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。     

产品集总加氢裂化动力学模型的研究及其在加氢裂化中的应用

在分析雪佛龙模型的基础上，提出了适于处理减压渣油加氢裂化过程的按产品划分集总的动力学模型（ＰＬＨＫ模型），同时给出相应的证明过程，并将该模型较为成功地应用于实际加氢裂化过程的模拟。     

四氢萘加氢裂化反应动力学

在双功能催化剂上,利用连续流动固定床微反装置,进行四氢萘加氢裂化反应动力学研究,推导出反应机理,得到了详细的产物分布并推测了７集总反应网络。反应温度为３８０℃时,四氢萘加氢裂化反应主要以异构裂解反应途径为主;反应温度为３２０℃时,主要以加氢裂解反应途径为主。为进一步研究和开发加氢裂化模型奠定了基础。     

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。     

Hydrocracking of Tetralin over Mo-Ni/Usy Dual Functional Catalysts

Tetralin was chosen as a model compound to investigate the reaction networks and kinetics of hydrocracking of polynuclear aromatic hydrocarbons on modified zeolite Y based molybdenum-nickel dual functional catalysts using a continuous flow microreactor at 320-380°C, 8.5 MPa. According to the product distributions, the reaction network of hydrocracking of tetralin was proposed. The pseudo-first-order kinetics rate constants of each step in the network of hydrocracking of tetralin were evaluated by the nonlinear parameter estimation method. The results showed that reaction of hydrocracking of tetralin was a complicated parallel and serial reaction including hydrogenation, isomerization, and cracking (ring opening and dealkylation). The key steps of hydrocracking of tetralin, the conversion of double ring compounds and the yields of mono-ring compounds were affected by reaction temperature and acidity of supports on the catalysts.     

Hydrocracking of Tetralin over Mo–Ni/Usy Dual Functional Catalysts

Abstract

Tetralin was chosen as a model compound to investigate the reaction networks and kinetics of hydrocracking of polynuclear aromatic hydrocarbons on modified zeolite Y based molybdenum–nickel dual functional catalysts using a continuous flow microreactor at 320–380°C, 8.5 MPa. According to the product distributions, the reaction network of hydrocracking of tetralin was proposed. The pseudo-first-order kinetics rate constants of each step in the network of hydrocracking of tetralin were evaluated by the nonlinear parameter estimation method. The results showed that reaction of hydrocracking of tetralin was a complicated parallel and serial reaction including hydrogenation, isomerization, and cracking (ring opening and dealkylation). The key steps of hydrocracking of tetralin, the conversion of double ring compounds and the yields of mono-ring compounds were affected by reaction temperature and acidity of supports on the catalysts.     

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%。     

工业加氢裂化反应器模型的建立

 以某工业加氢裂化反应器装置为研究对象,根据物料平衡、能量平衡和反应动力学方程,建立了加氢裂化反应器的数学模型,并根据工业数据,采用遗传算法对模型中的参数进行拟合,还以不同的工业数据对模型进行验证。结果表明,所建立的模型能够较好反映加氢裂化装置性能,且能较好地预测加氢裂化主要产品的收率分布及反应器的温度分布。     

中温煤焦油加氢裂化集总动力学研究

以集总动力学为建模思想,将中温煤焦油裂化反应网络按原料油四组分和产品油馏分为划分标准,归并为6个虚拟集总组分,考察了氢分压、液体体积空速、床层温度对中温煤焦油加氢裂化结果的影响,建立了中温煤焦油6集总加氢裂化动力学模型。在Visual C++平台上,采用四阶变步长的Runge-Kutta法求解微分方程,采用变尺度法(B-F-G-S)获得函数最优化求解,并进行模型验证。结果表明,该模型预测相对误差小于3%,对中温煤焦油加氢裂化的产品分布具有良好的预测性,为煤焦油加氢工艺的进一步优化提供了依据。     

基于半监督学习-多通道卷积神经网络的加氢裂化产品性质预测

提出了一种用于加氢裂化产品性质预测的半监督学习-多通道卷积神经网络(SSL-MCCNN),通过逐层卷积实现加氢裂化工艺流程空间域局部特征提取,并基于多通道采样实现了时域特征提取。在应对模型训练中由于产品性质数据量不足导致的小样本学习问题方面,基于教师-学生半监督学习(TS-SSL)生成虚拟样本集实现了数据扩充,进一步提升了模型预测性能。基于SSL-MCCNN对煤油-柴油加氢裂化工业装置重石脑油密度和柴油闪点预测的均方根误差(RMSE)分别为0.83和1.03,判定系数(R²)分别为0.90和0.98,与BP神经网络(BPNN)和径向基神经网络(RBFNN)相比,SSL-MCCNN在实现最小RMSE的同时达到了最优R²。实验结果表明,所提出的SSL-MCCNN有效提取了加氢裂化工艺流程的时空域特征,显著提升了模型预测性能。     

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.     

