Hydrocracking of Gudao Residual Oil with Dispersed Catalysts Using Supercritical Water-Syngas as a Hydrogen Source

Abstract:

Heavy oil upgrading is a very important process in the petroleum industry, but is very difficult because it has a high impurity content. A variety of heavy oil upgrading technologies have been developed in the world, including the catalytic hydrocracking process, which can process various heavy oils with a high yield of liquid products. Although this technology is one of the most widely used methods for upgrading heavy oil, the use of expensive molecular hydrogen is costly. The heavy oil upgrading technology with alternative hydrogen is very important. The catalytic hydroconversion of Gudao residue with different catalysts using water-syngas as an alternative hydrogen was investigated in this study. Hydrogen is provided in-situ for hydrocracking through the water-gas shift reaction (WGSR). The experimental results show that catalysts play a very important role in catalytic hydroconversion of Gudao residue using water-syngas as an alternative hydrogen. Addition of catalysts to residue was found to improve the distribution or properties of cracking products and inhibit the asphaltene or TI formation.     

Hydrocracking of Gudao Residual Oil with Dispersed Catalysts Using Supercritical Water-Syngas as a Hydrogen Source. Part II: The Comparison of Residue Hydrocracking in Different Hydrogen Sources

Different catalytical hydrogen sources were compared with molecular hydrogen gas in the hydrocracking of Gudao residue in the presence of catalysts (PMA). The results showed that alternative hydrogen sources were effective in catalytic hydroconversion of heavy oil. The hydroconversion of residue in supercritical water-syngas system showed similar results when performed with molecular hydrogen.     

Hydrocracking of Gudao Residual Oil with Dispersed Catalysts Using Supercritical Water-Syngas as a Hydrogen Source. Part II: The Comparison of Residue Hydrocracking in Different Hydrogen Sources

Abstract

Different catalytical hydrogen sources were compared with molecular hydrogen gas in the hydrocracking of Gudao residue in the presence of catalysts (PMA). The results showed that alternative hydrogen sources were effective in catalytic hydroconversion of heavy oil. The hydroconversion of residue in supercritical water-syngas system showed similar results when performed with molecular hydrogen.     

Hydrocracking Gudao Residual Oil Using Supercritical Water-Syngas as Hydrogen Source in Suspension Bed. Part III: Water-Gas Shift Reaction

Abstract

The catalytic hydroconversion of Gudao residue in supercritical water-syngas system is a heavy oil upgrading technology. The hydrogen derived from water-gas shift reaction can be used for residue hydrocracking, so, it is important for studying the water-gas shift reaction that takes place in the hydrocracking system. Here, the water-gas shift reaction in the supercritical water-syngas system was investigated. The results showed that the water-gas shift reaction could be effectively increased with dispersed catalysts, and more than 80% CO was conversed in the initial processes.     

孤岛减压渣油在CO-SCW体系中催化加氢

对孤岛减压渣油在CO -SCW体系中加氢改质研究表明 ,利用CO与SCW发生的水 -气变换反应获得加氢所需氢源是可行的。在适宜的条件下 ,渣油在CO -SCW体系中改质可达到在H2 -SCW体系中改质同样的效果     

Upgrading Heavy Oil Using Syngas as the Hydrogen Source with Dispersed Catalysts

Abstract

Upgrading heavy oil using syngas (CO + H₂) as an alternative hydrogen source with a dispersed catalyst was investigated. Finely dispersed catalysts for upgrading were prepared by means of microemulsion, and their performance was investigated in a batch-type autoclave. This process was compared to the traditional pure hydrogen hydro-upgrading process. Feedstock conversion, light-oil yield, coke yield, product distribution, sulfur, nitrogen and viscosity were investigated comprehensively to optimize the process. The addition of finely dispersed catalysts could improve the distribution and performance of cracking products, and inhibit the cracking gas and coke formation. This work shows that residue-syngas coprocessing is promising for heavy oil upgrading.     

The Mechanism of Diesel Hydrogenation Using Supercritical Water-Syngas

Many reactions were involved in the diesel hydrorefining processes in the supercritical water-syngas system, as the mechanism of diesel hydrogenation using supercritical water-syngas was investigated by using isotopic D₂. The ²H-NMR results of hydrogenated products revealed that the supercritical water-syngas could be used as an alternative hydrogen source for diesel hydrotreating because much higher deuterium content appeared in the products. The results also indicated that the hydrogen derived from supercritical water-syngas could exchange the sulfur, so hydrogen was added to the diesel molecule.     

