乙醇脱水制乙烯γ-Al_2O_3催化剂的分子模拟和实验研究
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摘要
生物质乙醇制乙烯是绿色可持续发展工艺路线。目前乙醇脱水制乙烯工业化装置上使用的催化剂主要是γ-Al_2O_3催化剂。从原子和分子水平上对该催化剂进行深入认识，可为设计开发在较低温度下使用的乙醇脱水制乙烯高选择性催化剂提供指导。本文采用分子模拟方法，对γ-Al_2O_3(100)表面结构及热稳定性进行了深入研究，探究了该表面对乙醇脱水制乙烯反应的催化性能，对该表面上乙醇脱水制乙烯过程各物种的吸附性能以及反应动力学进行了考察，并采用程序升温脱附和原位漫反射红外-质谱联用方法，对γ-Al_2O_3催化剂的酸碱中心和γ-Al_2O_3催化剂上乙醇脱水制乙烯的反应机理进行了研究。
γ-Al_2O_3(100)表面的Al终止面的f构型最稳定。当温度达到1000K时，表面发生再构；该表面的乙醇脱水制乙烯反应活性中心为Al_2和O_(2a)；醇脱水反应要求催化剂具有中等偏弱酸强度；根据多位理论的几何适应规则，较低温度时乙醇分子内脱水生成乙烯最有可能按照E1机理进行；γ-Al_2O_3(100)表面羟基化后，反应活性中心数目减少，不利于物种在γ-Al_2O_3(100)表面上的吸附活化及发生反应。
在温度为743K，压力为100~1500kPa时，乙醇、乙烯、乙醚和水单组分在γ-Al_2O_3(100)表面的吸附量由大到小依次为乙醚>乙醇>乙烯>水；各组分在γ-Al_2O_3(100)表面均为化学吸附，吸附热数值由大到小依次为乙烯>乙醇>水>乙醚；当以上物种形成共吸附时，乙醚的吸附热增大到246.9kJ/mol，成为吸附作用最强的物种，在原位继续发生反应，进而生成乙烯，是γ-Al_2O_3催化乙醇脱水生成乙烯具有高选择性的重要原因。
在γ-Al_2O_3(100)表面上乙醇脱水制乙烯三个可能发生的反应按照反应能垒由大到小排列依次为乙醇脱β-氢生成碳负离子>乙醇直接脱水生成乙烯>乙醇脱羟基生成碳正离子。基于谐波过渡态理论（Harmonic Transition State Theory），由反应物和过渡态的振动频率和活化能计算出反应过程中每一步基元反应的反应速率常数，当温度低于500K时，反应速率常数由大到小依次为乙醇脱羟基生成碳正离子>乙醇直接脱水生成乙烯>乙醇脱β-氢生成碳负离子，当温度达到500K时，反应速率常数由大到小依次为乙醇脱β-氢生成碳负离子>乙醇直接脱水生成乙烯>乙醇脱羟基生成碳正离子。
程序升温脱附和原位红外漫反射实验结果表明，真实的γ-Al_2O_3表面上存在不同强度的酸中心及碱中心，并存在少量B酸中心，说明真实的γ-Al_2O_3表面存在羟基化现象。原位漫反射红外-质谱联用研究结果表明，随温度的升高，乙烯的生成量增加，乙醚的生成量减少。乙醇脉冲进料实验发现，在停止乙醇进料一段时间后，体系中检测到乙炔，表明乙烯在γ-Al_2O_3催化剂上会被活化、继续反应生成乙炔，乙炔的多聚是造成催化剂表面积炭的可能原因。
The manufacture of ethylene from biomass-derived ethanol is an environmentallyfriendly and sustainable technological route. At present for the industrial manufactureof ethylene via ethanol dehydration, the γ-Al_2O_3catalyst is applied. The deep analysisof the catalyst could provide useful guidance to develop high selective catalyst used atlower temperature. In this work, by using molecular simulation approach, theappropriate γ-Al_2O_3(100) surface was choosed and the thermostability and catalyticproperties were studied. The adsorptive capabilities, as well as the reaction kineticswere also investigated. And the acidity and basicity of γ-Al_2O_3and reactionmechanism on γ-Al_2O_3were studied through TPD and DRIFTS.
