乙苯脱氢制苯乙烯反应器的技术进展

乙苯脱氢是工业生产苯乙烯的主要方法,传统生产方法有等温脱氢工艺和绝热脱氢工艺,分别采用等温列管式反应器和绝热轴向反应器,随着装置高效化和大型化的要求,负压脱氢工艺开发成功,反应器采用低阻力径向反应器,基本上为所有新建装置所采用。20世纪90年代我国开发了独特的轴径向反应器,首次应用于苯乙烯工业,形成了自主的负压脱氢制苯乙烯技术。     

大型乙苯脱氢轴径向反应器的研究与开发(Ⅰ) 流体力学特性

乙苯脱氢轴径向反应器是一种催化床上部采用催化剂自封结构的新颖径向反应器 ,其催化床中的流体流动是复杂的二维流动 .在催化床的表征体积元上应用连续性方程和Ergen方程描述了其流动 ,应用有限差分法通过数学模拟得出了轴径向反应器流场 ,其结果在Φ30 0 0× 10 0 0 0的冷模装置得到了验证 .以大型乙苯脱氢轴径向反应器为背景 ,讨论了流向和触媒封高对流场的影响 ,得出径向段主要以径向流动为主 ,在催化剂封区以轴向、径向二维流动为主 ;催化剂封高是影响流场的主要因素 ,对于向心流动δ在 0 .7附近是Q_a/Q与Q_r/Q相同的等比流量点 ,对于离心流动在δ为 1.1处 ,是Q_a/Q和Q_r/Q相同的等比流量点 .δ小于此值 ,是以轴向流动为主径向流动为次的二维流动区 ;δ大于此值 ,是轴向流动为次径向流动为主的二维流动区 ;与离心流动型相比 ,向心流动型轴径向床有明显的限流作用     

R&D OF LARGE AXIAL-RADIAL REACTOR FOR ETHYLBENZENE DEHYDROGENATION(Ⅰ) HYDRODYNAMICS STUDY

乙苯脱氢轴径向反应器是一种催化床上部采用催化剂自封结构的新颖径向反应器 ,其催化床中的流体流动是复杂的二维流动 .在催化床的表征体积元上应用连续性方程和Ergen方程描述了其流动 ,应用有限差分法通过数学模拟得出了轴径向反应器流场 ,其结果在Φ30 0 0× 10 0 0 0的冷模装置得到了验证 .以大型乙苯脱氢轴径向反应器为背景 ,讨论了流向和触媒封高对流场的影响 ,得出径向段主要以径向流动为主 ,在催化剂封区以轴向、径向二维流动为主 ;催化剂封高是影响流场的主要因素 ,对于向心流动δ在 0 .7附近是Q_a/Q与Q_r/Q相同的等比流量点 ,对于离心流动在δ为 1.1处 ,是Q_a/Q和Q_r/Q相同的等比流量点 .δ小于此值 ,是以轴向流动为主径向流动为次的二维流动区 ;δ大于此值 ,是轴向流动为次径向流动为主的二维流动区 ;与离心流动型相比 ,向心流动型轴径向床有明显的限流作用     

沸石膜反应器苯脱氢反应性能

采用管式沸石膜反应器,研究了乙苯脱氢反应生成苯乙烯的性能。考察了不同渗透分离性能的沸石膜对乙苯脱氢反应的影响和不同沸石膜反应器上乙苯脱氢反应的规律。结果表明,与固定床操作条件下相比,沸石膜反应器乙苯转化率可提高近10％－16％,苯乙烯选择性可提高3％－5％。渗透分离性能是决定沸石膜提高脱氢反应性能的最重要因素,H2渗透量越大、H2／C3H8分离系数越高,对反应越有利。渗透分离性能相近但类型不同的沸石膜对乙苯脱氢反应性能有差异,其中Fe-ZSM-5沸石膜反应性能较好,这是杂原子Fe进入沸石骨架后引起的。反应后膜的渗透分离性能略有变化。     

大型乙苯脱氢轴径向反应器的研究与开发(Ⅱ) 反应器模拟与分析

在轴径向反应器二维流动模型的基础上导出了基于二维流动的二维拟均相反应器模型 ,应用有限差分法求解此模型 ,发现轴径向反应器反应转化率略高于相应的径向反应器 0 .1%～ 0 .6 % ,而选择性两者基本相同 ;同时得出催化剂封中流体的二维流动使得轴径向反应器的温度场和浓度场极其复杂 ,对于乙苯脱氢反应 ,在催化剂封区域存在一个低温区和高苯乙烯浓度区 .此反应器模型得到了年产 3万吨乙苯脱氢轴径向反应器的工业数据的证实 ,可用于指导轴径向反应器的设计     

Steady State Modeling and Optimization of Styrene Production in an Industrial Axial Flow Adiabatic Reactor

In this study, the performance of industrial axial flow adiabatic reactors to produce styrene through ethylbenzene dehydrogenation on the potassium-promoted iron catalyst studied at steady state condition. The dehydrogenation reactors have been modeled heterogeneously based on the one-dimensional mass and energy governing laws and considering a detailed kinetic model. The catalytic and thermal kinetic models have been applied in the mathematical model of process. To prove the accuracy of the considered model and assumptions, the simulation results are compared with the plant data at the same process condition. Also, Genetic algorithm as a powerful method in the global optimization has been considered to maximize styrene production as the objective function. The inlet feed temperature to each reactor is selected as attainable decision variables due to severe effect of temperature on the equilibrium and kinetic constant. This configuration has enhanced styrene production rate by 1.2% compared to industrial adiabatic reactor.     

