An Orthogonal Method for Aromatization Reactions of Shenghua Liquefied Petroleum Gas

Abstract:

By using Shenghua liquefied petroleum gas, FCC gaoline as a feedstock, LBO-A and LBO-16 as catalysts, and a confined fluidized bed as a reactor, the aromatization reaction of liquefied petroleum gas and FCC gasoline has been studied in an orthogonal method, and the nine lumps model has been put forward based on the aromatization reaction of liquefied petroleum gas. A mathematical method obtained is first introduced to study the relationship of various products of aromatization, and it is beneficial to know the mechanism and kinetics of the aromatization reaction to adapt to the necessity of industrialization.     

An Orthogonal Method for Aromatization Reactions of Shenghua Liquefied Petroleum Gas

By using Shenghua liquefied petroleum gas, FCC gaoline as a feedstock, LBO-A and LBO-16 as catalysts, and a confined fluidized bed as a reactor, the aromatization reaction of liquefied petroleum gas and FCC gasoline has been studied in an orthogonal method, and the nine lumps model has been put forward based on the aromatization reaction of liquefied petroleum gas. A mathematical method obtained is first introduced to study the relationship of various products of aromatization, and it is beneficial to know the mechanism and kinetics of the aromatization reaction to adapt to the necessity of industrialization.     

Effects of Reaction Temperature on Distribution of Aromatization Reaction Products of Lanlian FCC Gasoline

Abstract

By using Lanlian FCC gasoline as a feedstock, the effects of temperature on the product distribution, light oil compound (gasoline and diesel), off-gas, and liquefied gas were researched in a confined fluidized bed reactor. The experimental results showed the off-gas, liquefied gas, and coke conversion were slowly increased with increasing temperature; the gasoline conversion had a maximum with increasing temperature; the diesel conversion showed no change; the olefins conversion was increased with increasing temperature; the aromatics yield was increased from 390°C to 430°C and from 430°C to 490°C, respectively; and the FCC gasoline Research Octane Number (RON) increased value was increased almost linearly with increasing the temperature. Aromatization index (AI) was put up in order to judge the aromatization degree of the FCC gasoline. The method obtained provided technical instruction for the petroleum chemical plant.     

Reaction Processing of Fraction of Yanhua FCC Gasoline

By using fraction of Yanhua FCC gasoline as a feedstock, the effects of reaction temperature, weight hour space velocity, feedstock performance on yields of liquefied petroleum gas production, and aromatics and propylene are researched in a confined fluidized bed reactor. Aromatization index (AI) and competent parameter (CP) are first proposed to study the mechanistic pathways of aromatization reaction of fraction of Yanhua FCC gasoline. The experimental result shows AI values of FCC gasoline decrease with the increase of the reaction temperature under the same catalyst; CP values and the aromatization reaction function for the same catalyst increase with the increase of the reaction temperature. The isomerization reaction for fraction of Yanhua FCC gasoline has more advantage than that of the aromatization reaction.     

COPROCESSING OF COAL WITH HEAVY PETROLEUM CRUDES AND RESIDUA

ABSTRACT

This work investigates the coprocessing of coal in six different heavy petroleum crudes and residua. Coprocessing reactions of coal and the petroleum solvents are performed under three sets of constant reaction conditions, yielding informative comparative data for processing applications. Definitive comparisons of coal reactivity and solvolysis in the petroleum solvents have been obtained using solvent fractionation which provides a measure of the degree of upgrading achieved by the liquefied coal. Regressive reactions and low coal conversions are observed in coprocessing reactions in N₂ at 400^°C. Higher conversions and a reduction in regressive reactions are observed in H₂ at 400^°C. Catalytic hydrotreatment and higher temperature, 425^°C, result in increased coal conversion and a net production of pentane soluble materials. The amount of product fractions obtained from the upgrading of the coal alone is calculated. The effect of reaction temperature using different solvents and reaction conditions on the product slate is also examined.     

