焦化汽油加氢装置增设预饱和反应器的工业应用

经过实验室研究,筛选出合适的催化剂,选择了合适的反应温度和空速等操作条件,可有效脱除焦化汽油中的二烯烃.在焦化汽油加氢装置主反应器前增设预饱和反应器,预饱和原料中二烯烃,减少了反应器顶生焦.并通过预饱和反应器在线处理,延长了焦化汽油装置的运行周期.     

裂解汽油一段加氢绝热反应器的开发

通过对裂解汽油一段加氢8601催化剂及 PGC 催化剂在绝热积分床反应器中的反应特性研究,考察了在工业原料条件下,入口双烯值 C_o、入口温度 T_o 以及液时空速 S_v 对双烯加氢率及反应温升的影响。并利用正交实验设计的方法,回归得到一组经验数学模型。通过误差分析以及将模型的计算值与工业实际生产数据的比较,其双烯加氢率误差小于4%,反应温升误差小于10℃,证明了该模型可以运用于入口双烯值4～12,入口温度30℃～50℃,液时空速6～12h,操作压力3.92MPa 以及氢油比0.2(分子比)的条件下,预示该催化剂在工业反应器中的反应结果,同时也可提供裂解汽油一段加氢绝热反应器的设计参考。     

FCC汽油加氢装置国V升级改造情况的比较

本文从流程设置、操作条件、操作性能、产品质量和能耗等方面对改造后的A公司50万吨催化汽油加氢装置和B公司50万吨催化重汽油加氢装置的情况进行了比较。改造后A公司投资和能耗较高,但装置操作灵活稳定有利于调整产品质量。改造后B公司的投资和能耗相对较低,但由于反应部分的三个反应器从单一热源取热,所以装置操作灵活性差。     

汽油加氢脱臭后硫醇超标的原因分析与对策

针对中石化洛阳分公司在加工含硫原油过程中,选择加氢后的催化汽油进行脱臭后出现的硫醇超标问题进行分析,提出优化加氢操作条件、采用轻、重汽油混合脱臭工艺、将固定床反应器加串联馏程等措施,实施后汽油质量得到明显改善.     

裂解汽油加氢催化剂活性动力学的考察

裂解汽油的一、二段加氢反应过程,因裂解原料组成复杂,其反应速率会随催化剂性能、反应器类型、原料组分及操作参数(入口温度、压力、液时空速、氢/油比及入口物料浓度)的变化而变化,反应过程十分复杂。为了解该加氢反应的规律及其用于工业装置的实际结果,在高压釜及模拟工业装置的小型绝热填充床滴流反应器上,对一段8001等催化剂进行了表观动力学和对8601进行了回归经验数学模型考察;对二段8602B加氢脱硫     

固定床丁醛气相加氢反应器工艺模拟与设计

在对丁醛固定床气相加氢反应体系进行热力学与动力学分析的基础上,采用Matlab软件对管壳式固定床丁醛气相加氢反应器进行了数学模拟。采用平推流反应器模型对列管微元段进行物料衡算和能量衡算,得到丁醛加氢反应器的一维均相数学模型。对加氢反应器的数学模型进行了验证,模拟结果与实际生产数据吻合良好。进一步预测了惰性气体含量、反应空速、温度、压力以及催化剂老化对加氢反应的影响,对固定床丁醛气相加氢反应器的设计具有指导作用,为实际生产中操作参数的优化提供了依据。     

环戊二烯及双环戊二烯对裂解汽油全馏分加氢装置运行的影响

介绍了裂解汽油全馏分加氢过程中发生的环戊二烯热二聚及双环戊二烯热分解反应。该转化反应导致了二段加氢反应器双烯值高于一段出料的双烯值,并缩短了二段加氢反应催化剂的运行周期,提出了降低影响的措施。     

环路反应器制备饱和脂肪酸甲酯的研究

用环路反应器进行椰油酸甲酯加氢制饱和甲酯的结构同搅拌釜对照，反应周期缩短６０％，对实验结果进行了动力学分析，表明环路反应器加氢为二级反应，搅拌釜加氢为一级反应。     

裂解汽油一段选择性加氢的工艺条件研究

采用高压搅拌釜式反应器,在消除催化剂内外扩散影响的基础上,以环戊二烯、苯乙烯和1-己烯与溶剂正庚烷组成的混合物为模型化合物,对裂解汽油一段选择性加氢的操作条件进行了研究.发现当反应温度和压力升高时,各个组分的转化率都随之增高,但是双烯的加氢选择性变差.当单烯和双烯组分共存时,环戊二烯和苯乙烯优先进行加氢反应,当双烯浓度降至一定程度时,1-己烯才进行加氢.此外还采用固定床考察了温度、压力和氢油比对裂解汽油加氢的影响.结果表明,较合适的反应条件为313 K,2.5～3.0 MPa和氢油比25.     

