H-ZSM-5分子筛不同孔道处的酸位在甲醇制烯烃反应中的催化作用

甲醇制烯烃(MTO)作为一条由煤、天然气和生物质等含碳资源制备重要有机化学品的非石油路线,近年来备受关注.作为MTO催化剂,分子筛的骨架拓扑结构和酸性质对于其催化活性、反应路径和产物分布等具有重要的影响.H-ZSM-5分子筛是一种典型的MTO反应催化剂,酸位可以分布在MFI拓扑结构的直孔道、正弦孔道和交叉位点处.虽然目前已普遍认可MTO反应遵循芳烃/烯烃双循环烃池机理,分子筛的催化性能与其骨架中酸中心的位置相关,但对于H-ZSM-5分子筛不同孔道位置处的酸中心在甲醇制烯烃反应中的催化作用仍缺乏足够认识.本文采用密度泛函理论计算和分子动力学模拟方法,对H-ZSM-5分子筛不同孔道处(包括正弦孔道、直孔道和交叉腔)酸位中心上的MTO反应网络(包括芳烃循环、烯烃循环和芳构化)及甲醇原料和烯烃/芳烃产物的扩散行为进行了比较研究.结果表明,与正弦孔道和直孔道相比,芳烃循环和芳构化反应在交叉腔的酸中心上因具有较低的能垒而更易进行.相比之下,在正弦孔道和直孔道中,多甲基苯的生成受到显著限制,而烯烃循环却可以在三种酸中心(正弦孔道、直孔道和交叉腔)上以相近的能垒和相似的几率进行.芳烃循环生成乙烯和丙烯的几率相近,而烯烃循坏产物以丙烯和较高的烯烃产物为主.落位于H-ZSM-5交叉腔的酸中心能促进芳烃中间体如多甲基苯的生成,推动芳烃循环,提高乙烯选择性,而正弦孔道和直孔道中的酸中心则能增强烯烃循环,生成较多的丙烯和较高的烯烃产物.因此,H-ZSM-5分子筛对MTO的催化性能(包括活性和产物选择性等),可以通过有目的地调节酸中心在分子筛骨架中的位置分布(即铝落位)而得到有效调变和提升.本文阐明了H-ZSM-5分子筛酸中心在MTO反应中的催化作用与其骨架中的落位之间的有机联系,为高效甲醇转化分子筛催化剂的设计和性能提升提供了参考思路.

Boudouard reaction driven by thermal plasma for efficient CO2 conversion and energy storage

Conversion of CO2 into CO using plasma processing powered by renewable energy is a promising method to convert intermittent sustainable electricity into storable chemical energy.Despite extensive research efforts worldwide,there is currently no process that achieves economically viable values for both CO2 conversion fraction and energy recovery efficiency simultaneously.Here we demonstrate that a process that utilizes the Boudouard reaction,CO^2++C→2 CO,driven by a thermal plasma allows both 95%CO2 conversion to CO and energy recovery efficiency of 70%,values far higher than seen so far.By comparing the conversion process with and without CO2 excitation by a plasma and by using optical emission spectroscopy we show that the improved performance is due to a novel mode of operation where CO2 is pyrolyzed into an active mixture of CO,O and O2 by an arc discharge which is then introduced into a fixed bed to interact with carbon material.In this way,the free oxygen in the mixture combusts with carbon to form CO,and residual plasma excited CO2 is reduced by carbon.In the overall process,the endothermic Boudouard reaction is partially replaced by an exothermic reaction,and the excess electric energy to produce CO2 plasma is reused in the carbon bed.

An acid-base responsive linear-cyclic polymer rotaxane molecular shuttle with fluorescence signal output

The preparation of intelligent-responsive materials with controllable topology structure has long been a significant objective for chemists in the field of materials science. In this paper, we designed and prepared a linear-cyclic reversible topological structure polymer based on the bistable [1]rotaxane molecular shuttle. A ferrocene-functionalized [1]rotaxane and naphthalimide fluorophore group are introduced into the both ends of the polymer, which exhibit distance-induced photo-electron transfer effect. The structural transformation between linear and cyclic state of polymer is demonstrated by simple acid-base stimuli, accompanying visual fluorescence changes. The transformation process was characterized by 1H NMR spectra and fluorescence spectra. This work provides a novel strategy to construct functionalized polymers with topological structure.

Thermodynamic analysis of ethanol synthesis from hydration of ethylene coupled with a sequential reaction

Coal-based ethanol production by hydration of ethylene is limited by the low equilibrium ethylene conversion at elevated temperature.To improve ethylene conversion,coupling hydration of ethylene with a potential ethanol consumption reaction was analyzed thermodyna-mically.Five reactions have been attempted and compared:(1)dehydration of ethanol to ethyl ether(2C2H2OH5■C2H5OC2H5+H2O),(2)dehydrogenation of ethanol to acetaldehyde(C2H2OH5■CH3CHO+H2),(3)esterifica-tion of acetic acid with ethanol(C2H3OH+CH,COOH■CH3COOC2H5+H2O),(4)dehydrogenation of etha-nol to ethyl acetate(2C2H5OH■CH3COOC2H5+2H2),and(5)oxidative dehydrogenation of ethanol to ethyl acetate(2C2H2OH+O2■CH3COOC2H5+2H2O).The equilibrium constants and equilibrium distributions of the coupled reactions were calculated and the effects of feed composition,temperature and pressure upon the ethylene equilibrium conversion were examined.The results show that dehydrogenation of ethanol to acetaldehyde has lttle effect on ethylene conversion,whereas for dehydrogenation of ethanol to acetaldehyde and ethyl acetate,ethylene conversion can be improved from 8%to 12.8%and 18.5%,respectively,under conditions of H2O/C2H4=2,10 atm and 300℃.The esterification of acetic acid with ethanol can greatly enhance the ethylene conversion to 22.5%;in particular,ethylene can be actually completely converted to ethyl acetate by coupling oxidative dehydrogenation of ethanol.

A logic-based controller for the mitigation of ventilation air methane in a catalytic flow reversal reactor

The control system of a catalytic flow reversal reactor （CFRR） for the mitigation of ventilation air methane was investigated. A one-dimensional heteroge- neous model with a logic-based controller was applied to simulate the CFRR. The simulation results indicated that the controller developed in this work performs well under normal conditions. Air dilution and auxiliary methane injection are effective to avoid the catalyst overheating and reaction extinction caused by prolonged rich and lean feed conditions, respectively. In contrast, the reactor is prone to lose control by adjusting the switching time solely. Air dilution exhibits the effects of two contradictory aspects on the operation of CFRR, i.e., cooling the bed and accumulating heat, though the former is in general more prominent. Lowering the reference temperature for flow reversal can decrease the bed temperature and benefit stable operation under rich methane feed condition.