Manufacture of motor fuels by the hydrogenation of coals of the Itatskoe deposit

The hydrogenation of coals from the Itatskoe deposit in the Kansk-Achinsk basin was studied. It was found that low-ash power-generating coals from the Itatskoe deposit are high-quality raw materials for the production of liquid fuel, and they can be used for hydrogenation conversion into motor fuels at a hydrogen pressure of 10 MPa on an industrial scale. To obtain Euro compliant gasoline and diesel fuel components, the fractions of hydrogenated coal from the Itatskoe deposit with boiling points of <425 and 180–360°C were subjected to hydrofining in the presence of an Al-Ni-Mo catalyst from the Boreskov Institute of Catalysis, Siberian Branch, Russian Academy of Sciences and a tungsten-nickel sulfide catalyst from the All-Russia Research Institute of Oil Refining Institute. The heat effects of typical reactions in the hydrofining process were calculated for fractions with boiling points of 55–425 and 180–360°C in the presence of the test catalysts.     

Hydrogenation of coal from the Zashulanskoe field in Chita oblast

The results of evaluation of coal from the Zashulanskoe field of Chita oblast as a feedstock for liquid fuel manufacturing by hydrogenation are reported. Zashulanskoe coals whose reserves exceed 250 million tons have favorable mining and geological occurrence conditions, are recovered by high-performance openpit mining, and are characterized by low ash and sulfur contents; they can be regarded as a promising raw material for processing into liquid fuel in Trans-Baikal regions having a shortage of motor fuels and lubricants, a conclusion that has been confirmed by studying their reactivity in hydrogenation at a hydrogen pressure of up to 10 MPa.     

Hydrogenation of the semicoking tar of coal from the Shubarkol deposit

The results of the hydrogenation processing of the semicoking tar (AO Sary Arka Spetskoks, Karaganda, Republic of Kazakhstan) of coal from the Shubarkol deposit in the presence of Mo- and Ni-containing pseudohomogeneous catalytic systems for the production of motor fuel components and chemical substances are reported. It was established that the yield of a gasoline fraction at a temperature of 400°C (5.0 MPa, a 0.015% S additive) was 18.7% with the use of a molybdenum catalyst or 10.6% with a nickel catalyst; therefore, the coal tar can be considered as a potential raw material for obtaining motor fuel components.     

液相加氢工艺在航空煤油生产上的工业应用

介绍了抚顺石油化工研究院开发的航煤液相加氢工艺在镇海炼化公司70万t/a航煤液相加氢装置工业应用情况,通过与采用常规气相循环加氢工艺的100万t/a航煤加氢装置工况、原料、产品质量、氢气利用率和能量消耗的对比,证明航煤液相加氢工艺成熟可靠,产品质量稳定,可以在较高空速下生产满足GB6537-2006 3#喷气燃料标准的航空煤油,同时采用航煤液相加氢工艺装置操作更简单,运行空速更高,氢气利用率高,能耗和单位生产成本低,拥有较大的市场潜力。     

Rare and rare-earth elements in the metal-bearing coals of the north of the Lena Coal Basin

The increased metal-bearing capacity of coals from the Salga-Tabakh area in the north of the Lena Basin was established. In terms of the composition of rare-earth elements, they can be attributed to the collectors of the most expensive yttrium group. A process flowsheet was proposed for the extraction of rare-earth elements from coal ashes; this flowsheet can be used both independently and as a part of coal conversion processes with the production of liquid fuels and other valuable chemical products.     

Application of modified iron-containing catalysts and preliminary ozonization of coal from the Shubarkol deposit to the hydrogenation of this coal

The results of the hydrogenation processing of coal from the Shubarkol deposit in the presence of natural bauxites from the Turgai deposit in the Republic of Kazakhstan are reported. With the use of a sample of bauxite containing 23.7% Fe₂O₃ as a catalyst, a higher yield of liquid products (54.2%) was obtained, as compared with those on other bauxite samples (49.5–53.8%). It was established that the modification of catalysts containing iron with elemental sulfur additives (0.75–1.25%) makes it possible to increase the yield of liquid products to 62.3–67.3%. A positive role of the preliminary ozonization of coal, which makes it possible to increase the yield of total liquid products upon hydrogenation by 13.3% in comparison with the yield of liquid products obtained with the use of coal not treated with ozone, was demonstrated.     