The f model of Al terminal surface was the most stable γ-Al_2O_3(100) surfacemodel. The reconstruction of surface would take place at temperature of1000K; thesurface reactive sites were the Al_2a cidic site and O_(2a) alkalic site; the moderate aciditywas required for ethanol dehydration; and according to the geometric adaptability rulein multi-site theory, it was reasonable to deduce that ethylene from ethanoldehydration at lower temperature might comply to the E1mechanism, as with thetemperature was increased, the ethylene formation would comply to E1、E2or E1cBmechanism. After the hydroxylation of γ-Al_2O_3(100) surface, the characteristics ofsurface was changed dramatically, and the hydroxyl groups were consistentlyadsorbed on the surface of catalyst, which could inhibit the adsorption and activationof ethanol molecules.
At temperature743K and pressure100~1500kPa, the corresponding sequence ofadsorption amount of single components, such as ethanol, ethylene, diethyl ether andwater, was as following: diethyl ether>ethanol>ethylene>water; all of the fourcomponents could be chemically adsorbed on γ-Al_2O_3(100) surface, and thecorresponding sequence of adsorption heat was as following: ethylene>ethanol>water>diethyl ether; when above components co-adsorbed on γ-Al_2O_3(100) surface,diethyl ether was the strongest adsorption specie with the adsorption heat246.9kJ mol-1, which generated ethylene on adsorption site. It was the importantreason why γ-Al_2O_3catalyst performanced high dehydration selectivity.
On the γ-Al_2O_3(100) surface, the sequence of reaction barriers were as following:β-dehydrogenation of ethanol to form carbanions> direct dehydration of ethanol toform ethylene>dehydroxylation of ethanol to form carbonium ions. With the harmonic transition state theory, the reaction rate constant for each elementary step wascalculated using the reaction barrier and the vibration frequencies of reactant andtransition state. When temperature under500K, the sequence of reaction rate constantwas as following: dehydroxylation of ethanol to form carbonium ions>directdehydration of ethanol to form ethylene>β-dehydrogenation of ethanol to formcarbanions. When temperature above500K, the sequence of reaction rate constantswere as following: β-dehydrogenation of ethanol>direct dehydration of ethanol toform ethylene>dehydroxylation of ethanol to form carbonium ions.
The result of TPD and DRIFTS experiment showed that there were acid andalkali centers with different intensity on the real γ-Al_2O_3surface, and the presence ofa small amount of B acid center, showed that there was hydroxylation phenomenon onthe real γ-Al_2O_3surface. The result of DRIFTS-MS experiment showed that, with therise of temperature, the ethylene production increases and diethyl ether production isreduced from ethanol dehydration on γ-Al_2O_3. The result of ethanol pulse feedingexperiment showed that when ethanol feeding is stopped, acetylene was detected aftera short time, and ethylene may be activated to generate acetylene on γ-Al_2O_3catalystsurface. Polymerization of acetylene may cause carbon deposition on catalyst surfacearea.
γ-Al_2O_3(100)表面的Al终止面的f构型最稳定。当温度达到1000K时，表面发生再构；该表面的乙醇脱水制乙烯反应活性中心为Al_2和O_(2a)；醇脱水反应要求催化剂具有中等偏弱酸强度；根据多位理论的几何适应规则，较低温度时乙醇分子内脱水生成乙烯最有可能按照E1机理进行；γ-Al_2O_3(100)表面羟基化后，反应活性中心数目减少，不利于物种在γ-Al_2O_3(100)表面上的吸附活化及发生反应。
在温度为743K，压力为100~1500kPa时，乙醇、乙烯、乙醚和水单组分在γ-Al_2O_3(100)表面的吸附量由大到小依次为乙醚>乙醇>乙烯>水；各组分在γ-Al_2O_3(100)表面均为化学吸附，吸附热数值由大到小依次为乙烯>乙醇>水>乙醚；当以上物种形成共吸附时，乙醚的吸附热增大到246.9kJ/mol，成为吸附作用最强的物种，在原位继续发生反应，进而生成乙烯，是γ-Al_2O_3催化乙醇脱水生成乙烯具有高选择性的重要原因。
在γ-Al_2O_3(100)表面上乙醇脱水制乙烯三个可能发生的反应按照反应能垒由大到小排列依次为乙醇脱β-氢生成碳负离子>乙醇直接脱水生成乙烯>乙醇脱羟基生成碳正离子。基于谐波过渡态理论（Harmonic Transition State Theory），由反应物和过渡态的振动频率和活化能计算出反应过程中每一步基元反应的反应速率常数，当温度低于500K时，反应速率常数由大到小依次为乙醇脱羟基生成碳正离子>乙醇直接脱水生成乙烯>乙醇脱β-氢生成碳负离子，当温度达到500K时，反应速率常数由大到小依次为乙醇脱β-氢生成碳负离子>乙醇直接脱水生成乙烯>乙醇脱羟基生成碳正离子。
程序升温脱附和原位红外漫反射实验结果表明，真实的γ-Al_2O_3表面上存在不同强度的酸中心及碱中心，并存在少量B酸中心，说明真实的γ-Al_2O_3表面存在羟基化现象。原位漫反射红外-质谱联用研究结果表明，随温度的升高，乙烯的生成量增加，乙醚的生成量减少。乙醇脉冲进料实验发现，在停止乙醇进料一段时间后，体系中检测到乙炔，表明乙烯在γ-Al_2O_3催化剂上会被活化、继续反应生成乙炔，乙炔的多聚是造成催化剂表面积炭的可能原因。