减压蜡油加氢裂化六集总动力学模型研究

以加氢裂化催化剂A的加氢裂化实验结果为基础,建立了减压蜡油加氢裂化六集总动力学模型。六集总的划分原则以实际加氢裂化产品切割方案为参照,具体划分如下：按固定馏程间隔把石油馏分（原料油和生成油）划分为六个集总,即减压蜡油-加氢裂化尾油（>360 ℃）、柴油馏分（290~360 ℃）、航空煤油馏分（175~290 ℃）、重石脑油（65~175 ℃）、轻石脑油（<65 ℃）和炼厂气（C4－）。在Matlab 2011b数值计算软件上,利用非线性最小二乘法对动力学模型参数进行了优化回归。通过统计分析,忽略了部分集总间的反应。模型预测所得加氢裂化产物收率与实验结果的最大偏差为1.80%,满足工业应用要求。     

加氢裂化集总反应动力学模型研究

根据加氢裂化反应机理和反应特征，建立了通用性较强的加氢裂化集总动力学模型；采用序列二次规划方法进行参数估计，确定了反应动力学参数。研究结果表明，模型能很好地拟合实验数据，并具有良好的预测性能。     

中压加氢改质装置动态数学模型的开发

以加氢裂化集总动力学模型为基础建立了中压加氢装置的仿真培训系统,重点是表征反应器的开工过程,并开发相应的加氢精制和加氢裂化反应器动态数学模型,使其在较宽的工艺条件范围内与试验值吻合。在仿真培训系统的实际应用表明,所开发的模型逼真度高,可满足实时性的要求,能产生较好的培训效果     

Maximizing Diesel Production From Vacuum Gas Oil Using a Two Stage Hydrocracker

In this study, a six-lump model was sufficient to describe the kinetics of vacuum gas oil (VGO) hydrocracking in order to maximize the production of middle distillate diesel. The kinetic lump model target was to obtain the reaction rate constants that represent all the hydrocracking reactions in the process. The operating conditions such as temperature, pressure, and hydrogen severity were tested to find the optimum parameters that maximize diesel yields. Mild hydrocracking operating conditions of temperature and pressure were used in a commercial hydrocracker with hydrogen severity similar to hydrotreating processes. The main reaction was the VGO conversion to diesel based on its high reaction rate constant compared with other reactions. In addition, the main reaction had the highest effect on catalyst deactivation based on the resulted deactivation factor. A multi-linear regression correlation was obtained for maximizing diesel production as a function of operating pressure, temperature, and hydrogen amount, keeping the diesel specifications within the market demand.     

HYDROZEN TRANSFER HYDROCRAKING OF C.PROCERA UNDER AMBIENT PRESSURE CONDITIONS TO GET VALUE ADDED CHEMICALS AND FUELS

Biomass is renewable source of energy while the reserves of petroleum arc being depleted. The latex of a potential petrocrop, Colotropis procera, a lalicifcr, arid-plant which is rich in hydrocarbon type triterpene compounds etc. was found lo be a better feed slock for thermal hydrocracking as compared to whole plant biomass inlcrms of liquid product yield. Studies of chemical reaction dynamics of the thermal cracking of latex at 200-400°C showed that the process should be termed as hydrogen-tranfer (H-T) hydrocracking of latex under ambient pressure conditions. The hydrogen rich cracked trilcrpenoids act as the H-donors in this process, where nascent hydrogen atoms and free radicals chemically plug the cracked moities to stabilise these. Latex was also coagulated and the H-T hydrocracking of the feedstock coagulum gave a higher yield of cracked oil in comparision lo that from the dried latex. A model triterpene compound, ursolic acid has been subjected to H-T hydrocracking to understand the process of hydrocracking of latex under similar conditions and it was found that triterpencs on H-T hydrocracking produced only liquid and gaseous products and no solid char. The temperature for hydrocracking of latex has been optimized to 350°C and molecular sieve was round to catalyse the H-T Hytrocraking process to yield more liquid product The distillation range of cracked latex on(CLO)Obtained from H.T Hytrocracking of C procera Latex indicated that it can be used as fuel. Moreover CLO resembled diesel fuels and was predominantly paraffinic in nature as characterised by NMR and FTIR spectral analysis. A process has been recommended for gelling value added fuels and chemicals from C. procera latex.     

HYDROZEN TRANSFER HYDROCRAKING OF C.PROCERA UNDER AMBIENT PRESSURE CONDITIONS TO GET VALUE ADDED CHEMICALS AND FUELS

ABSTRACT

Biomass is renewable source of energy while the reserves of petroleum arc being depleted. The latex of a potential petrocrop, Colotropis procera, a lalicifcr, arid-plant which is rich in hydrocarbon type triterpene compounds etc. was found lo be a better feed slock for thermal hydrocracking as compared to whole plant biomass inlcrms of liquid product yield. Studies of chemical reaction dynamics of the thermal cracking of latex at 200-400°C showed that the process should be termed as hydrogen-tranfer (H-T) hydrocracking of latex under ambient pressure conditions. The hydrogen rich cracked trilcrpenoids act as the H-donors in this process, where nascent hydrogen atoms and free radicals chemically plug the cracked moities to stabilise these. Latex was also coagulated and the H-T hydrocracking of the feedstock coagulum gave a higher yield of cracked oil in comparision lo that from the dried latex. A model triterpene compound, ursolic acid has been subjected to H-T hydrocracking to understand the process of hydrocracking of latex under similar conditions and it was found that triterpencs on H-T hydrocracking produced only liquid and gaseous products and no solid char. The temperature for hydrocracking of latex has been optimized to 350°C and molecular sieve was round to catalyse the H-T Hytrocraking process to yield more liquid product The distillation range of cracked latex on(CLO)Obtained from H.T Hytrocracking of C procera Latex indicated that it can be used as fuel. Moreover CLO resembled diesel fuels and was predominantly paraffinic in nature as characterised by NMR and FTIR spectral analysis. A process has been recommended for gelling value added fuels and chemicals from C. procera latex.     

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。     

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.     

对新建炼油厂规划总加工流程的优化

通过建立PIMS模型,对新建炼油厂3种总加工流程进行了分析。各方案总体采用渣油加氢脱硫(ARDS)、重油催化裂化(RFCC)和加氢裂化(HCU)总工艺流程。三者主要区别在于各装置进料组合及HCU所采取工艺的不同。结果表明,方案二综合商品率、财务净现值和内部收益率最高,方案相对最优。