液化油中含氮化合物的研究进展

综述了液化油的研究现状,石油、焦化行业中含氮化合物的分离方法和技术现状,阐述了液化油中含氮化合物的研究现状,介绍了油品中含氮化合物的分离效果和性质表征,最后对液化油中含氮化合物的研究前景进行了展望。     

Relationships between hydrogen donor abilities and chemical structure of aromatic compounds in terms of coal liquefaction

To obtain fundamental information about hydrogen transfer, the relationships between hydrogen donor ability and chemical structure of model compounds representing donor solvents is studied using gas chromatography,¹H n.m.r. and computing calculation methods. The order of the model compounds in terms of the ability as donor solvent to release hydrogen is: decalin < tetralin < 1,2-dihydronaphthalene < < 1,4-dihydronaphthalene. This trend closely correlates with the difference in binding energies of the hydroaromatic compounds and their radicals, determined by intermediate neglect of differential overlap (INDO) calculation. Electron spin resonance spectroscopy (e.s.r.) confirms that radical species are created after heat-treatment of the donor compounds. The ability of model compounds representing coal to accept hydrogen is assessed from a comparison of the¹H n.m.r. spectra. It is established that donor and acceptor efficacies are dependent upon chemical structure.     

Coal liquefaction using ore catalysts

Ores and ore concentrates containing minerals of Co, Mo, Ni, Fe, and other potentially active metals have been investigated as slurry catalysts for liquefaction of Blacksville mine, Pittsburgh seam, bituminous coal. The tests were conducted batchwise in a stirred autoclave for 30 min at 425°C and 13.79 MPa (2000 psig) hydrogen pressure according to a two-cycle scheme. In the first cycle, the reaction charge consisted of ground coal, catalyst, hydrogen, and SRC-II heavy distillate. The product of the first cycle was hot-filtered, and the liquid product served as a vehicle for the second cycle, which was otherwise run identically to the first. Reaction products from each cycle were analysed to determine conversion of coal, yield of liquids, liquid product viscosity, and group type (preasphaltene, asphaltene, and oil). Mixtures of ores containing iron pyrites and minerals containing other catalytically active transition metals were compared to pyrites alone and to a pulverized supported Co-Mo-alumina catalyst. An ore catalyst containing both Fe and Ni was superior to another that contained an equivalent mass of iron alone. The best ore catalysts tested, in terms of high liquid yields and low product viscosities, were mixtures of pyrites and molybdenum- and cobalt-containing ores. The latter yielded results that approached those obtained with an equivalent mass of cobalt and molybdenum on an alumina support.     

Coal liquefaction in lignin-derived liquids under low severity conditions

It is found that lignin-derived liquids when reacted with coal under mild reaction conditions (375 °C and 2.17 × 10⁶ − 3.55 × 10⁶ N m⁻¹) enhance the rate of coal depolymerization. Up to 30% enhancement in coal conversion rate is achieved using lignin-derived liquids. The influence of time of reaction and temperature on the degree of reaction was investigated. The lignin liquid-assisted coal depolymerization products (liquid) are observed to contain a significant amount of the desirable pentane-soluble fraction. Influence of the time of storage of lignin-derived liquids on coal conversion was also determined. Also reported are data on elemental analyses of the solid and liquid products. The liquid product analyses using n.m.r. and s.e.c. techniques are also presented. Based upon the experimental data collected, it is hypothesized that enhancement in coal depolymerization rate can be explained by a reaction pathway involving intermediates formed from lignin-derived lignin liquids. A mathematical model describing the reaction chemistry has been developed. Computed rate constants are also reported. The analysis indicates that the lignin-derived intermediates are short-lived as compared to the time needed for complete coal depolymerization.     

煤的直接加氢液化工艺

提出中国搞煤液化的必要性,介绍了煤液化的方法,重点对目前世界上较先进成熟的煤直接液化技术的工艺特点进行了总结和比较,提出了综合利用煤直接和氢液化技术炼油的可行性方案。     

Coal liquefaction by colloidal iron sulphide catalyst

Taiheiyo coal, which was treated with an aqueous solution of dodecyltrimethylammonium chloride, adsorbed colloidal iron sulphide prepared from FeS0₄ · 7H₂O and Na₂S · 9H₂O in aqueous media. The adsorbed colloidal iron sulphide was much more effective as a catalyst for the liquefaction of the coal itself than the usual powder-type iron sulphide. Thus in differential thermal analysis under hydrogen, the coal with 0.35wt% adsorbed colloidal iron sulphide gave an exothermic peak at 401 °C, which was ≈20 °C lower than when using the powder-type iron sulphide. The coal was smoothly hydrogenated at 450 °C to give a yield of ≈60% liquid products.     

Coal liquefaction induced by hydrogen atoms

Reactions between coals and hydrogen atoms were studied using a discharge flow apparatus at temperatures ranging from 403 to 523 K under 133 Pa pressure. Australian brown coal (Yallourn) and Japanese subbituminous coal (Taiheiyo) both yielded liquid hydrocarbons of similar composition. In contrast to conventional coal liquefaction, the present system led to the formation of exhaustively hydrogenated products composed mainly of monocyclic alkanes.     

