重油接触裂解制乙烯集总反应动力学模型研究

从重油接触裂解 (HCC)工艺特点出发 ,在分析HCC工艺原料油结构族组成、考察不同原料油HCC反应行为的基础上 ,利用集总的方法 ,建立了HCC工艺 1 6集总反应动力学网络 (物理模型 ) ,并推导建立了数学模型。该模型体现了反应温度、反应压力、剂油比、水油比及催化剂活性等因素的影响 ,能够比较准确地描述HCC工艺的反应行为。采用分层测定和多参数估算方法 ,求取了反应网络中 70个反应速率常数和相应的活化能 ,并对该模型进行了实验验证。结果表明 ,模型计算值与实测值吻合良好 ,各产品产率计算值与实测值的绝对偏差一般在 0 5%左右 ,表明该软件具有较高计算精度和良好的预测能力     

加氢尾油裂解集总动力学模型的研究

用集总的方法,对大庆化工研究中心模拟裂解装置得到的27次实验数据进行了分析,建立了5个反应的集总动力学物理模型.并根据上述实验数据,用Marquardt++法编写的Matlab语言程序进行了优化计算,求得了该加氢尾油的反应速度常数、指前因子和活化能.将模型计算结果与实验数据进行了对比,结果表明:该模型能较好地描述加氢尾油的裂解规律,可为重质油裂解提供计算机模拟数据.     

催化裂化（裂解）集总反应动力学模型研究进展

分别从催化裂化集总反应动力学模型、催化裂解集总反应动力学模型、集总反应 流动耦合的催化裂化模型、集总反应 催化剂性质耦合的催化裂化模型、催化剂失活模型、建模数据来源、参数估算方法和集总动力学模型的关联模型等方面,系统地介绍了催化裂化(裂解)集总反应动力学模型的研究进展。在分析总结的基础上,针对催化裂化(裂解)集总反应动力学模型研究的后续发展提出了几点建议。     

催化重整集总反应动力学模型研究

本文提出了一个包括16个集总组分的催化重整动力学模型,在氢气压力为(8～12)×10~5Pa、温度为460～500℃、氢油摩尔比为10的条件下测定了该模型的动力学参数.用最佳步长策略方法、Marquadt 方法及区域约束的参数估计方法估计出反应网络的动力学参数,计算出各个反应的活化能和频率因子.模型中各个组分的实验值与计算值的拟合很好,模型能较好地预测各组分的浓度分布.     

基于结构导向集总的石脑油蒸汽裂解过程分子尺度动力学模型

用结构导向集总方法描述原料分子和构建反应网络,分别采用Materials Studio软件和四五阶龙格库塔法计算反应速率常数和求解动力学微分方程组,建立了1个石脑油蒸汽裂解过程的结构导向集总模型.模型选用7种结构向量描述石脑油分子组成,74条反应规则建立石脑油蒸汽裂解过程的反应网络.它可以在不同操作条件下预测不同石脑油原料蒸汽裂解过程中132种种子分子收率随时间的分布.模型计算结果表明,乙烯和丙烯收率的计算值和实验结果符合良好,相对误差不超过8%.模型对丁二烯,甲烷,乙烷等非主要产物也具有一定的预测能力.     

催化重整集总反应动力学模拟

在Smith集总反应动力学模型基础上,建立催化重整轴向和径向反应器的数学模型,对工业装置进行模拟。并利用实际生产操作数据,对Smith模型动力学参数进行了优化。用优化后的模型对装置进行模拟计算,其结果与实际操作吻合较好。     

稠油水热裂解反应动力学研究

根据辽河稠油水热裂解实验中各种产物的变化规律,建立了五集总(气体、饱和分、芳香分、胶质、沥青质)动力学模型。并将Runge-Kutm积分法与复合形法联用,求取模型中的动力学参数。计算结果表明,稠油水热裂解五集总动力学模型与实验数据吻合很好。     

