Regulating catalyst morphology to boost the stability of Ni–Mo/Al_(2)O_(3) catalyst for ebullated-bed residue hydrotreating

Hydrotreating of vacuum residue by ebullated-bed shows tremendous significance due to more stringent environmental regulations and growing demand for lighter fuels. However, enhancing the catalyst stability still remains as a challenging task. Herein, two Ni–Mo/Al_(2)O_(3) catalysts with distinct morphologies(i.e., spherical and cylindrical) were first designed, and the morphology effect on deactivation was systematically elucidated employing multi-characterizations, such as HRTEM with EDX mapping, electron microprobe analysis, FT-IR, TGA and Raman. It is found that spherical catalyst exhibits superior hydrotreating stability over 1600 h. The carbonaceous deposits on spherical catalyst with less graphite structure are lighter, and the coke weight is also smaller. In addition, the metal deposits uniformly distribute in the spherical catalyst, which is better than the concentrated distribution near the pore mouth for the cylindrical catalyst. Furthermore, the intrinsic reason for the differences was analyzed by the bed expansion experiment. Higher bed expansion rate together with the better mass transfer ability leads to the enhanced performance. This work sheds new light on the design of more efficient industrial hydrotreating catalyst based on morphology effect.

Thermodynamics and kinetics insights into naphthalene hydrogenation over a Ni-Mo catalyst

Hydrocracking represents an important process in modern petroleum refining industry,whose performance mainly relies on the identity of catalyst.In this work,we perform a combined thermodynamics and kinetics study on the hydrogenation of naphthalene over a commercialized NiMo/HY catalyst.The reaction network is constructed for the respective production of decalin and methylindane via the intermediate product of tetralin,which could further undergo hydrogenation to butylbenzene,ethylbenzene,xylene,toluene,benzene,methylcyclohexane and cyclohexane.The thermodynamics analysis suggests the optimum operating conditions for the production of monoaromatics are 400℃,8.0 MPa,and 4.0 hydrogen/naphthalene ratio.Based on these,the influences of reaction temperature,pressure,hydrogen/-naphthalene ratio,and liquid hourly space velocity(LHSV)are investigated to fit the Langmuir-Hinshelwood model.It is found that the higher temperature and pressure while lower LHSV favors monoaromatics production,which is insensitive to the hydrogen/naphthalene ratio.Furthermore,the high consistence between the experimental and simulated data further validates the as-obtained kinetics model on the prediction of catalytic performance over this kind of catalyst.

Simultaneous recovery of carbon and sulfur resources from reduction of CO_2 with H_2S using catalysts

An approach to the simultaneous reclamation of carbon and sulfur resources from CO2 and H2S has been proposed and effectively implemented with the aid of catalysts. A brief thermodynamic study reveals the potential of direct reduction of CO2 with H2S（15：15 mol% balanced with N2） for selective production of CO and elemental sulfur. The experiments carried out in a fixed-bed flow reactor over the temperature range of 400–800 °C give evidence of the importance of the employment of catalysts. Both the conversions of the reactants and the selectivities of the target products can be substantially promoted over most catalysts studied. Nevertheless, little difference appears among their catalytic performance. The results also prove that the presence of CO2 can remarkably enhance H2S conversion and the sulfur yield in comparison with H2S direct decomposition. A longtime reaction test on Mg O catalyst manifests its superior durability at high temperature（700 °C） and huge gas hourly space velocity（100,000 h-1）. Free radicals initiated by catalysts are supposed to dominate the reactions between CO2 and H2S.

Separation-and-Recovery Technology for Organic Waste Liquid with a High Concentration of Inorganic Particles

The environmentally friendly and resourceful utilization of organic waste liquid is one of the frontiers of environmental engineering. With the increasing demand for chemicals, the problem of organic waste liq- uid with a high concentration of inorganic pollutants in the processing of petroleum, coal, and natural gas is becoming more serious. In this study, the high-speed self-rotation and flipping of particles in a three- dimensional cyclonic turbulent field was examined using a synchronous high-speed camera technique; the self-rotation speed was found to reach 2000-6000 rad.s 1. Based on these findings, a cyclonic gas- stripping method for the removal of organic matter from the pores of particles was invented. A techno- logical process was developed to recover organic matter from waste liquid by cyclonic gas stripping and classifying inorganic particles by means of airflow acceleration classification. A demonstration device was built in Sinopec＇s first ebullated-bed hydro-treatment unit for residual oil. Compared with the T-STAR fixed-bed gas-stripping technology designed in the United States, the maximum liquid-removal effi- ciency of the catalyst particles in this new process is 44.9% greater at the same temperature, and the time required to realize 95% liquid-removal efficiency is decreased from 1956.5 to 8.4 s. In addition, we achieved the classification and reuse of the catalyst particles contained in waste liquid according to their activity. A proposal to use this new technology was put forward regarding the control of organic waste liquid and the classification recovery of inorganic particles in an ebullated-bed hydro-treatment process for residual oil with a processing capacity of 2×106 t.a^1. It is estimated that the use of this new tech- nology will lead to the recovery of 3100 t.a 1 of diesel fuel and 647 t.a^1 of high-activity catalyst; in addi- tion, it will reduce the consumption of fresh catalyst by 518 t.a^1. The direct economic benefits of this process will be as high as 37.28 million CNY per year.

沸石分子筛催化剂的“限域”效应

沸石分子筛催化剂因其独特的酸性、规则的孔道结构和良好的水热及化学稳定性被广泛应用于石油化工、煤化工和精细化工等重要领域.沸石分子筛活性位点的数目和分布,以及孔结构效应是沸石分子筛催化科学研究中最根本的问题,直接影响催化反应历程和反应结果.几十年来,沸石分子筛催化研究多集中在对活性位点的基本认识和合成设计,而忽视了活性位点、反应分子和沸石分子筛孔道微环境之间的相互作用.受益于先进的化学分析表征技术和化学理论计算科学的发展,沸石分子筛催化剂孔道内的微环境研究引起了越来越多研究人员的重视.通过对相关文献的分析整理,本文从沸石分子筛结构"限域"理论的发展历程,对分子扩散、吸附和催化过程的影响及其应用拓展等几个方面讨论了沸石分子筛催化剂中的"限域"效应.

Development and application of ex-situ presulfurization technology for hydrotreating catalysts in China

The development and application of ex-situ presulfurization(EPRES)technology for hydrotreating catalysts has been reviewed in the present article.The studies in laboratory scale and commercial practice indicated that the adoption of the EPRES catalyst in industrial application can significantly enhance the degree of presulfurization of metal oxide components,shorten the start-up period,and effectively reduce the environmental impact as well as the danger of start-up procedure in industrial hydrotreating unit.This catalyst has been proved to be versatile for different types of hydrogenation reactions.Different types of active site models are also discussed for better understanding the nature of presulfur-ized catalysts.