重质油加氢裂化反应动力学的研究

本文依据大量文献资料，介绍了重质油加氢裂化反应动力学的研究现状，对各种动力学模型的优缺点进行了评论，指出了催化裂化和加氢裂化反应动力学的相似性和进一步深化研究的方向。     

加氢裂化集总动力学模型的研究Ⅱ．正十烷加氢裂化集总模型

选用３８２４加氢裂化催化剂，对正十烷加氢裂化动力学进行了研究。根据Ｗｅｅｋｍａｎ集总理论，建立了正十烷加氢裂化四集总动力学模型。用Ｍａｒｑｕａｒｄｔ法估计了各反应速率常数，确定了较完善的速率表达式和表现活化能，同时讨论了空速、温度、压力和反应活化能对产物分布的影响，为石油馏份加氢裂化集总动力学研究提供了基础数据。     

分散型铁催化剂存在下孤岛渣油加氢裂化的七集总动力学模型

本文研究了孤岛渣油在分散型铁催化剂存在下加氢裂化反应的动力学规律，建立了孤岛渣油加氢裂化反应七集总（气体Ｃ１－Ｃ４、馏分油Ｃ５－４８０℃、饱和分、芳香分、胶质、沥青质及苯不溶物－焦）动力学反应模型。在此，提出了在处理动力学模型时虑到反应物结构的变化，并且构造出了结构变化的计算函数，结果表明，当考虑到结构变化时，理论计算的动力学模型与试验数据能较好地吻合。     

重质油加氢裂化反应动力学的研究

本文依据大量文献资料,介绍了重质油加氢裂化反应动力学的研究现状,对各种动力学模型的优缺点进行了评价,指出了催化裂化和加氢裂化反应动力学的相似性和进一步深化研究的方向。     

基于Single Event方法的正辛烷加氢裂化机理动力学研究

研究了Ni-W催化剂催化正辛烷加氢裂化的详细机理动力学。管式固定床反应器采集动力学实验数据，各实验条件下加氢裂化产物均通过色质联用分析获取其详细的产物组成。根据碳正离子反应机理建立了简化的反应网络，各基元步骤中PCP异构化和β位断裂为速率控制步。通过Single Event方法对速率系数的模型化，基于详细基元步骤的正辛烷加氢裂化动力学模型独立参数个数得到简化，遗传算法和Marquardt算法对12个动力学参数进行回归。对于不同反应条件下的产物生成速率，模型计算值与实验值符合良好。由于Single Event方法所得的动力学模型参数与原料的碳数组成无关，因此该结果可以为进一步外推到高碳数的模型化合物和费-托蜡等复杂油品的加氢裂化动力学计算提供有意义的参考。     

中低温煤焦油加氢裂化集总动力学模型的研究

以煤焦油为原料,在高压固定滴流床反应器中,以工业NiMo/Al2O3为催化剂,考察了360-380℃范围内煤焦油的产物分布,基于此建立了5集总煤焦油加氢裂化动力学模型。动力学模型的集总包括：未反应的煤焦油、柴油、汽油、气体和焦炭。通过对实验产物与模型预测产物的对比数据,发现本文所建立的动力学模型可以用于煤焦油加氢裂化过程。同时,基于动力学模型,进一步分析了煤焦油的加氢裂化机理：在整个煤焦油加氢裂化过程中,柴油馏分可作为反应中间组分。     

用正交配置法模拟加氢裂化反应器

结合物料平衡、能量平衡和加氢裂化反应动力学方程,按照加氢裂化反应的特点,建立了加氢裂化反应器6集总动态机理模型。反应动力学采用原料油、柴油、航空煤油、重石脑油、轻石脑油、气体6集总模型。对总动态机理模型提出了正交配置法和龙格-库塔法相结合的求解方法。新的求解方法计算量小、精度高,并且能求得微分数学模型的近似解析解。应用6集总动态机理模型对加氢裂化反应器进行了模拟,考察了模型的预测精度。模拟结果表明,该模型能较好地模拟和预测加氢裂化产品的收率分布和反应器的温度分布,具有较高的预测精度,模型可靠。     

加氢型化集总动力学模型的研究：Ⅰ.四氢萘加氢裂化集总模型

在国产加氢裂化催化剂３８２４上，利用连续流动微型反应装置，对四氢萘加氢裂化动力学进行了研究。根据四氢萘加氢裂化的反应结果，在一定的简化条件下，建立了四氢萘加氢裂化应集总网络。用Ｍａｒｇｕａｒｄｔ法估计了条步反应速率常数，预测了各反应产物分布，其结果与实验吻合。同时，讨论了空速、温度、反应活化能对产物分布的影响，为馏分油加氢裂化集总动力学研究提供了基础数据。     

加氢裂化动力学模型及其工业应用

在文献调查及对加氢加过程深入研究的基础上，建立了稳态的加氢裂化反应动力学模型，并将该模型较成功地应用于工业加氢氧化反应过程的模拟。     

加氢裂化反应动力学模型的建立及参数拟合方法的研究

本文分析了参数互补作用对参数拟合结果的影响在Ｃｈｅｖｒｏｎ加氢裂化应动力学模型基础上，提出了四参数模型，并讨论了参数的数值范围。本文提出的两步逐次修正法，可快速拟合复杂交变温反应的动力学模型参数。     

Kinetic model for hydrocracking of Iranian heavy crude with dispersed catalysts in slurry-phase

A five-lump kinetic model has been presented to describe the process of heavy oil hydrocracking, and tested in moderate condition. In the condition of low temperature and pressure relatively, coke formation can be controlled and the model is well applied with product distribution. In this paper, we explored the process of hydrocracking in slurry-phase by using dispersed catalyst at higher temperature and pressure, it was found that at the high residue conversion, the coke formation could be controlled even if the residue conversion is up to 90%. Then, a five-lump model by analytical method based on Monte Carlo technique was used to calculate the kinetic parameters, and the product distribution in the condition of high conversion was predicted successfully.     

