Hydrogenation of coal from the Chaidakh deposit in the Lena Basin

The results of the evaluation of coal from the Chaidakh deposit in the Lena Basin as a raw material for the production of liquid fuel by hydrogenation are reported. Coals from the Chaidakh deposit, whose reserves exceed 250 million tons, have favorable mining and geological positions and low ash and sulfur contents. They can be considered as promising raw materials in the northern regions of the Lena Basin (with deficiencies in motor fuels and lubricants) for conversion into liquid fuel, as supported by this study of their reactivity toward hydrogenation under hydrogen pressures to 10 MPa.     

Hydrogenation of coal from transbaikalia deposits in the presence of a recirculating paste-forming agent

Data on the hydrogenation of coal from the Zashulanskoe field in Transbaikalia in three cycles in the presence of a recirculating coal distillate solvent with a boiling point of 300–425°C are reported. It was found that the degrees of conversion of the organic matter of coal (OMC) into liquid and gaseous products reached in the second and third cycles were 85–88%. The yields of liquid products and gases were 81–85 and 6.9–7.4%, respectively, and the consumption of hydrogen was 2.3–2.4%.     

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。     

Chemical structure of the high-molecular-weight hydrogenation products of coal from the Zashulanskoe field

The results of experimental studies on the determination of the chemical structure of asphaltenes and preasphaltenes in the liquid products of the hydrogenation of coal from the Zashulanskoe field in the Chita oblast. It was found that, in the preasphaltenes, the value of f _a and the concentrations of oxygen groups (OH, COOH, and C=O) were greater and the concentrations of CH₂ and CH₃ groups were smaller that those in the asphaltenes. The highest concentration of CH₂ groups was found in substances soluble in n-hexane (oils). It is likely that the change in the character of high-molecular-weight hydrogenation products formed from the structural fragments of the organic matter of coal (OMC) largely depended on reaction conditions, namely, the rate of heating and the isothermal exposure time.     

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.     

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).     

Chemical structure of asphaltenes and preasphaltenes obtained by coal hydrogenation under high-speed heating conditions

The results of experimental studies on the determination of the chemical structure of asphaltenes and preasphaltenes in the liquid hydrogenates of coal from the Zashulanskoe field in Transbaikalia are reported. These results were obtained under the conditions of high-speed heating (～200 K/min; reaction time, 10 min). It was found that the structural characteristics of asphaltenes and preasphaltenes obtained by high-speed hydrogenation at 425°C and 10 MPa exhibited a number of special features. At similar fractions of aromatic carbon, these products differed from the coal hydrogenates obtained at a slow rate of heating (5 K/min; reaction time, 120 min) in terms of the distribution of hydrogen and oxygen over structural groups. In them, the hydrogen content of CH₂ and CH_ar groups was smaller and that of CH₃ groups was greater. The highest concentration of total oxygen-containing groups was detected in the high-speed process preasphaltenes, whereas it was lower in the asphaltenes.     

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。     

Coal hydrogenation under short-term reaction conditions

The results of the hydrogenation of coal from the Zashulanskoe deposit in the Chita oblast under conditions of a short reaction time (no longer than 10 min) are given. It was found that, to reach a 78–80% degree of coal conversion under the conditions of high-speed heating (∼200 K/min), the reaction time can be no longer than 10 min (the coal: paste-forming agent ratio = 50: 50), which corresponds to a feed space velocity of 2.5–3.0 kg l⁻¹·h⁻¹. This value, which determines the process productivity of coal hydrogenation, is higher by a factor of 3–3.5 than that under analogous conditions used in second generation processes, which were developed in the 1990s.     

煤焦油加氢采用二段工艺的必要性

煤焦油是一种复杂的混合物,含有大小相差悬殊的各种分子,将这些分子转化为优质的汽、柴油分子,需进行不同程度的裂解和加氢反应。如果采用一段加氢工艺,给其同样的裂解程度,势必造成目的产物的质量差或产率低等问题。醒段加氢工艺,分别进行液棚加氨和气相加氢。大大提高了产品的质量与收率。     

Processes for the conversion of coals in a mixture with rubber-containing wastes into liquid fuel

Promising processes for the utilization of worn tires in a mixture with coal by converting them into synthetic liquid fuel are considered, namely, the combined pyrolysis of both components, the destructive hydrogenation, the extraction, and the process of ground tire rubber combustion.     

Current status of the hydrogenation of coals

The theoretical and experimental studies carried out at the Institute for Fossil Fuels during recent years in the modernization of hydrogenation technologies for coal conversion into a liquid fuel under low hydrogen pressure (10 MPa for bituminous coals and 6 MPa for a number of brown coals) are surveyed. These studies are based on the advances of catalysis science and on the current concepts of the hydrogenation of organic compounds and coal multimer. The capacity and cost efficiency of a coal chemical enterprise in the commercialization of the technology are substantiated.     