R&D OF LARGE AXIAL-RADIAL REACTOR FOR ETHYLBENZENE DEHYDROGENATION(Ⅱ) REACTOR SIMULATION AND ANALYSIS

在轴径向反应器二维流动模型的基础上导出了基于二维流动的二维拟均相反应器模型 ,应用有限差分法求解此模型 ,发现轴径向反应器反应转化率略高于相应的径向反应器 0 .1%～ 0 .6 % ,而选择性两者基本相同 ;同时得出催化剂封中流体的二维流动使得轴径向反应器的温度场和浓度场极其复杂 ,对于乙苯脱氢反应 ,在催化剂封区域存在一个低温区和高苯乙烯浓度区 .此反应器模型得到了年产 3万吨乙苯脱氢轴径向反应器的工业数据的证实 ,可用于指导轴径向反应器的设计     

VxTi复合氧化物催化剂用于二氧化碳气氛乙苯脱氢的研究

采用溶胶-凝胶法制备了以TiO₂为基体的VxTi复合氧化物催化剂,该催化剂用于乙苯二氧化碳低温氧化脱氢制苯乙烯反应。考察了活性组分含量和焙烧温度对催化剂活性的影响。结果表明,活性金属钒的添加有助于提高脱氢反应性能,但存在一适量值,摩尔分数超过5%,催化脱氢活性下降。通过XRD分析发现,不同焙烧温度制备的VxTi催化剂中TiO₂的晶相不同,随着温度的升高,TiO₂的晶相将由锐钛矿型转变为金红石晶相。TiO₂锐钛矿型晶相有利于苯乙烯选择性的提高,而金红石晶相则不利于催化剂的脱氢反应。     

乙苯催化脱氢制苯乙烯技术研究进展

主要介绍了国内外乙苯脱氢制苯乙烯催化剂的研制现状及新型反应器、新工艺的开发，并探讨了乙苯脱氢制苯乙烯技术的发展方向。     

节能型乙苯脱氢催化剂的开发及其性能评价

在GS-11乙苯脱氢制苯乙烯催化剂基础上通过增加铈含量、引入选择性调变剂和优化孔结构,开发了节能型催化剂。在负压绝热评价装置上,乙苯空速0.5 h-1、一反/二反入口温度615℃/620℃、水油质量比1.15,二反出口压力-55 kPa条件下,乙苯转化率67.3%,苯乙烯选择性大于97.0%。催速老化实验结果表明,该催化剂的失活速率为-0.004 04%/h,优于最新引进催化剂和GS-11催化剂。     

Amorphous porous MxTi mixed oxides as catalysts for the oxidative dehydrogenation of ethylbenzene

The properties of different metal‐oxide‐doped porous titanium oxides as catalysts for the oxidative dehydrogenation of ethylbenzene were investigated. Amorphous porous mixed oxides based on the amorphous titania matrix with selected metal ion centers as active sites have been prepared by an acid‐catalyzed sol–gel method. The dehydrogenation of ethylbenzene was studied in a continuous gas phase flow reactor under different reaction temperatures at ambient pressure. Among the 23 catalysts studied the amorphous porous AM‐Cr₅Ti mixed oxide is the most promising catalyst. At 350 °C a 75% selectivity to styrene at a 29% conversion of ethylbenzene was obtained. BET, HRTEM, XRD, GC, MS, TGA and optical microscopy were employed to characterize the fresh and used AM‐Cr₅Ti catalyst. This revised version was published online in August 2006 with corrections to the Cover Date.     

乙苯脱氢-氢选择氧化苯乙烯生产工艺探析

乙苯催化脱氢是生产苯乙烯的主要方法。介绍了近年来日益受到广泛关注的乙苯脱氢一氢选择氧化技术。包括该工艺的原理、典型脱氢反应器、以及催化剂的研究进展情况。并对国内采用该项技术新建苯乙烯装置或对现有苯乙烯装置进行技术改造提出了建议。     

Hydrotalcite-like compounds as precursors for mixed oxides catalysts in the oxydehydrogenation of ethylbenzene

