science and Technology Support Program of China(2011BAC06B01)
文摘In this work, the synthesis of epichlorohydrin(ECH) from 1,3-dichloropropanol(DCP) by using solid sodium hydroxide(NaOH) is carefully investigated. Inert organic solvent, 1-octanol, is introduced to ensure reaction intensity under control. The reaction performances with respect to apparent kinetics and selectivity are determined to explore optimized reaction conditions and confirm potentials for enhancing productivity in one batch. The dissolution and liquid phase reaction mechanism and instant reaction assumption are proposed and verified through process analysis. A process design towards free additional water is schematically figured out to manipulate solid NaOH, by-product,and unreacted starting materials to realize a nearly closed circuit. This process allows high selectivity over 97% and complete DCP conversion at 323.2 K within a reaction time less than 20 min. Other advantages include near-zero wastewater emission, economically possible NaOH regeneration from NaCl, and robust operating condition window.
