Fluid catalytic cracking feed hydrotreatment and its severity impact on product yields and quality

This paper investigates the effect of fluid catalytic cracking (FCC) feed hydrotreatment and its severity increase on product yields and quality obtained in a commercial and a laboratory MAT FCC units. The hydrotreatment of Ural heavy vacuum gas oil reduces not only sulfur, nitrogen, Conradson carbon and metals content in the FCC feed but also increases the mononuclear aromatic hydrocarbons content by 8% absolute at almost no change in the total aromatics content. Regardless of this 8% increase of the mononuclear aromatics in the hydrotreated FCC feed the conversion increase in both commercial and laboratory MAT units was only 2%. The severity increase in the FCC feed hydrotreater leads to a higher conversion in the FCC, higher hydrogen transfer rate that results in higher isobutane/butylenes ratio, lower gasoline olefins content, and higher gasoline motor octane number. The hydrotreatment of the Ural heavy vacuum gas oil exhibited the same changes in FCC catalyst selectivities: lower coke and LCO selectivities and higher gasoline selectivity in both commercial riser FCC unit that has between 2 and 3 s time on stream, and the fixed bed reactor MAT unit, that has 30 s time on stream.     

STRONG沸腾床示范装置工业应用

随着原油重质化程度的不断加深,沸腾床渣油加氢技术成为了炼厂提高渣油附加值的重要手段。抚顺石油化工研究院开发的STRONG沸腾床渣油加氢成套技术无需使用传统沸腾床技术中的高温高压循环泵及配套设备,提高了反应体系的稳定性与反应器空间利用率,降低了投资。首套采用STRONG沸腾床技术的工业化装置累计平稳运行8000 h,540℃+单程转化率达到了78%以上。     

分子筛预加氢及后加氢生产D40溶剂油和3#白油

利用分子筛脱蜡预加氢和后加氢装置改产D40溶剂油和3^#白油，现有原料条件下，生产出硫和氮含量均小于1 μg·g^-1的合格生成油，满足二段脱芳催化剂要求，各项主要指标达到设计值，特种溶剂油产品质量与国外同类油品质量相当。     

Aromatic and hetero-aromatic compositional changes during catalytic hydrotreatment of shale oil

Oil shale from the Kimmeridge Clay, of Jurassic age from the UK was pyrolysed in a 5 kg fixed bed reactor at 525°C in a nitrogen atmosphere. The derived shale oil was then hydrotreated at 15.0 Mpa pressure and 400°C in a stirred reactor with a nickel–molybdenum (Ni–Mo) catalyst and residence times from 8 to 56 h. The shale oils were analysed for polycyclic aromatic hydrocarbons (PAH) and for nitrogen-PAH (PANH) and sulphur-PAH (PASH), before and after hydrotreatment. The results showed that generally the higher molecular weight three and four ring PAH decreased with increasing hydrotreatment time, however, single ring aromatic compounds and two ring PAH were increased. Nitrogen and sulphur containing PAH were significantly reduced in concentration in the oils with increasing hydrotreatment time to reach negligible concentrations after 56 h. The reduction in PANH and PASH coincided with a reduction in the overall nitrogen and sulphur contents of the oils.     

重馏分油加氢处理催化剂发展现状

总结和回顾了国内外重馏分油加氢处理技术的最新研究进展。对Akzo公司的Nebula、Criterion公司的DN-3100和中国石化抚顺石油化工研究院(FRIPP)开发的FF-16等催化剂作了重点介绍。     

植物油加氢制备高十六烷值柴油组分研究进展

介绍了植物油加氢制备柴油的主要化学反应、工艺方法以及该项技术的工业化状况,分析了植物油直接加氢、先加氢后异构、直接脱羧工艺以及植物油与矿物柴油掺炼工艺的特点,阐述了各工艺采用的催化剂类型、工艺条件以及产品属性。指出了该领域存在的问题和研究方向。     

Coal-derived asphaltenes. Relationship between chemical character and process history

The chemical character of asphaltenes isolated from coal-derived liquids and the relative ease of their catalytic and noncatalytic conversion to oil has been found to depend upon their processing history. To facilitate chemical characterization, a simple analytical method was developed for separation of the asphaltenes into three subfractions according to their relative strength of absorption on silica gel. Using this separation technique, differences in the relative content of polar molecules were found among asphaltenes of various processing histories. In general, the relative content of polar compounds in the asphaltenes decreases with increasing conversion to oil. The relative rate of conversion also declines after the asphaltene content reaches a low level. The asphaltenes remaining after long hydrotreatment are more aromatic, contain fewer polar functional groups and are of somewhat smaller molecular size than those obtained after short hydrotreatment. The initial rates of asphaltene conversion were considerably enhanced by a commercial CoMo hydrodesulfurization catalyst. The catalyst increased the conversion of the nonpolar subfraction to a greater extent than the polar subfraction.     