液化石油气制芳烃技术的研究与应用进展

在分析液化石油气芳构化生产芳烃的反应机理的基础上，介绍了利用移动床反应器生产芳烃的Cyclar工艺和利用固定床反应器生产芳烃的Z-forming工艺、GTA工艺。通过分析认为GTA工艺具有流程短，投资少，操作费用低等优点，并有一套工业装置已开工运行。     

丁烷芳构化反应规律的研究

利用100 mL等温固定床实验装置,采用LAC芳构化催化剂,研究了丁烷芳构化生产芳烃的反应规律,主要考察了反应温度和空速对丁烷芳构化产品分布的影响。实验结果表明,高温和低空速可得到较高的液体收率和芳烃收率。随着反应温度的升高,丁烷芳构化反应的液体收率逐渐增大,同时干气产率也增加较快;随着进料空速的增大,丁烷芳构化反应的液体收率和干气收率逐渐减小,而液化石油气收率逐渐增大。反应温度和进料空速对n-C4H10的芳构化反应影响较大,而对i-C4H10的影响较小;i-C4H10较n-C4H10易转化为芳烃,当反应温度为460～540℃、质量空速为0.25～1.00 h-1时,以n-C4H10为原料能得到质量分数为17%～30%的轻质芳烃和质量分数为10%～16%的液化石油气,以i-C4H10为原料能得到质量分数为33%～41%的轻质芳烃和质量分数为21%～34%的液化石油气。在大量实验的基础上得到了丁烷单体烃芳构化反应的液体收率随工艺条件变化的经验关联式,利用此关联式在一定条件下可以预测不同组成丁烷芳构化反应的液体收率,关联式的绝对误差小于2.5%。     

The Effects of Weight Hour Space Velocity on the Products Distribution of Aromatization Reaction of Lanlian FCC Gasoline

Abstract

By using Lanlian fluid catalytic cracked (FCC) gasoline as a feedstock, the effects of weight hour space velocity (WHSV) on the product distribution, light oil compound, off-gas, and liquefied petroleum gas were researched in a confined fluidized bed reactor. The equation of off-gas yield, liquefied petroleum gas yield, coke yield, and light oil yield with increasing WHSV were established in the experimental data. The experimental result showed that with increasing WHSV, coke, off-gas, and liquefied petroleum gas yield decreased gradually, and light oil yield increased piece by piece; the amount of olefin was enhanced step by step, that of aromatics dropped slowly, and that of saturated hydrocarbon did not change. However, olefin conversion and increasing ratio of aromatics presented a slowly decreasing trend and increasing ratio of saturated hydrocarbon showed no change; hydrogen yield was low and did not change; i-butane and propane decreased, but n-butane increased gradually; C⁰ ₃/C⁼ ₃ and nC⁰ ₄/nC⁼ ₄ values did not change, iC⁰ ₄/iC⁼ ₄ variety had no order; C⁰ ₃/C⁼ ₃, C⁰ ₄/C⁼ ₄, and (C⁰ ₃ + C⁰ ₄)/(C⁼ ₃ + C⁼ ₄) values showed a decreasing trend.     

液化石油气芳构化反应体系的热力学分析

利用液化石油气生产芳烃,对于提高液化石油气的利用率和经济效益均具有重要意义。开发液化石油气芳构化技术,首先利用热力学分析液化气芳构化反应体系的可能性。本文利用原子系数矩阵法确定了液化石油气芳构化反应体系的独立反应数和一组独立反应,利用热力学方法计算了该反应体系中各独立反应在不同条件下的吉布斯自由能变,平衡常数及体系在给定初始组成条件下的平衡组成,据此可判断各独立反应在指定条件下进行的方向及发生的可能性,分析结果可为反应器的设计及反应条件的选择提供指导。     