裂解汽油中噻吩加氢脱硫反应宏观动力学

采用微型等温积分反应器,以组分苯、苯乙烯、噻吩与溶剂正己烷的混合物作为模型化合物,在消除催化剂外扩散影响的基础上,建立了幂函数型的噻吩加氢脱硫反应宏观动力学模型并研究裂解汽油二段加氢过程中噻吩在Co-Mo/Al2O3催化剂上的加氢脱硫反应动力学.通过对比研究噻吩在单一体系和模型化合物中的加氢脱硫反应,探讨了裂解汽油中不饱和烃对噻吩加氢脱硫的影响.实验结果表明,裂解汽油中的不饱和烃会影响噻吩加氢脱硫反应速率,但并不改变其反应机理.噻吩转化率的模型计算值与实验值吻合较好,说明所建立的动力学模型适合描述裂解汽油二段加氢过程中噻吩的加氢脱硫反应.     

PTA加氢反应器改造运行状况分析

分析了PTA加氢反应器扩能改造的可行性及其效果 ,介绍了改造前后加氢反应系统的运行情况 ,实际生产分析认为 ,加氢反应器单线生产能力由 45 0kt/a扩大至 70 0kt/a后 ,设备运行安全状况得到彻底改变 ,运行经济性及催化剂寿命较原加氢反应器有很大改善 ,优化调整后的工艺参数为配料质量分数 2 7%～2 8%、反应温度 2 82～ 2 83℃、操作压力 7.4～ 7.5MPa、氢气分压 0 .5～ 0 .9MPa ,预计反应系统生产能力可以达到 40 0kt/a。     

Estimation of Kinetic Parameters for Hydrogenation Reactions Using a Genetic Algorithm

The kinetics of acetylene hydrogenation in a fixed‐bed reactor of a commercial Pd/Al₂O₃ catalyst has been studied. The hydrogenation reactor considered in this work is an essential part of a vinyl chloride monomer (VCM) plant. Three well‐known kinetic models were used to simulate the hydrogenation reactor under industrial operating conditions. Since none of the models provide appropriate prediction, the industrial data and calculated values were compared and optimum kinetic parameters were evaluated utilizing a genetic algorithm (GA) technique. The best kinetic parameters for the three models were determined under specified industrial operating conditions. The hydrogenation reactor was simulated using the estimated optimum kinetic parameters of the three models. Simulation results from the three models were compared to industrial data and the best kinetic model was found. This kinetic model with the evaluated optimum kinetic parameters can well predict the behavior of the industrial hydrogenation reactor to improve the performance of the process.     

Numerical investigation of continuous processes for catalytic hydrogenation of nitrile butadiene rubber

Dynamic behavior of continuous processes was numerically investigated for the catalytic hydrogenation of nitrile butadiene rubber, based on developed models, which took into account the coupling between kinetics and mass transfer. The evolution of hydrogenation reaction trajectories in both cases were analyzed. It is proposed that the coupling behavior between the catalytic hydrogenation and mass transfer was completely determined by the ability of the catalyst in activating hydrogen, carbon‐carbon double bond loading level and the relative capacity of reaction to mass transfer as well as the residence time in the reactor. Four dimensionless parameters were derived to characterize these aspects. The effects of operation conditions on the hydrogenation processes were investigated. The application of the ideal flow models to non‐ideal flows was in addition discussed. It is suggested that the optimal reactor for such a hydrogenation system would be a plug flow reactor with an instantaneous well‐mixing component in the inlet of it, and a reasonable approach to the proposed optimal reactor should be with the flow behavior of at least three continuous stirred tank reactors in series. Further research directions are suggested.     

Numerical investigation and experimental validation of the performance of a tubular packed bed reactor for hydrogenation of diene‐based polymers

A process which comprised a tubular reactor (that can be packed with different internal structures) has been modeled and theoretically analyzed for conducting the hydrogenation of nitrile butadiene rubber (NBR). The dynamics of the tubular reactor and the intrinsic hydrogenation kinetics are coupled, and detailed numerical simulations are performed under isothermal and isobaric conditions. The proposed model thus obtained involves coupled, nonlinear, partial differential equations (distributed parameter system). The effect of different reactor design parameters such as Peclet number, carbon–carbon double bond loading, mass transfer to reaction resistance, and solubility of hydrogen with respect to hydrogenation of the NBR has been investigated numerically. The conversions predicted using the proposed model for tubular packed bed reactor are compared with those possible in conventional plug flow reactor and continuous stirred tank reactor models. The optimal parameters and operating conditions for efficient production of hydrogenated NBR are suggested. Finally, the validity of the proposed model is confirmed by comparing the predicted and the experimental degree of hydrogenation obtained in a tubular reactor packed with Intalox saddles. POLYM. ENG. SCI., 2009. © 2009 Society of Plastics Engineers     

Modelling of kinetics and mass transfer in the hydrogenation of xylose over Raney nickel catalyst