Characterization and HDS activities of mixed Fe–Mo sulphides supported on alumina and carbon

Alumina and activated carbon-supported mixed sulphides (FeMoS) were prepared as hydrotreating catalysts. Previous work had shown bulk Fe–Mo mixed sulphides to be promising catalysts for hydrotreatment. Characterizations of the solids by NH₃-TPD proved to be a good technique to classify the solids according to their acidic strength. Thiophene hydrodesulphurization (HDS) and High vacuum gas oil (HVGO) hydrotreatment, performed at atmospheric pressure and high pressure respectively, were used as catalytic tests. Depending on the support, a more or less important synergetic effect is observed. The results are in agreement with a possible direct desulphurization process. The acidic strength plays an important role in determining the hydrogenolysis/hydrogenation ratio of the catalysts.     

Production of Biocomponent Containing Gas Oil with the Coprocessing of Vegetable Oil�CGas Oil Mixture

We investigated the impact of the enhanced sulphur content of feedstocks during the production of gas oil with bio-component content in one catalytic step, on a NiMo/Al₂O₃ catalyst from sunflower oil-containing gas oil. The mixing of vegetable oil reduces the efficiency of hydrodesulphurization compared to the pure gas oil feedstock, but using the favourable process parameter combination high scale desulphurization can be achieved.     

Hydrotreatment of Cracked Light Gas Oil

Since worldwide conversion processes are used to upgrade heavy oil to distillates, the hydrotreatment of light gas oil (LGO) as a downstream process has been used more extensively. This fraction (LGO) is produced from thermal or catalytic cracking or hydrocracking processes. It contains high amounts of unsaturates, nitrogen, and sulfur compounds which cause instability while in storage due to gum formation. The use of LGO as a fuel oil for diesel engines plugs the filter and produces sulfur and nitrogen emissions. These sulfur and nitrogen compounds arise from the cracking of heavy cuts and are aromatic-type molecules which are difficult to hydrogenate. This cut also possesses a low cetane index (CI) which must be increased (by aromatic hydrogenation) because of its poor motor performance. Color and color stability are associated with a high bromine number (BN, unsaturated content), nitrogen, and aromatic content. In order to improve these properties, a deep hydrogenation is sometimes required.     

Hydrotreatment of Cracked Light Gas Oil

Since worldwide conversion processes are used to upgrade heavy oil to distillates, the hydrotreatment of light gas oil (LGO) as a downstream process has been used more extensively. This fraction (LGO) is produced from thermal or catalytic cracking or hydrocracking processes. It contains high amounts of unsaturates, nitrogen, and sulfur compounds which cause instability while in storage due to gum formation. The use of LGO as a fuel oil for diesel engines plugs the filter and produces sulfur and nitrogen emissions. These sulfur and nitrogen compounds arise from the cracking of heavy cuts and are aromatic-type molecules which are difficult to hydrogenate. This cut also possesses a low cetane index (CI) which must be increased (by aromatic hydrogenation) because of its poor motor performance. Color and color stability are associated with a high bromine number (BN, unsaturated content), nitrogen, and aromatic content. In order to improve these properties, a deep hydrogenation is sometimes required.     

不溶性硫磺的制备研究

开发了低温液相法—浸取剂ＴＥ浸取制备不溶性硫磺新工艺。采用正交试验法得出了低温液相法制备不溶性硫磺粗产品的适宜条件：稳定剂用量０．０６％，恒温温度２５０℃，恒温时间６０ｍｉｎ，急冷液浓度６．０％。并以单因素法对浸取温度、物料比等浸取工艺参量进行了探讨，其合适条件分别为７５～８０℃，粗粉料∶浸取剂＝１∶（１２～１５）。在最适宜条件下，产品不溶性硫含量可达９２％以上。     

FCC汽油脱硫降烯烃技术最新进展

介绍了国内外降低催化汽油中硫和烯烃的技术。降低FCC汽油烯烃和硫含量的主要技术有对FCC原料油进行加氢预处理、在FCC过程中使用具有降低汽油烯烃和硫含量的催化剂或助剂以及对 FCC 汽油进行脱硫和降烯烃精制处理三类。     

Reactivation of an industrial batch of CoMo/Al<Subscript>2</Subscript>O<Subscript>3</Subscript> catalyst for the deep hydrotreatment of oil fractions

The results from industrial tests of technology developed earlier for the reactivation of CoMo/Al₂O₃ catalyst for the deep hydrotreating of diesel fuel, including the oxidative regeneration of the catalyst with subsequent treatment using organic complexing agents, are presented. Samples of the catalyst, fresh and at different stages of its reactivation, are investigated using a set of analytical and physicochemical methods. The chemical composition, textural characteristics, mechanical strength, structure of the active sulfide component (TEM, XPS) are determined. Catalytic tests are performed that include lifetime tests (360 h) in the hydrotreatment of a straight-run diesel fraction. The restoration of the physicochemical and catalytic properties is observed for a sample subjected to oxidative regeneration with subsequent treatment using organic complexing agents. An industrial batch of deep hydrotreatment catalyst reactivated by this technology is loaded into an L-24-6 industrial plant facility and ensures stable purification of straight-run diesel fuel containing up to 10% of light catalytic cracking gas oil to a residual sulfur content of less than 10 ppm. Comparison of the obtained results and data on the industrial operation of fresh catalysts shows that the technology developed by the Institute of Catalysis and PAO Gazprom Neft ensures almost complete restoration of the properties of the deactivated catalysts.     