石蜡裂解制α-烯烃集总动力学模型

 将集总动力学模型运用于石蜡裂解反应研究，建立了石蜡裂解的集总动力学模型，并通过实际试验中所得的数据验证了模型的准确性，讨论了反应温度及反应时间对模型的影响，为预测产品收率及产品分布、工业装置的生产调试提供了理论依据。     

渣油加氢脱硫反应集总动力学模型的事前模拟

 通过渣油加氢脱硫(HDS)中试装置实测数据，对渣油HDS反应集总动力学进行事前模拟。根据渣油中硫化物加氢反应速率的快慢，将其分别划分为2~6个集总，建立了5种渣油HDS反应集总动力学模型。通过对该5种模型拟合误差的比较分析，得到三、四集总模型的拟合平均相对误差最小。然后分别针对三、四集总渣油HDS反应动力学模型，求取了其动力学参数，并采用实测数据对模型的稳定性和外推性进行了验证。结果表明，模型参数中，温度、空速和氢分压等因素对HDS反应的影响符合硫化物加氢反应规律，对三、四集总模型验证的平均相对误差分别为2.32%和1.98%，说明模型的拟合性和预测性良好。所建模型可为渣油HDS反应集总动力学的深入研究提供参考。     

重油加氢裂化四集总反应动力学模型的研究

以800 kt/a重油加氢裂化装置为背景,根据加氢裂化反应机理,建立了四集总模型作为加氢裂化反应动力学模型。采用高斯-牛顿法对模型的参数进行了估计和四阶龙格-库塔法计算有初始值的常微分方程,并用现场实测数据进行了验证。结果表明:模型的计算值与实测值平均相对误差小于5%,因此该集总模型具有较高的模拟精度。     

A six-lumped kinetic model of pyrolysis of heavy oil in supercritical methanol

The product distribution of pyrolysis of heavy oil in the supercritical methanol (SC-MeOH) was studied. It could be found that the pyrolysis reaction rate enhanced with the increase of temperature. Compared with reaction in N₂, the coking formation was promoted in SC-MeOH. It was attributed to “cage effect” caused by methanol. The aromatics and resins which can dissolve asphaltenes were isolated by cages. Therefore, more coke was formed by condensation of asphaltenes. A lumped reaction kinetic model modified by equilibrium mass fraction of aromatics and resins was established, which could describe and predict the products distribution in SC-MeOH.     

Thermogravimetric analysis and kinetic study of heavy oil pyrolysis

Pyrolysis, so-called devolatilization, is one of the first steps of all thermochemical processes occurring in an inert atmosphere. The authors discuss the main kinetic features of heavy oil pyrolysis, on the basis of the data derived m from a TGA analysis and by using a kinetic model. The samples were heated over a range of temperature from 400 K to 430°C at various heating rates between 10 and 80°C/min. Experimental results showed that the effect of time is considerable in the case of tar conversion, compared to char and gases.     

石脑油蒸汽热裂解过程中的结焦速率研究

在实验室蒸汽热裂解装置(BSPA)上,考察了石脑油进料质量流速、裂解温度、烃分压和运行时间等反应条件对石脑油热裂解过程中裂解炉管结焦速率的影响。结果表明,在石脑油进料速率为90 g/h,水油质量比为0.6,炉管进口压力为0.05 MPa的条件下运行6 h,随着裂解温度的升高,裂解炉管结焦速率逐渐增大;当裂解温度为850℃时,结焦速率与烃分压呈线性关系;随着裂解炉运行时间的延长,结焦速率下降。     

大豆油及石脑油蒸汽裂解加工工艺的研究

以大豆油和石脑油为原料,分别进行了蒸汽裂解实验,考察了温度和水油质量比对产品收率的影响。结果表明,石脑油和大豆油生产乙烯、丙烯以及丁二烯时,产品收率变化趋势相同,随着裂解温度和水油比的升高,乙烯收率均增加,丙烯和丁二烯收率则先增加后降低。在裂解温度为750℃,水油比为0.8的条件下,大豆油的乙烯收率为22.8%,丙烯收率为9.5%,丁二烯收率为4.3%;石脑油的乙烯收率为21.8%,丙烯收率为14.2%,丁二烯收率为3.4%。     