A Kinetics Lumped Model for VGO Catalytic Cracking in a Fluidized Bed Reactor

Abstract

Fluid catalytic cracking (FCC) is a process used to converted heavy petroleum products to light products such as gasoline, light fuel oil, and petroleum gas. In the fluid catalytic cracking reactor heavy gas oil is cracked into more valuable lighter hydrocarbon products. The reactor input is a mixture of hydrocarbons that makes the reaction kinetics very complicated due to the involved reactions. In this article, a four-lump model is proposed to describe the kinetics of vacuum gas–oil (VGO) cracking in the FCC process. This model is different from other models mainly in that the deposition rate of coke on catalyst can be predicted from gas–oil conversion and isolated from the C1-C4 gas yield. By this lumped model for the kinetic of cracking VGO we can also conclude that the C1-C4 gas yield increases with increasing reactor temperature, whereas the production of gasoline and coke decreases. We can also conclude that with decreasing space velocity the product yield will increase.     

Aromatization Reactions of Three Gasoline Fractions

Abstract

Using a confined fluidized bed reactor and aromatization catalysts (LBO-A and LBO-16), three fluid catalytic cracking (FCC) narrow fraction gasoline (Lanlian gasoline, Shandong gasoline, and Fushun gasoline) at 420°C has been studied. The results reveal that at 420°C and a mass ratio of catalyst to oil of 5, the olefin content is remarkably reduced from about 20 to 30% (by mass) over 75% LBO-A and 25% LBO-16, and the octane number is kept at a high level after the aromatization reaction, at the same time the nine lumps model of aromatization reaction is put forward based on the corresponding mechanism. The method obtained can provide the technical instruction for the petroleum chemical plant.     

液化石油气深加工技术进展

介绍了目前国内炼油化工企业对不同来源的液化石油气（LPG）的利用方法。综述了LPG芳构化、烷烃催化脱氢等技术,并对不同工艺进行了比较。针对不同装置的LPG提出了以炼油厂的芳烃LPG为原料的LPG芳构化、烷烃催化脱氢制烯烃,以烯烃裂解C4抽余液为原料制取高纯异丁烯及异丁烯下游产品深度开发的建议。     

Predictions for Yields of Huabei Liquefied Petroleum Gas by Using the Classical Apriori Algorithm Model

The classical Apriori algorithm model for predicting yields of Huabei liquefied petroleum gas have been introduced based on Visual FoxPro software in the present article. The experimental results show that the classical Apriori algorithm model can predict yields of Huabei liquefied petroleum gas and the experimental data are in agreement with the quantitative analytic conclusions drawn from the predicted data. This proves that it can be used to predict yields of Huabei liquefied petroleum gas. It results in good economic and social benefits for Chinese chemical plant.     

The Kinetics of Catalytic Oxidation of 1-Butanethiol in a Gas Liquid System

Abstract

In the present study the kinetics of liquid phase oxidation of light thiols using reformulated cobalt phthalocyanine based catalyst has been investigated in a semi batch bubble column reactor. 1-Butanethiol is chosen to represent thiols in lighter range of petroleum fractions like liquefied petroleum gas and light straight run naphtha. The study has shown that rate of catalytic oxidation of 1-butanethiol is linear at lower concentrations and of nonlinear nature at higher concentrations. A mechanism based rate expression has been obtained to explain this behavior and its parameters are estimated. The derived rate law is similar to Michaelis-Menten rate equation.     