尾油循环的煤焦油加氢实验研究

利用小型固定床加氢实验装置,将煤焦油和其加氢后的尾油混合,在温度(360~420)℃、压力(13~15)MPa、氢油体积比(1 500~1 700)∶1和液体体积空速0.25 h-1条件下进行加氢处理,所得产品切割得到的汽油馏分、柴油馏分和尾油馏分,分别占产物质量的16.12%、78.83%和5.05%,且产品中硫、氮含量很低,汽油中硫含量16.7μg·g~(-1),氮含量36μg·g~(-1),柴油中硫含量102.6μg·g~(-1),氮含量97μg·g~(-1),可用作清洁燃料。结果表明,尾油循环在煤焦油加氢过程中对煤焦油具有稀释作用,不仅减轻了设备负荷,同时也可以提高汽油和柴油收率。因此,以煤焦油加氢尾油循环加氢是一种高效、绿色环保制备燃料油的方法。     

降低凝析油中硫化氢含量的研究

研究了永22储气库凝析油中硫的形态及分布、分析了在用脱硫剂脱硫效果不佳的原因,针对性的进行新型脱硫剂的选择配比,并通过现场试验验证脱硫效果,最终达到了下游闪蒸气中硫化氢含量达到II类标准天然气要求的目标,研发成功了一种新型的脱硫剂。     

Kinetics of the hydrotreatment of rapeseed oil fatty acid triglycerides under mild conditions

To establish principal regularities of the hydrotreatment of rapeseed oil fatty acid triglycerides (FATs), the kinetics of this process has been studied at temperatures of 300–380°C, contact times of 0.38–0.10 h, and a hydrogen pressure of 1.0 MPa in a flow fixed-bed reactor. The process is performed over nonsulfided nickel catalysts, which are of great practical interest for the production of green diesel. The kinetic scheme of the process with consideration for target products (alkanes) and all oxygen-containing by-products has been proposed. The quantitative estimate, which enables the prediction of the composition of products for other process conditions, has been obtained for the principal paths of the hydrotreatment of rapeseed oil FATs.     

In bed and downstream hot gas desulphurization during solid fuel gasification: A review

Syngas produced by gasification process of biomass fuels is an environmental friendly alternative to conventional petrochemical fuels for the production of electricity, hydrogen, synthetic transportation biofuels and other chemicals. However, the advanced utilization of syngas is significantly limited due to the contaminants which can seriously deactivate the catalysts used for downstream reaction such as steam reforming methane, Fischer-Tropsch synthesis and corrosion of downstream equipments such as a gas turbine. Among the contaminants, sulphur compounds produced in the gasification process, which are mainly H₂S with small amounts of COS, CS₂ and thiophenes depending on process conditions, must be removed. For biomass feedstock advances are required in the cleanup technologies and processes to upgrade the raw product gas with minimal impact on the overall process efficiency. Hot gas desulphurization (HGD) can improve the overall thermal efficiency due to the elimination of fuel gas cooling and associated heat exchangers. With this aim, the present review paper highlights currently developed methods used for desulphurization of hot gas produced from gasification process of solid fuels. The methods presented here are for both in situ and downstream sulphur capture. Also, the attention is paid to the regeneration of the used materials. In situ sulphur capture is mainly done by using calcium-based sorbents such as limestone and dolomite, whereas downstream sulphur capture is mainly focused on the use of regenerable single, mixed, and supported metal oxides. A comparison is indicated at the end to show the sulphur loading of various materials.     

磷改性拟薄水铝石性能及在蜡油加氢催化剂中的应用

在碳化法拟薄水铝石生产过程中加入磷改性剂制备磷改性拟薄水铝石。考察了磷含量对拟薄水铝石和模式载体的物理性能和酸性能的影响。结果表明,随着磷含量的增加,拟薄水铝石和载体的孔容和比表面积增大,但到一定程度后,孔容和比表面积下降,磷存在最佳加入量。磷改性后的拟薄水铝石和模式载体随着磷含量的增加,弱酸量增加,中强酸量降低,总酸量减少。以磷改性拟薄水铝石和不合磷碳化法拟薄水铝石为原料,制备了不同磷含量的氧化铝载体及催化剂,采用中国石油胜利炼油厂生产的减压蜡油在100mL小型加氢装置上进行评价实验,优化制备出适宜的蜡油加氢处理催化剂。     

天然气脱硫工艺在塔河油田天然气处理中的应用

首先对天然气脱硫工艺做了概要介绍,然后主要介绍了天然气脱硫工艺在塔河油田三号联合站轻烃处理站的应用。按照该站天然气气质条件和处理规模设计了3套脱硫及硫磺回收方案。通过对3套不同的方案进行对比和分析,最后认为MDEA法＋自循环LO-CAT工艺是最适合该站采用的天然气脱硫和硫磺回收方案。