Industrial delayed coking process optimization on the basis of lumped kinetic model

Delayed coking is an economic and practical technic for the conversion of residua to naphtha and diesel. In this work, a 10-lumped reaction scheme is applied to investigate the industrial delayed coking process. The feed is decomposed to four lumps, including saturate, aromatics, resin and asphaltenes, and the products are decomposed to six lumps according to the boiling points. Industrial data from a Chinese petroleum refinery are used to validate the model. It is shown that the proposed kinetic model is able to predict yields of delayed coking products at a wide range of feedstock properties. On the basis of this model, the feed distribution and reaction temperature of an industrial delayed coking process are optimized, which significantly increases the economic benefits.     

A lumped kinetic model for heavy oil catalytic cracking FDFCC process

Based on the reaction mechanisms and the characteristics of flexible dual-riser fluid catalytic cracking (FDFCC) process, the reaction networks of 10 lumps for heavy oil and seven lumps for gasoline were put forward. The cracking reactions of resin and asphaltene into gasoline and gases in heavy oil riser reactor were considered as second-order ones while the other reactions were described as first-order ones. The kinetic parameters indicate good consistence with the reaction rules of heavy oil catalytic cracking. The relative errors between calculated values and actual values of products are all less than 4%, which shows the reliability of the models.     

A lumped kinetic model for heavy oil catalytic cracking FDFCC process

Based on the reaction mechanisms and the characteristics of flexible dual-riser fluid catalytic cracking (FDFCC) process, the reaction networks of 10 lumps for heavy oil and seven lumps for gasoline were put forward. The cracking reactions of resin and asphaltene into gasoline and gases in heavy oil riser reactor were considered as second-order ones while the other reactions were described as first-order ones. The kinetic parameters indicate good consistence with the reaction rules of heavy oil catalytic cracking. The relative errors between calculated values and actual values of products are all less than 4%, which shows the reliability of the models.     

Study and Analysis on Naphtha Catalytic Reforming Reactor Simulation

1 IntroductionCatalytic reforming of naphtha or mixture of naphthas with acertain amount of cracked oil is a process of great interest tothe petrochemical industry for the production of aromaticcompounds that are raw materials for plastics, elastomers andresins manufacture. Catalytic reforming unit uses naphtha orcracked oil as feedstock to produce aromatic-rich compoundsand high-octane liquid products through reactions such asaromatization, cyclization, and hydrocracking. At the sametime, it …     

炼厂丙烷与拔头油的裂解性能及利用研究

采用裂解制乙烯实验室评价装置,对兰州石化公司炼油厂催化裂化装置副产的丙烷、催化重整装置副产的拔头油进行了裂解性能评价实验。结果表明：丙烷和拔头油均为优质的裂解原料,在适宜的裂解条件下,其所得乙烯产物的收率可分别达到37．62％和34．09％,三烯收率可分别达到52．60％和53．94％。提出了丙烷、拔头油的裂解利用方案,即丙烷与乙烷共裂解、拔头油单独裂解、或丙烷与拔头油共裂解。使丙烷和拔头油在乙烯装置上得到了利用,将原来的燃油转化成高附加值的化工产品,获得了较好的经济效益。     

A kinetic model for pyrolysis of petroleum residue under nonisothermal conditions

Kinetic study on pyrolysis of petroleum residue was carried out by an accurate Arrhenius type equation at heating rate of 0.5–30.0°C/min under nonisothermal conditions. The influence of some critical parameters including temperature, heating rate and activation energy on mass conversion was evaluated. The apparent activation energies for during the pyrolysis process were in the range of 198–361 kJ/mol at various mass conversions of 5–94%. The reaction temperature was introduced as the most important parameter for the improvement of mass conversion, compared to that of other parameters. The pyrolysis of petroleum residue was occurred in a broad temperature range, from 150–650°C, yielding 33 wt% unpyrolyzed residue. It also was found that an increase in heating rate has a minor impact in the process. Model predictions were compared with experimental data, which showed fully good agreement.