The manufacture of ethylene from biomass-derived ethanol is an environmentallyfriendly and sustainable technological route. At present for the industrial manufactureof ethylene via ethanol dehydration, the γ-Al_2O_3catalyst is applied. The deep analysisof the catalyst could provide useful guidance to develop high selective catalyst used atlower temperature. In this work, by using molecular simulation approach, theappropriate γ-Al_2O_3(100) surface was choosed and the thermostability and catalyticproperties were studied. The adsorptive capabilities, as well as the reaction kineticswere also investigated. And the acidity and basicity of γ-Al_2O_3and reactionmechanism on γ-Al_2O_3were studied through TPD and DRIFTS.
The f model of Al terminal surface was the most stable γ-Al_2O_3(100) surfacemodel. The reconstruction of surface would take place at temperature of1000K; thesurface reactive sites were the Al_2a cidic site and O_(2a) alkalic site; the moderate aciditywas required for ethanol dehydration; and according to the geometric adaptability rulein multi-site theory, it was reasonable to deduce that ethylene from ethanoldehydration at lower temperature might comply to the E1mechanism, as with thetemperature was increased, the ethylene formation would comply to E1、E2or E1cBmechanism. After the hydroxylation of γ-Al_2O_3(100) surface, the characteristics ofsurface was changed dramatically, and the hydroxyl groups were consistentlyadsorbed on the surface of catalyst, which could inhibit the adsorption and activationof ethanol molecules.
At temperature743K and pressure100~1500kPa, the corresponding sequence ofadsorption amount of single components, such as ethanol, ethylene, diethyl ether andwater, was as following: diethyl ether>ethanol>ethylene>water; all of the fourcomponents could be chemically adsorbed on γ-Al_2O_3(100) surface, and thecorresponding sequence of adsorption heat was as following: ethylene>ethanol>water>diethyl ether; when above components co-adsorbed on γ-Al_2O_3(100) surface,diethyl ether was the strongest adsorption specie with the adsorption heat246.9kJ mol-1, which generated ethylene on adsorption site. It was the importantreason why γ-Al_2O_3catalyst performanced high dehydration selectivity.
On the γ-Al_2O_3(100) surface, the sequence of reaction barriers were as following:β-dehydrogenation of ethanol to form carbanions> direct dehydration of ethanol toform ethylene>dehydroxylation of ethanol to form carbonium ions. With the harmonic transition state theory, the reaction rate constant for each elementary step wascalculated using the reaction barrier and the vibration frequencies of reactant andtransition state. When temperature under500K, the sequence of reaction rate constantwas as following: dehydroxylation of ethanol to form carbonium ions>directdehydration of ethanol to form ethylene>β-dehydrogenation of ethanol to formcarbanions. When temperature above500K, the sequence of reaction rate constantswere as following: β-dehydrogenation of ethanol>direct dehydration of ethanol toform ethylene>dehydroxylation of ethanol to form carbonium ions.
The result of TPD and DRIFTS experiment showed that there were acid andalkali centers with different intensity on the real γ-Al_2O_3surface, and the presence ofa small amount of B acid center, showed that there was hydroxylation phenomenon onthe real γ-Al_2O_3surface. The result of DRIFTS-MS experiment showed that, with therise of temperature, the ethylene production increases and diethyl ether production isreduced from ethanol dehydration on γ-Al_2O_3. The result of ethanol pulse feedingexperiment showed that when ethanol feeding is stopped, acetylene was detected aftera short time, and ethylene may be activated to generate acetylene on γ-Al_2O_3catalystsurface. Polymerization of acetylene may cause carbon deposition on catalyst surfacearea.
引文
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