生产国Ⅴ柴油的液相循环加氢技术

介绍了抚顺石油化工研究院开发的柴油液相循环加氢技术及其在柴油加氢工业装置上生产国Ⅴ标准柴油的应用情况。结果表明,采用柴油液相循环加氢技术处理直馏柴油、直馏柴油和焦化柴油的混合油及直馏柴油和催化柴油的混合油时,均可以生产满足国Ⅴ标准的清洁车用柴油调和组分。在反应器入口压力9.5 MPa、体积空速1.3 h~(-1)、循环比1.5和入口反应温度360℃的工艺条件下,加工直馏柴油和催化柴油的混合油,可以生产国Ⅴ标准的车用柴油产品调和组分,并可以满足装置长周期稳定运行的要求。     

挂式四氢双环戊二烯合成工艺研究进展

以双环戊二烯为原料,通过加氢、异构化两个过程得到一种高能量密度燃料——挂式四氢双环戊二烯(exo-THDCPD)。综述了exo-THDCPD制备过程涉及的技术现状,包括反应原理、工艺路线、主要技术参数等内容。重点介绍了加氢与异构化催化剂种类及制备方法、加氢与异构化工艺流程的研究进展。总结出非贵金属合金催化剂为加氢催化剂的研究重点;延长固载化Al Cl3催化剂的使用寿命、提高分子筛催化剂的抗积碳能力、降低离子液体催化剂的生产成本是异构化催化剂的3个研究方向;提高双功能催化剂的选择性对"一锅法"制备exo-THDCPD意义重大;液相串联工艺有望实现exo-THDCPD的连续化工业生产。     

Translating clean liquid fuels synthesis with low aromatics over NaFe@C/HZSM-22 directly in CO2 hydrogenation

Fuel production is an option for valorizing CO₂, yet deficient catalysts meeting the standard fuel production has impeded progress of this promising technology. Herein, liquid fuel synthesis is rationalized over a catalyst consisting ‘C′, ‘Na’, and ‘Fe’, as in NaFe@C, configured with ZSM-22 and ZSM-5 in CO₂ hydrogenation. While the ‘Na’ and ‘C′ functioned as structural promoters on Fe to enhance CO₂ conversion and olefins synthesis, the characteristics of the zeolites facilitated oligomerization of lighter hydrocarbons. A high C₅ + selectivity was obtained over the HZSM-22 composite in CO₂ hydrogenation dominated by olefins and isoparaffins. Model reactions for exemplar oligomerization activity over the zeolites revealed ZSM-5 as highly active with selectivity towards isoparaffins and aromatic. The ‘Na’ cations induce Lewis’s acid sites (LAS) which suppresses hydrocracking during chain growth. This consistency, revealed between the model and CO₂ hydrogenation unlocks a door to zeolite usage in CO₂ hydrogenation to clean heavy hydrocarbons.     

木质纤维素基平台化合物催化转化制备液体燃料及燃料添加剂

随着不可再生的石化资源的不断消耗以及生态环境的不断恶化,可再生资源和能源的开发和利用受到越来越多的重视。木质纤维素是地球上最丰富的可再生生物质资源,蕴藏量和产量巨大,具有广阔的开发利用前景。本文在介绍国内外木质纤维素资源开发利用研究的基础上,结合当今世界生物质能领域的研发现状,分别概述了经由呋喃类化合物及乙酰丙酸等木质纤维素基平台化合物分子,制备液体燃料和燃料添加剂的最新研究进展。在总结归纳合成途径的同时,分析了现阶段面临的主要问题及可能的解决办法,以期能为木质纤维素类生物质能源化利用的研究提供有益的参考与借鉴。     

Hydrotreating coal-derived liquid distillation fractions. 1. Study of single-stage treated products for transport fuel use

A coal-derived liquid distillate obtained from catalytic hydrogenation of Wandoan coal at Australian Coal Industry Research Laboratories has been fractionated into three main distillation fractions: naphtha, kerosine, and diesel. Compositional properties of each fraction are reported, particularly elemental, ¹H and ¹³C n.m.r. and h.p.l.c. results. Hydrorefining of each fraction was undertaken in a trickle-bed reactor at various conditions using commercial nickel-molybdenum hydrotreating catalysts. The hydrotreated liquid products were assessed for transport fuel use or as feedstocks for further processing.     

FCC柴油加氢精制催化剂与工艺研究

以氢氧化铝干胶和分子筛混合作为载体,采用浸渍法制备出Ni-W型催化剂;采用BET和Py-IR对所制备的催化剂进行了表征,以FCC柴油为原料进行了加氢活性评价。结果表明：由于催化剂载体中加入了分子筛,使该催化剂具有较强的酸性,从而为柴油十六烷值的提高提供了条件;该催化剂适宜的操作条件为：350℃,7 MPa,450∶1,1.0 h-1。     

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.     

Evaluation of the maximum yields of synthetic petroleum and methane in coal conversion processes

A procedure for the calculation of minimum consumptions of coals of different ranks for the production of liquid motor fuels and methane from them by direct hydrogenation and gasification followed by the Fischer-Tropsch synthesis is proposed. This procedure takes into account the composition of the initial coal, the degree of conversion of its organic matter into a mixture of CO + H₂, and the H₂/CO ratio in this mixture. As an example of its application, the yields of liquid motor fuel and methane from brown and black coals (D, G, and SS) from a number of deposits, which are of interest for performing these processes, were calculated.