渣油悬浮床加氢用催化剂的研究进展

结合渣油悬浮床加氢技术用催化剂类型,系统分析了固体颗粒催化剂、负载型催化剂、分散性催化剂的优缺点、研究现状及应用前景.固体颗粒催化剂价格低廉,活性低,对设备磨损大,污染严重;负载型催化剂应用较少,且不适于加工金属含量过高的渣油;分散型催化剂有较好的分散性、活性和抑焦性.指出开发高性价比的油溶性催化剂是悬浮床加氢技术研究热点.     

模型化合物十六烷在超临界水中的热解

为了解重质油中饱和分在超临界水中的热解机理,将十六烷作为模型化合物,在间歇反应器内研究了它在超临界水中的热解反应,反应温度420~460℃,压力23~27M Pa。在超临界水中,十六烷热解为较轻、较重的碳氢化合物和气体。与无超临界水、常压下十六烷的热解反应相比,超临界水中十六烷热解反应的活化能(300.0kJ/m ol)低,因而反应速率快。通过对产物的分析,推断反应遵循自由基机理,反应过程包括自由基的产生、传递、分解和终结。在超临界水中,十六烷的热解反应存在超临界水的供氢机制,减压渣油在超临界水中的热解反应也存在这种供氢机制,而该机制有利于改善热解产物的质量。     

渣油悬浮床加氢裂化技术的研究

介绍了抚顺石油化工研究院开发的渣油悬浮床加氢裂化工艺及催化剂 ,采用该催化剂加氢处理常、减压渣油 ,馏分油 (<5 3 8℃ ) ,单程收率达到 70 %以上。并在 2 0 0ml小型装置上进行了 5 0 0h的连续运转。采用尾油循环和其它组合工艺 ,可以得到较高的重渣油加氢转化率。     

低温煤焦油在超临界汽油中的加氢裂化模拟

本文的目的在于在能量自给的设计原则下,利用 aspen plus 软件对低温煤焦油在超临界汽油中的加氢裂化流程进行初步的设计。为了保证模拟的正确性和准确性,对低温煤焦油的模型化合物进行了合理的选取,对产物汽油和柴油的性质进行了较为准确的描述,对每个模块适用的物性方法进行了最佳选择。系统能量的自给可通过冷热物流的热交换,流股的温度优化控制,以及利用系统自身产生的气体燃烧后再为系统提供能量而实现。结果表明,该系统每处理1000kg低温煤焦油,只需净正热负荷268KW/h;系统共回收热量2229KW/h,其中845KW/h 来自于气体的燃烧,1116KW/h来自于反应器的出口物流。此外,该系统的分离效果很好,汽油的纯度为0.972,柴油为1。     

Performance Evaluation Studies of First- and Second-Stage Hydrocracking Catalysts Using Kuwait Vacuum Gas Oil Feedstocks

Abstract

In a two-stage hydrocracking process, two types of catalyst are used to remove undesirable contaminants (such as S, N, hydrogenation of aromatic compounds, etc.) and convert the heavy feedstock to lighter products. In the present work, individual set of experiments were conducted to obtain information regarding activity and selectivity with emphasis on the evaluation of kinetic parameters of first- and second-stage commercial catalysts used in hydrocracking process. The performance tests were conducted in a down-flow fixed-bed hydrocracking pilot plant using a single reactor. The hydrotreating type A catalyst and hydrocracking type B catalyst were used individually with typical Kuwaiti refinery feedstocks, namely, hydrotreated vacuum gas oil (HVGO) and unconverted residual oil (UCRO), respectively. The order of reaction in this study shows first-order kinetics for HDS and HDN over CAT-A, and first-order hydrocracking conversion over CAT-B. For CAT-A the activation energies were found for HDS and HDN reactions at 22 and 27.3 kcal/gmole, while for CAT-B activation energies were 27.4 kcal/gmole.     