原料组成对液化气芳构化过程的影响

轻质芳烃是主要的化工原料,一直供不应求,利用液化气芳构化生成轻质芳烃,可获得经济效益。液化气中的烯烃含量是液化气芳构化过程的主要影响因素,液化气芳构化所得液体产物中芳烃含量不受原料组成的影响,但芳烃产率随着烯烃含量尤其是丁烯含量的增加而增加,干气产率相应降低。随着原料中丁烯含量的增加,液体产物中苯含量降低,相应二甲苯的含量增加,气相产物中丙烷和H2含量升高。     

液化石油气在ZnNi/HZSM-5催化剂上的芳构化

用浸渍法制备ZnNi/HZSM -5催化剂 ,通过对液化石油气的芳构化试验表明 ,其活性明显高于HZSM -5催化剂。在常压、温度 540℃、质量空速 1h- 1条件下 ,芳烃和苯 -甲苯 -二甲苯 (BTX)混合物收率分别达到 4 8%和4 5%左右 ,液态产品中芳烃质量分数高达 98%。同时还考察再生活化温度、再生活化时间和反应温度对芳构化催化作用的影响。结果表明 ,再生活化温度对催化剂的恢复影响比较大 ,只有达到 575℃ ,活化时间至少 2h ,催化剂活性才能完全恢复 ;低温段 ( 550℃ )再生活化时 ,再生活化时间将影响催化剂活性 ;反应温度在 50 0～ 550℃时 ,随着反应温度增加 ,液体收率和芳烃收率随之增加 ,对芳烃选择性影响不大 ,BTX收率幅度波动较大。用金属改性的ZnNi/HZSM -5催化剂具有较强的芳构化能力。     

Influence of the preparation conditions on the properties of Cr/SiO<Subscript>2</Subscript> catalysts in conversion reactions of liquefied petroleum gas

The effect of the particle size and chemical state of chromium in Cr/SiO₂ catalysts with different chromium contents (2–10%) prepared under different conditions upon the properties in the conversion reaction of liquefied petroleum gas (LPG) in the absence and presence of water vapor was studied. It was shown that the degree of conversion of LPG decreases in the presence of water vapor and the selectivity for C₂–C₄ olefins increases over the Cr/SiO₂ catalysts with a chromium content of 5–7%.     

A Predictive Kinetic Model for Delayed Coking

Abstract

Lumping of the residue charge stock is based on saturate, light and heavy aromatics, soft and hard resins, as well as asphaltenes, whose concentrations can be obtained by solvent sedimentation and Al₂O₃ column separation. The reaction scheme contains 11 lumped species, including two middle fractions, naphtha, gas, and coke in addition to the above six lumps for residua. It is shown that these kinetic parameters are all invariant with respect to residue compositions and therefore this model is able to predict yields of delayed coking products for a wide variety of ranges of charge stock and operating conditions beyond that of the tests.     

ASPHALTENE AND RESID PYROLYSIS: EFFECT OF REACTION ENVIRONMENT

ABSTRACT

Hondo and Maya vacuum resids and their isolated asphaltenes were pyrolyzed at 400, 425, and 450^°C (752, 797, 842^°F) for batch holding limes ranging from 20 to 180 minutes. Maltene, asphaltene, and coke product fractions were isolated by a solvent extraction sequence; gas yield was determined gravimetrically. Results were summarized in terms of a lumped reaction network. The variation of product yields, kinetics, and apparent activation energies with feedstock and asphaltene environment provided insight into asphaltene structure and thermal reaction pathways.     

轻汽油芳构化工艺条件优化

以催化裂化轻汽油为原料,采用大连理工大学开发的SHY-DL催化剂在200 mL多功能固定床试验装置上进行了芳构化反应工艺条件的优化及长周期稳定运行试验。结果表明:随着反应温度升高,烯烃转化率,干气和液化石油气(LPG)收率,C_5～205℃馏分中芳烃质量分数均增加,C_(≥5)液体收率下降;随着反应压力增大,C_5～205℃馏分中芳烃质量分数和C_(≥5)液体收率减小;随着质量空速提高,烯烃转化率和C_5～205℃馏分中芳烃质量分数降低,而C_(≥5)液体收率则增加;在反应温度为380℃,反应压力为1.6 MPa,质量空速为3.0 h~(-1)的最佳工艺条件下,运行1 500 h后,C_(≥5)液体收率大于50%,C_5～205℃馏分中芳烃质量分数高于40%。