Application of Mechanochemical Activation and γ-Radiation to Increase the Reactivity of Coal from the Shubarkol Deposit in Hydrogenation

The results of the mechanochemical activation of coal from the Shubarkol deposit in an impactgrinding mill and under exposure to γ-radiation with an electron beam on a LU-6 electron accelerator are reported. It was established that, upon the hydrogenation of dispersed coal, the yields of both total liquid products and different distillate fractions increased. The maximum yields of liquid products (66.8%) and gasoline (12.8%) and diesel (18.5%) fractions were noted upon the hydrogenation of coal ground for 30 min. It was shown that the irradiation of coal with an electron beam (a dose of 150 kGy) increased its reactivity in the process of hydrogenation and also facilitated the formation of free radicals and changed the compounds of iron that are the constituents of the catalyst based on natural bauxite from the Turgai deposit.     

The mechanism of hydrocarbon synthesis from CO and H2 on cobalt catalysts

Basic process for manufacturing liquid fuel and valuable chemicals from nonpetroleum feedstock (coal, natural gas, biomass) is the synthesis of hydrocarbons from CO and H₂ on catalysts containing Group VIII transition metals. There are also other processes for producing hydrocarbon mixtures from nonpetroleum feedstock (for example, coal or biomass hydrogenation, coal devolatilization and pyrolysis), but the preferential development of the Fischer-Tropsch process confirms its viability and prospects, which are determined by a huge source of raw materials—coal reserves in the energy equivalent are an order of magnitude higher than those of crude oil.     

催化剂形态与酚类化合物加氢反应活性构效关系的研究进展

木质素是一种重要的生物质可再生资源,其降解后得到的酚类物质加氢后可得大量高附加值化学品,在环境治理和原料利用方面都有着十分重要的影响。本文综述了近年来国内外木质素酚类加氢反应催化剂的研究进展,总结了液相酚类催化加氢催化剂的种类、反应机理及结构敏感性因素对酚类催化加氢反应活性的影响,阐述了催化剂颗粒尺寸对液相酚类加氢反应活性影响,并以木质素液相酚类加氢反应催化剂的活性金属和载体为体系,对现有的结构敏感性反应中催化剂存在的形貌效应、晶相效应进行了讨论。提出未来可通过控制催化剂形貌和晶相来研究催化剂形态与催化活性之间的构效关系,为今后设计高活性木质素液相酚类加氢催化剂提供借鉴和参考。     

Composition of hydrogenation products of Borodino brown coal

The composition of liquid products of hydrogenation of brown coal from the Borodino deposit was determined by means of ¹³C NMR spectroscopy and chemical thermodynamics methods. It was shown that the group composition of the liquid hydrogenation products at thermodynamic equilibrium is predictable from the elemental composition of the organic matter of parent coal.     

10万t/a高温煤焦油加氢装置的技术标定

以黑龙江省七台河宝泰隆煤化工股份有限公司10万t/a炼焦油轻质化项目为例,介绍了高温煤焦油加氢工艺。在高温煤焦油加氢生产燃料油的过程中,为得到高燃料油收率,采用了加氢精制和加氢裂化相结合的工艺。主要对本套煤焦油加氢装置进行了操作条件和物料分析的技术标定总结,并进行技术分析,提出了合理化建议,以对今后的生产操作提供依据,保证装置的连续稳定运行。     

Hydroliquefaction of Sulcis low-rank coal. 1. Conversion to low-sulphur fuel oil

A low-rank Italian coal was subjected to high-pressure and high-temperature hydroliquefaction with and without a hydrogenation catalyst. A low-sulphur oil was produced, showing properties similar to those of a standard fuel oil. The hydroliquefaction product may be used directly either as a fuel or as raw material for petrochemical processes. Sulcis coal displayed particular reactivity towards hydrogen, as shown also by comparison with a widely used North American coal.     

Preparation of granulated domestic fuel from small coal fractions of the Moscow and Kansk-Achinsk Basins

Data on the preparation of granulated fuel for domestic use from thermally prepared small fractions of brown coal from the Moscow and Kansk-Achinsk Basins are reported. As a result of thermotechnical tests, the high efficiency of the fuel granules obtained from coal mixtures (50 : 50 and 70 : 30) was demonstrated, as compared with raw lump coal from the Moscow Basin. The developed process chart and the design of industrial processing apparatus with an output of 50000–100000 t of granulated fuel per year are given.     