超临界水中聚乙烯降解油化的研究和开发进展

从聚乙烯热解和超临界水中聚乙烯热解工艺的比较出发,综述了超临界水中水密度、反应气氛对超临界水中聚乙烯降解油化的影响及超临界状态下水分子在聚乙烯分解反应过程中的供氢、供氧途径和聚乙烯的相行为;考察了超临界水中聚乙烯降解反应的机理与反应模型;介绍了东北电力与三菱重工合作开发的超临界水中聚乙烯降解油化的小试、中试和示范试验开发过程的进展。     

Performance Evaluation Studies of First- and Second-Stage Hydrocracking Catalysts Using Kuwait Vacuum Gas Oil Feedstocks

In a two-stage hydrocracking process, two types of catalyst are used to remove undesirable contaminants (such as S, N, hydrogenation of aromatic compounds, etc.) and convert the heavy feedstock to lighter products. In the present work, individual set of experiments were conducted to obtain information regarding activity and selectivity with emphasis on the evaluation of kinetic parameters of first- and second-stage commercial catalysts used in hydrocracking process. The performance tests were conducted in a down-flow fixed-bed hydrocracking pilot plant using a single reactor. The hydrotreating type A catalyst and hydrocracking type B catalyst were used individually with typical Kuwaiti refinery feedstocks, namely, hydrotreated vacuum gas oil (HVGO) and unconverted residual oil (UCRO), respectively. The order of reaction in this study shows first-order kinetics for HDS and HDN over CAT-A, and first-order hydrocracking conversion over CAT-B. For CAT-A the activation energies were found for HDS and HDN reactions at 22 and 27.3 kcal/gmole, while for CAT-B activation energies were 27.4 kcal/gmole.     

含硫渣油悬浮床加氢裂化性能釜式反应评定

在无外加硫化剂的情况下,在高压釜中对含硫常压渣油进行了悬浮床加氢裂化试验,得到了较优的加氢裂化条件。实验表明,由于原料本身含硫量较高,其中的硫作为硫化剂对所加入的催化剂进行了充分地硫化,在选定的实验条件下,可以得到较高的裂化转化率及相对较少的生焦量,有较好的加氢裂化效果     

超临界流体萃取技术

介绍了超临界流体萃取(SFE)技术在化学工业、环保领域、食品工业、医药工业上的应用进展。该技术较高的萃取效率及温和的操作条件保证了药物成分分析制样的要求；在环境分析中，SFE能够减少试样用量、缩短试样处理时间．且无二次污染。同时分析了制约SFE应用扩大的原因．对继续发展SFE技术提出了建议。     

超临界水中渣油加氢转化的生焦行为及焦炭形貌

采用高压反应釜进行渣油加氢转化实验,通过加入超临界水(SCW),考察焦炭产率的变化。结果表明,添加少量的SCW,其物理方面的分散作用和溶解作用会降低体系的生焦量。增加SCW的添加量,水分子阻碍了加氢反应的发生,生焦量开始增加;继续增大SCW的添加量,大量水分子形成的"笼效应"抑制了重组分的聚集缩合,焦炭产率又开始降低。对比有无添加SCW条件下生焦颗粒的形貌,发现添加SCW条件下,焦炭颗粒具有明显的层状结构,颗粒整体性较差,是由于焦炭颗粒形成过程中存在水分子的阻碍作用。     

分散型催化剂催化重油胶质的水热裂解反应

从辽河重油中分离出胶质,对比了胶质在无催化剂、水溶性催化剂(NiSO_4和FeSO_4)和油溶性催化剂(环烷酸镍和环烷酸铁)作用下的水热裂解反应结果;采用元素分析、蒸气压渗透法和核磁共振等方法对水热裂解反应前后胶质的性质进行了表征。实验结果表明,胶质转化率的大小顺序为:环烷酸铁>环烷酸镍>FeSO_4>NiSO_4>无催化剂,油溶性催化剂的性能好于水溶性催化剂;加入催化剂促进了裂解气中H_2和CO的生成,使H_2S生成量减少;随反应温度的升高,胶质转化率增大,反应60 h后胶质的转化基本完成。表征结果显示,水热裂解反应后,胶质的相对分子质量增大,胶质发生了缩聚。     

Kinetic Study on the Hydrocracking Reaction of Vacuum Residue Using a Lumping Model

Abstract

Based on the experimental hydrocracking of vacuum residue, a kinetic study using a lumping model was carried out to gain insight into the characteristics of catalytic reactions. The lumped species were the saturates, aromatics, resins, and asphaltenes (SARA) constituents in the residue (798 K⁺) fraction and gas, naphtha, kerosene, gas oil, vacuum gas oil, and coke in the products. The pyrite reaction favoring hydrocracking to lighter products was more temperature-dependent than that using a mixture of pyrite and active carbon. The kinetic study showed that the addition of active carbon to pyrite limited the transformation of resins to asphaltenes.