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.     

Oxygen sorption by coal from the Shubarkol deposit

The results of an experimental study of the rate constant of sorption and the critical temperature of self-heating in the low-temperature oxidation of coal from the Shubarkol deposit by oxygen with the use of gas chromatography are reported.     

半焦催化裂解煤热解焦油模型化合物的研究

在固定床反应器内研究了不同半焦催化剂对煤焦油模型化合物(甲苯、环己烷、正庚烷)的催化裂解效果。结合BET、XRD、SEM-EDS等表征手段,对催化半焦的性质进行分析,采用FTIR对液相产品进行分析。结果表明,活化后半焦的表面积增大,半焦表面的金属矿物质含量增加,都会提高其对焦油模型化合物的催化裂解能力。通过FTIR对3种不同模型化合物经AC-15催化剂作用后的产物分析可知,环己烷主要发生了开环反应,正庚烷主要发生了脱氢反应,甲苯被裂解产物的芳香性有所下降,最终生成一系列链烃化合物。     

Producing lignite pitch from high-boiling semicoking tar

The heat treatment of high-boiling tar fractions from Berezovsk lignite (Kansk–Achinsk Basin) in a solid-fuel reactor to obtain lignite pitch is investigated. In addition, the use of the semicoke to reduce granulated phosphorus pellets from Dzhanatas ore is studied. The lignite pitch and semicoke may also be used in coking batch for the production of blast-furnace coke with improved properties; as binder in the production of domestic lignite-based fuel briquets; as binder in the sintering of Kovdorsk and Olenegorsk iron-ore concentrates at AO Severstal’; as binder in the production of anode masses for aluminum production; as binder in bricks and cold packing employed in the manufacture and sealing of electrolyzer hearths; and for pyrolysis with natural methane to increase the yield of ethylene.     

Effect of iron additives on the thermal degradation of coal from the Shubarkol deposit

The kinetic parameters of the thermal degradation of coal in a temperature range of 32–458°C without additives and in the presence of nanosized iron powder as a catalyst were calculated based on thermogravimetric analysis data. The rate constants and activation energies of the first and second steps of thermal degradation processes were determined. The influence of the catalytic additive on the value of activation energy was found. The results of the thermogravimetric analysis can be used in a study of thermocatalytic modification processes for the hydrogenation of fossil coals.     

Generation of pitch-like products by the thermal dissolution of coal in heavy semicoking tar

The influence of hydrogenating upgrading of heavy semicoking tar from long-flame coal on its properties and composition is studied when it is used as the solvent in the thermal dissolution of bituminous gas coal (GZh coal). It was found that the concentration of oxygen-bearing compounds declines on catalytic hydrogenation of tar at 5 MPa and on combined treatment with two hydrogen donors: tetralin and the anthracene oil. After hydrogenating treatment, the heavy semicoking tar may be used as the solvent in the thermal dissolution of GZh coal so as to obtain pitch-like products.     

Organomineral sorbent from Shubarkol coal

The sorption properties of an adjoining rock and its modified forms obtained by treatment with modifier solutions, including coal humic acids, were studied. The applicability of new organomineral sorbents to the extraction of copper, nickel, and calcium ions from model mineralized aqueous solutions and industrial wastewater was demonstrated. It was found that the efficiency of the test sorbents was comparable to the sorption capacity of commercial carboxylic cation-exchange resins.     

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 iron chloride to the hydrogenation of coal from the Shubarkol deposit in a mixture with polyethylene

The results of the hydrogenation of Shubarkol coal with an applied catalytic additive of iron chloride and a polymer as a solvent and a source of hydrogen are described. The donor properties of the polymer in the process of hydrogenation were demonstrated by the reaction of anthracene as a model compound with polyethylene in the absence of external hydrogen, which leads to the formation of hydrogenated derivatives.     

Catalytic reforming of coal tar pitch in supercritical fluid

This paper describes a new method to remove nitrogen from coal derived pitches, using catalytic hydrotreating in supercritical toluene-tetralin. The results obtained suggest that nitrogen was selectively removed from the mother pitch, the reaction rate was much higher than that in conventional processes due to higher diffusivity, and coke deposition on the catalyst could be prevented perhaps due to the high solvent power of the supercritical fluid.     

Catalytic cracking of tar in biomass pyrolysis gas in the presence of calcined dolomite

The possibility of decreasing the content of tar in the fuel gas obtained by biomass pyrolysis has been studied. Catalytic cracking of the tar in presence of dolomite was used. Dolomite showed a high catalytic activity. The overall effect of the dolomite is to increase the gas yield by decreasing the tar yield. The dolomite and the steam used seem to affect the amount of naphthalene produced. By adjusting both the amounts of catalyst and steam, we were able to decrease significantly naphthalene (13 mg/kg dry substance biomass) and amount of tar (164 mg/kg dry substance biomass).     