A Four Lump Kinetic Model for the Simulation of the Hydrocracking Process

Hydrocracking is a very important secondary refining process used to convert low value vacuum gas oils into high value fuels. The chemistry of the hydrocracking process is very complex due to the involvement of high molecular weight complex hydrocarbons in the reactions. Process modeling and simulation of the hydrocracking unit is very challenging due to the complexities of chemistry and the process. In the present work, a mathematical model is described to analyze the performance of the hydrocracking process in terms of product yields. A four lump discrete lumping approach is employed with a hydrocracking reaction scheme involving six reactions. The kinetic constants for the reactions were estimated by minimizing the error between the experimental and predicted yields of kinetic lumps. Experimental data reported by Ali et al. (2002) were used to validate the proposed model. The model predictions were found to agree well with the experimental data. The proposed model can be used to simulate the performance of commercial hydrocrackers using kinetic parameters estimated from pilot plant experiments.     

悬浮床加氢裂化集总动力学模型的研究

在不同反应温度、氢初压条件下,通过高压反应釜对克拉玛依常压渣油（KLAR）进行加氢裂化实验,以此模拟悬浮床加氢裂化过程,并根据实验数据及实际工艺中对各种轻油产品收率预测的需求建立了悬浮床加氢裂化六集总（气体、汽油、柴油、蜡油、减压渣油、焦）动力学模型,用matlab软件进行编程,采用最小二乘法对动力学参数进行估算,并进行误差分析。结果表明,建立的六集总动力学模型能很好的对各集总产品收率进行预测,计算结果与实验值基本吻合,大部分误差在5%以内。     

A Kinetic Model for Hydrocracking Process

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减压蜡油加氢裂化催化剂组合动力学模型

以高压加氢裂化六集总动力学模型为基础,建立预测催化剂组合体系产品分布的数学模型。按固定馏程间隔将原料油和加氢裂化生成油划分为减压蜡油 加氢裂化尾油（>360℃）、柴油馏分（290～360℃）、喷气燃料馏分（175～290℃）、重石脑油馏分（65～175℃）、轻石脑油馏分（<65℃）和炼厂气（C4-）6个集总。分别以2种不同类型加氢裂化催化剂的实验数据为基础,采用Matlab 2011b数值计算软件和非线性最小二乘法对动力学模型参数进行了优化回归。以优化回归后的动力学模型参数为初值,调整部分模型参数,建立了预测催化剂组合体系产品分布的数学模型。用该模型计算得到的加氢裂化产品分布与实验值之间的一致性较好,其偏差均小于2%。     

Mild Hydrocracking—A Review of the Process,Catalysts, Reactions,Kinetics, and Advantages

Abstract

The demand for high quality middle distillates is increasing world wide while the demand for residue and fuel oil is decreasing. Hydrocracking is the major conversion process that meets the twin objectives of producing more middle distillates of very high quality. Since hydrocracking is a capital-intensive process, many refiners consider the option of converting their existing vacuum gas oil hydrotreating units into mild hydrocracking units. The use of mild hydrocracker bottom as FCC feedstock can improve the quality of FCC products. In view of the advantages of mild hydrocracking process, it is essential to understand the process, catalysts used, reactions, kinetics, and advantages. This article reviews recent literature on MHC process, various catalysts used, reactions involved and advantages of mild hydrocracking process in terms of improved product qualities and increased distillates. The kinetics of the mild hydrocracking process and kinetic challenges with respect to aromatic saturation have been summarized. The limitations of the process and future scope of work in this area are also discussed briefly.     

Mild Hydrocracking—A Review of the Process, Catalysts, Reactions, Kinetics, and Advantages

The demand for high quality middle distillates is increasing world wide while the demand for residue and fuel oil is decreasing. Hydrocracking is the major conversion process that meets the twin objectives of producing more middle distillates of very high quality. Since hydrocracking is a capital-intensive process, many refiners consider the option of converting their existing vacuum gas oil hydrotreating units into mild hydrocracking units. The use of mild hydrocracker bottom as FCC feedstock can improve the quality of FCC products. In view of the advantages of mild hydrocracking process, it is essential to understand the process, catalysts used, reactions, kinetics, and advantages. This article reviews recent literature on MHC process, various catalysts used, reactions involved and advantages of mild hydrocracking process in terms of improved product qualities and increased distillates. The kinetics of the mild hydrocracking process and kinetic challenges with respect to aromatic saturation have been summarized. The limitations of the process and future scope of work in this area are also discussed briefly.