The dehydrogenation of ethylbenzene to styrene is a very important industrial reaction due to the multiple applications of styrene as a monomer for synthetic polymers. Reported catalysts that are active and selective in the oxidative dehydrogenation of alkylaromatics include supported metals through both main group and transition metal oxides to polymers and activated carbons. However, most of these catalysts are acid oxides, inducing the formation of an active coke layer that is the actual catalyst. We report in this work the use of various hydrotalcite-like compounds as precursors for the preparation of mixed oxides which are then used as basic catalysts in the oxydehydrogenation reaction. A series of materials has been synthesised by coprecipitation at constant pH and fully characterised by usual analytical techniques. The catalytic screening tests were carried out in a fixed bed quartz reactor at a temperature of 450°C and the liquid products were analysed off-line by gas chromatography. Some particularities of these materials are brought forward, like the absence of coking which however, does not seem to affect the activity, thus suggesting a different mechanism; the results show high selectivity in styrene, while the activity of the catalysts needs some improvements. For example, with vanadium containing oxides a selectivity of 98% in styrene is achieved with a conversion of 38% in ethylbenzene.     

High Performance of Fe–K Oxide Catalysts for Dehydrogenation of Ethylbenzene to Styrene with an aid of ppm-order Pd

Styrene is manufactured industrially through catalytic dehydrogenation of ethylbenzene on Fe–K oxide-based catalysts. It was invented by Süd-Chemie Group that the activity of the industrial ethylbenzene dehydrogenation catalysts (Styromax) based on the oxides of Fe and K is highly promoted by the addition of small amount (hundreds ppm-order) of precious metals such as Pd. The present work is intended to elucidate the role of Pd on the Fe–K catalyst empirically by use of a periodical pulse technique from a mechanistic point of view. The oxidative dehydrogenation was faster than the simple dehydrogenation, and it proceeded by consuming the surface lattice oxygen in the catalyst. The lattice oxygen was subsequently supplied from steam. Palladium added to the Fe–K oxide catalysts was found to enhance the rate of regeneration (supplying) of the lattice oxygen, although it hardly changed the rate of dehydrogenation of ethylbenzene or consumption of surface lattice O^2? anions. This study demonstrated that steam works not only as a diluent but also as a reactant to form hydrogen and lattice oxygen.     

苯乙烯及乙苯脱氢制苯乙烯催化剂的现状和发展

对国内外苯乙烯的生产能力和市场需求进行了评述,并着重探讨乙苯脱氢制苯乙烯催化剂的研究现状,分析了该领域的发展趋势,指出了国内催化剂存在的差距和新品开发原则,提出了催化剂的开发建议。     

锂对二氧化碳气氛下乙苯脱氢催化剂铁(Fe)/活性炭(AC)的促进作用

研究了助剂Li对CO2气氛下活性炭负载的Fe氧化物(Fe/AC)催化剂上的乙苯脱氢性能的影响和CO2的作用。助剂Li的添加提高了Fe/AC催化剂在CO2气氛下的乙苯脱氢活性和稳定性;CO2气氛下的苯乙烯收率明显高于N2气氛下,表明CO2显著促进了乙苯脱氢反应。     

高收率乙苯脱氢催化剂GS-12的工艺条件研究

介绍了高收率乙苯脱氢催化剂GS-12的特性,研究了乙苯脱氢反应温度、水蒸汽与乙苯物质的量比、空速与转化率和选择性的关系,确定了乙苯脱氢催化剂GS-12在实际生产中适宜的工艺条件。工业应用表明,GS-12催化剂活性较高,能够适应较低水蒸汽与乙苯物质的量比,机械强度高,抗粉化性能好,床层阻力降小,使用寿命预期在30个月以上,综合性能达到国际先进水平。     

低钾型乙苯脱氢催化剂机械强度的优化

考察了各种因素对低钾乙苯脱氢制苯乙烯催化剂机械强度的影响。实验结果表明,通过优化催化剂的化学组成,改进催化剂的制备条件,完全可以开发出机械强度好的低钾乙苯脱氢催化剂。     

On the link between intrinsic catalytic reactions kinetics and the development of catalytic processes: Catalytic dehydrogenation of ethylbenzene to styrene

A procedure linking kinetic modeling of catalytic reactions to reactor modeling for different configurations is developed and applied to the catalytic dehydrogenation of ethylbenzene to styrene. The procedure is applied to four configurations, namely fixed bed with/without hydrogen selective membranes and bubbling fluidized beds with/without selective membranes. The kinetic data for the industrial catalyst are extracted from industrial fixed bed data using a rigorous heterogeneous model. The kinetic data for the three in-house prepared catalysts are obtained from the laboratory scale experiments using pseudo-homogeneous models.     

乙苯脱氢催化剂的发展现状

阐述了乙苯催化脱氢催化剂的发展历程和国内外比较知名的进行乙苯催化脱氢催化剂研发和生产的公司。针对当前乙苯脱氢制苯乙烯领域的发展现状,对乙苯脱氢-氢氧化工艺和乙苯氧化脱氢工艺进行了介绍,并对新工艺配套催化剂的研发进行了概括性总结。