双金属催化剂对煤焦油模型化合物催化裂解行为的影响

以Al₂O₃为载体,Ce、Co和Fe为助剂,采用机械化学法制备了4种镍基催化剂,对其进行了XRD、H₂-TPR、BET、NH₃-TPD等表征。当载气流量为50 ml·min^-1,裂解温度为750℃时,在固定床反应器中考察了各催化剂对煤焦油模型化合物甲苯+芘裂解行为的影响。结果表明：4种催化剂均为介孔催化剂,且双金属催化剂的介孔有序度更高;催化剂中活性组分Ni主要以尖晶石NiAl₂O₄的形式存在;添加Fe助剂后,催化剂的酸强度较Ni/Al₂O₃增加,添加Ce和Co时则相反。评价实验表明,助剂对重质组分芘的裂解率影响较小,约为67%,然而Ce和Co对催化剂的抗积炭性能有利,其析碳分别较无助剂时降低28.8%和18.0%。     

Influence of tall oil and ultrasound treatment on pitch production from semicoking tar or the anthracene fraction

The properties of coal pitch obtained from blends of tall oil and semicoking tar or the anthracene fraction are investigated. Small additions of tall oil to semicoking tar (in the ratio 1: 6) increase the yield of pitch on thermal oxidation and its softening temperature but decrease the coke residue. On ultrasound treatment, chemical transformations of the molecules under the action of cavitation change the characteristics of the pitch produced on thermal oxidation. Primarily, however, the ultrasound permits reduction in the benzo[a]pyrene concentration in the mixture by almost half. On thermal oxidation, the benzo[a]pyrene concentration is further reduced, but most of its mass is concentrated in the pitch.     

Determining the suitability of coal for semicoking in internally heated vertical furnaces

A method of determining the semicoking products of coal is proposed as a means of evaluating the suitability of the coal for industrial semicoking in an internally heated vertical furnace. As an example, long-flame Kuznetsk Basin coal is evaluated. The method has been adopted at Leninsk-Kuznetsk semicoking plant.     

水蒸气对煤焦油模化物裂解行为及析碳的影响

采用机械化学法制备Ni-Ce/Al₂O₃催化剂,在固定床反应器中考察了水蒸气气氛对煤焦油模型化合物甲苯＋芘催化裂解行为的影响。根据产物生成规律提出了芘向萘转化的裂解机理,并以D₂O对其进行了验证。通过XRD、TG-DTG和Raman等表征了析碳的类型与结构特征。结果表明：相较于纯氮气气氛,水的加入可明显提升重质组分芘的裂解率,且随水碳比（S/C）增加呈先增加后降低的趋势,在S/C=0.15时达到最大值98.93%,比S/C=0时增加32.09%。析碳率随S/C比增加一直呈下降趋势,由S/C=0时的10.04%降至S/C=0.26时的5.39%。析碳分析结果表明,S/C=0时,生成的积炭类型主要是β型碳及γ型碳,水蒸气存在时,活性较高的α型碳含量增加,说明水蒸气的持续消碳作用抑制了C_α向C_β与C_γ方向转化。     

Isomerization of phenols from a coal tar fraction

A new method for the hydrogenation of a primary coal tar fraction in the presence of a nanocatalyst at an elevated pressure in an atmosphere of hydrogen was proposed. The effect of the relative H-donor ability of the primary coal tar fraction on the yields of hydrocarbon fractions to 300°C and the solid residue was studied.     

Production of chemicals by cracking pyrolytic tar from Loy Yang coal over iron oxide catalysts in a steam atmosphere

Iron oxide catalysts containing metal promoters were tested to evaluate whether they could be applied to the coal tar obtained from the pyrolysis of Loy Yang coal. Catalytic cracking of the coal tar in a steam atmosphere was conducted in a fixed-bed reactor at 773 K and ambient atmospheric pressure. For iron oxide catalysts containing cerium, zirconium, and aluminium, the total yield of monocyclic aromatic hydrocarbons, phenols, and ketones exceeded 40 mol-C% on a tar basis, while about 97 wt.% of the initial heavy tar was decomposed. The combination of cerium, zirconium, and aluminium improved the activity of the iron oxide catalyst. Moreover, the addition of steam to the tar vapour increased the yield of ketones and made the catalyst more durable.     

快速热解低温煤焦油的初步分析

对多联产煤焦油的基本性质进行测定,利用色谱-质谱联用仪（GC-MS）对其主要成分进行了分析,结果表明多联产煤焦油与常规煤焦油有很大区别,甲苯不溶物、软化点、水分和灰分比常规煤焦油高得多;酚类化合物含量较高。     

Characterisation of the neutral oil from a low-temperature coal tar

Tar resulting from fluidised-bed, low-temperature carbonisation of coal was treated to yield a neutral oil from which a series of six other samples was extracted. These were examined by proton magnetic resonance (p.m.r.) spectroscopy, low-ionising-voltage (11 eV) mass spectroscopy (m.s.), gel chromatography followed by fluorescent indicator analysis, and cryoscopy. Aliphatic fractions separated chromatographically were also examined by infra-red spectroscopy. Distributions of hydrogen between chemical types were found for the several fractions from 60 MHz p.m.r. spectra and presented in terms of average structural parameters. M.s. analysis indicated negligible cracking of paraffin components, and the average molecular weight of 197 agreed well with cryoscopic determinations. For the carbon ratio, f_a, between aromatic and total, agreement between m.s. and p.m.r. depends on the p.m.r. structural analysis scheme adopted. P.m.r. and m.s. structural analyses of the aromatics emphasise the predominance of di- and tri-nuclears, with about 40% of available sites substituted, and the importance of acenes in lowtemperature carbonisation material. Gas and gel chromatography showed urea-adductable paraffins to be largely straight-chain C₁₀-C₂₆, much as for tars from carbonisation at higher temperature.