Shale hydrogenation

The hydrogenation of solid fuels is a universal method for the manufacture of liquid products; as applied to the organic matter of shale (OMS), this process can be performed at a low pressure of hydrogen because of the specific structure of OMS. Upon the hydrogenation of enriched Baltic shale at 10 MPa, a 96–98% conversion of OMS into liquid products (76–78%) and gas (18–20%) was achieved. Schematic diagrams were developed for the production of gasoline, diesel fuel, and jet engine fuel (a total yield of ∼62% on an OMS basis, fuel version), and the yield of motor fuels was 53.8% upon the separation of chemical products by liquid solvent extraction (chemical version).     

Tire processing using pyrolysis and hydrogenation methods

The products of the pyrolysis and hydrogenation of worn tires were studied. The main physicochemical characteristics of the liquid and solid products of their processing by these methods were determined. The functional groups of compounds that are the constituents of the liquid products were identified by IR spectrometry. The component composition was studied by gas chromatography. It was found that higher quality liquid fuel can be obtained by hydrogenation, as compared with that prepared by pyrolysis.     

Production of liquid organic substances from the oil shale of the Kotsebinskoe deposit

Two methods are proposed for the production of liquid organic substances from the oil shale of the Kotsebinskoe deposit in Saratov oblast. The areas of possible applications of these organic substances as fuel and additives introduced into organic and mineral matrices.     

Classification of coal hydrogenation products,as compared to the properties of natural oil

Hydrogenated brown coal from the Borodino deposit in the Kansk-Achinsk Basin was considered as synthetic petroleum, whose characteristics and the properties of individual fractions were compared with the physicochemical properties of native natural oils. It was found that brown coal hydrogenation products prepared in accordance with a technology developed at the Institute for Fossil Fuels (IGI) were comparable with medium petroleum in terms of a set of characteristics. After mild hydrofining, they can be classified as sweet light synthetic petroleum in accordance with the API index of the American Petroleum Institute and a sulfur content of <0.3%.     

SRH液相循环加氢技术的开发及工业应用

SRH柴油液相循环加氢技术是利用油品中的溶解氢来满足加氢反应的需要,以油品中氢浓度的梯度变化作为反应的推动力。该技术催化剂床层处于全液相中、接近等温操作,反应效率高、目的产品收率高;整套装置高压设备少,热量损失小,装置投资和操作费用均低。中型装置试验结果证明,SRH液相循环加氢技术可以在适宜的工艺条件下加工各种柴油原料,对原料适应性强、产品质量好。长岭20万吨/年SRH液相循环加氢装置工业应用结果表明:以煤油为原料可以生产合格的3#喷气燃料;以常二柴油、催化柴油和常二柴油、焦化柴油的混合油为原料可以生产满足国Ⅲ质量标准的清洁柴油;以常二线柴油为原料,可以生产满足欧Ⅳ质量标准的清洁柴油,同时该装置长期稳定生产运行表明SRH液相循环加氢技术和关键设备成熟可靠。     

分子筛脱蜡装置预精制段催化剂的优化试验

通过对国内外四种加氢精制催化剂的对比评价试验 ,筛选出可替代进口产品的适用于航煤加氢精制的催化剂 ,并针对该催化剂进行了最佳工艺参数的研究和再生性能的评价 ,试验结果表明 ,该催化剂具有良好的稳定性、抗积炭能力及再生性能 ,对不同航煤原料具有较好的适应性。     

Cu/HMS催化剂上丙二酸二乙酯催化加氢制备1,3-丙二醇

目前工业上生产1,3-丙二醇的方法存在一定局限性,为了开发出避免醛类副产物生成的1,3-丙二醇合成工艺,在高压连续固定床反应器上,以丙二酸二乙酯为原料,使用Cu/HMS催化剂催化加氢制备1,3-丙二醇。考察了原料液浓度、氢酯摩尔比、液时空速、反应温度、反应压力对反应的影响,之后进一步考察了催化剂的稳定性,并通过XRD及TEM表征分析了催化剂失活的主要原因。结果表明：在原料液质量分数7.5%、氢酯摩尔比400、液时空速1.8h^-1、反应温度200℃、反应压力1.8MPa的工艺条件下,催化剂表现出了较佳的催化加氢性能,丙二酸二乙酯转化率为93.4%,1,3-丙二醇收率可达到52.8%。反应120h后催化剂完全失活,结合XRD及TEM表征,认为粒径增大、活性组分流失或被部分氧化为Cu⁺是催化剂失活的主要原因。