This paper discusses the modelling of xylose hydrogenation kinetics over Raney nickel in aqueous solutions, the determination of the hydrogen solubility in the reaction mixture as well as evaluation of mass transfer effects in the reaction system. The hydrogenation experiments were carried out batchwise in an automatic laboratory‐scale reactor. The reactor system operated at a pressure range of 40–70 bar and at temperatures between 80 and 140 °C. The catalyst‐to‐xylose ratio was approximately 5 wt‐% of the xylose weight normally. The reactor contents were analysed off‐line with a high performance liquid chromatograph. Hydrogen solubility in the reaction medium was determined with a gas‐chromatographic system. The solubility was found to remain fairly constant during the hydrogenation. Only a slight increase in the hydrogen solubility was detected as xylose was hydrogenated to xylitol. The overall hydrogen solubility in the reaction mixture was significantly lower than in pure water, as expected. The main hydrogenation product was xylitol, but small amounts of xylulose and arabinitol were detected as by‐products. A semi‐competitive kinetic model, based on hydrogen and xylose adsorption, was developed. The model accounts for the very different areas covered by a hydrogen atom and an organic species on the catalyst surface. The parameters of the kinetic model were determined with non‐linear regression analysis. It turned out that the kinetic model is able to describe the formation of both xylitol and the by‐products. The mass transfer effects in the batch hydrogenation were evaluated by using measured viscosities and estimated diffusion and mass transfer coefficients. A process simulator, utilizing the kinetic and mass transfer effects, was developed to predict the behaviour of industrial reactors. © 1999 Society of Chemical Industry     

加氢反应器管道设计要点

从加氢装置的核心部分—加氢反应器的设备多种平面布置、反应器框架及平台的设置、反应器的相关附属管道(进料及出料管道、冷氢管道、注硫管道和注氨管道、测压管道和消防管道等)、管道支吊架设置等几个方面,系统论述了加氢反应器的设计要点。     

加氢装置高压反应器床层温度测量

通过柴油加氢装置反应系统温度测量方式不同方案的对比,提出采用新型的热电偶提高加氢装置高压反应器床层温度测量的精确性,实现柴油加氢装置反应系统温度平稳控制。     

Simulation of an Industrial Pyrolysis Gasoline Hydrogenation Unit

A model is developed based on a two‐stage hydrogenation of pyrolysis gasoline to obtain a C₆–C₈ cut suitable for extraction of aromatics. In order to model the hydrogenation reactors, suitable hydrodynamic and reaction submodels should be solved simultaneously. The first stage hydrogenation takes place in a trickle bed reactor. The reaction rates of different di‐olefines as well as hydrodynamic parameters of the trickle bed (i.e., catalyst wetting efficiency, pressure drop, mass transfer coefficient and liquid hold‐up) have been combined to derive the equations to model this reactor. The second stage hydrogenation takes place in a two compartment fixed bed reactor. Hydrogenation of olefines takes place in the first compartment while sulfur is eliminated from the flow in the second compartment. These reactions occur at relatively higher temperature and pressure compared to the first stage. The key component in this stage is considered to be cyclohexene, of which the hydrogenation was found to be the most difficult of the olefines present in the feed. The Langmuir‐Hinshelwood kinetic expression was adopted for the hydrogenation of cyclohexene and its kinetic parameters were determined experimentally in a micro‐reactor in the presence of the industrial catalyst. The model was solved for the whole process of hydrogenation, including hydro‐desulfurization. The predictions of the model were compared with actual plant data from an industrial scale pyrolysis gasoline hydrogenation unit and satisfactory agreement was found between the model and plant data.     

共轭双烯聚合物选择性加氢反应器技术进展

对以橡胶、弹性体为代表的含共轭双烯聚合物进行烯属双键的选择性加氢,可显著提高聚合物的稳定性;加氢反应器和反应工艺是制约加氢度和产率的关键技术之一。该文综述了目前共轭双烯聚合物选择性加氢反应器的技术进展,包括以机械搅拌反应器、鼓泡反应器、外循环反应器为代表的全混流型反应器;以填料塔和静态混合管式反应器为代表的平推流型反应器;以及各种反应器的组合技术、特殊操作方式。结合加氢体系的流体力学特征和反应动力学特征,分析了制约加氢度和产率的关键问题,总结了进一步提高加氢度和产率、降低能耗物耗的潜在途径。     

Modeling of an industrial fixed bed reactor based on lumped kinetic models for hydrogenation of pyrolysis gasoline

In this work, a mathematical model of an industrial fixed bed reactor for the catalytic hydrogenation of pyrolysis gasoline produced from olefin production plant is developed based on a lumped kinetic model. A pseudo-homogeneous system for liquid and solid phases and three pseudo-components: diolefins, olefins, and parraffins, are taken into account in the development of the reactor model. Temperature profile and product distribution from real plant data on a gasoline hydrogenation reactor are used to estimate reaction kinetic parameters. The developed model is validated by comparing the results of simulation with those collected from the plant data. From simulation results, it is found that the prediction of significant state variables agrees well with the actual plant data for a wide range of operating conditions; the developed model adequately represents the fixed-bed reactor.