Coal liquefaction by the hydrogen produced from methanol: 2. Model compound studies

Coal can be converted into a material soluble in solvents using methanol as an in-situ hydrogen source and also as an alkylating agent. This paper presents the results of the reaction of selected model compounds with methanol using two different hydrogenation catalysts: stabilized nickel at 365 °C, and stabilized cobalt at 405 °C and 445 °C. Stabilized nickel is a much better hydrogenation catalyst than stabilized cobalt. The alkylation reaction is strongly dependent on the presence of specific functional groups (-OH, -NH, etc). Also, the alkylation reaction appears to be independent of the hydrogenation catalyst used and it seems to depend more on the temperature. The alkylated products from the reactions at 405 °C showed an order as follows: carbazole phenol ? phenanthrene dibenzofuran diphenylether dibenzothiophene diphenylmethane. A free radical mechanism is proposed for the alkylation reaction.     

Coal liquefaction using iron complexes as catalysts

Hydroliquefaction of Japanese Miike and Taiheiyo coals was carried out using various iron complexes as catalysts in tetralin at 375–445 °C. Iron pentacarbonyl (Fe(CO)₅) showed the highest catalytic activity, increasing coal conversion by about 10% at 425 °C under an initial hydrogen pressure of 5 MPa. Amounts of hydrogen transferred to coal increased from 1.4–2.3 wt% of daf coal in the absence of the catalyst to 2.5–4.2 wt% of daf coal in the presence of Fe(CO)₅ at 425 °C.     

煤直接液化油中硫氮化合物的类型分布

为研究煤直接液化油中硫氮化合物的类型分布,根据煤直接液化油的特点,采用GC-PFPD和GC-NCD方法分别优化煤直接液化油中硫氮化合物的分析条件,获得了煤直接液化油中硫、氮化合物的组成及含量。结果表明,煤直接液化油中硫主要以苯并噻吩类和二苯并噻吩类化合物存在,两者占原料油中总硫含量的90%以上,是煤直接液化油加工脱硫的主要对象;煤直接液化油中氮主要以五元杂环含氮化合物形式存在,占比32%,主要代表物质是吲哚类和咔唑类化合物,两者占原料中总氮含量的50%左右,是煤直接液化油加工脱氮的主要对象。     

Coal liquefaction catalysis: Iron pyrite and hydrogen sulphide

An unreactive hvC bituminous coal has been hydrogenated in a batch-stirred reactor using pyrite, hydrogen sulphide, and pyrite+hydrogen sulphide as catalysts. The data indicate that H₂S is an active homogeneous catalyst for coal liquefaction, and suggest that pyrite may be acting indirectly as a catalytic agent via H₂S release.     

Coal liquefaction by the hydrogen produced from methanol

Methanol was used as an in-situ hydrogen source, following its decomposition over ZnO-Cr₂O₃, for the hydrogenation of coal. The reaction was carried out in a high pressure autoclave at ≈400–440 °C, in the presence of different hydrogenation catalysts. Stabilized nickel, stabilized Co and Ni-Cr-Cu catalysts gave excellent results. The maximum conversion was 100% for pyridine, 94.4% for benzene and 66.2% for straight-chain hexane.     

煤炭直接液化油中酚类化合物的分离与利用

酚类化合物是煤炭直接液化产物中具有较高附加值的主要含氧化合物,也是煤液化油酸性物质的主要成分。它不仅对油品的提质加工的技术路线有影响,而且也对煤炭直接液化的经济性具有较大的影响。由于该方面的研究工作尚属起步阶段,借鉴煤焦油和石油系产品中酚类化合物的有关分离与利用情况,结合笔者的研究实践和认识,提出了在煤直接液化油中酚类的分离与利用方面应开展的工作和研究方向。     

煤直接液化研究评述

比较了中国与国际基础研究水平的差距,对主要的新老工艺进行了分类和比较,发现成功的液化工艺都符合煤分子结构的特点。高温快速液化是一种基于煤分子结构特殊性的直接液化方案,在理论上提供了实现最高液化效率和最低液化成本的可能性,联产芳香族化合物和燃料油,开辟了一个新的研究方向。     

Synergistic effects between light and heavy solvent components during coal liquefaction

As part of research to examine coal conversion in solvents containing high-boiling-point components, experimental studies were carried out with model compound solvents. The dissolution of bituminous and subbituminous coals was investigated in pyrene-tetralin and 2-methylnaphthalene-tetralin mixtures. The effects of donor level, gas atmosphere, hydrogen pressure and conversion temperature were determined. At 400 °C, in the presence of hydrogen gas, pyrene-tetralin solvent mixtures show synergism in coal conversion. At donor concentrations as low at 15 wt%, the degree of conversion was almost as high as in pure tetralin. This phenomenon was not apparent in 2-methylnaphthalene-tetralin mixtures. The relative ease of reduction of pyrene and its ability to shuttle hydrogen is considered to be a principal reason for this difference in behaviour. Conversion in pure pyrene and in pyrene-tetralin mixtures at low donor concentrations increased with increasing hydrogen pressure. At 427 °C, bituminous coal conversion was higher in a 30 wt% tetralin-70 wt% pyrene mixture than in either pure compound. It was found that in the absence of coal pyrene can be hydrogenated by H-transfer from tetralin as well as by reaction with hydrogen gas. This can provide a means to increase the rate of transfer of hydrogen to the dissolving coal through the formation of a very active donor (dihydropyrene). During coal liquefaction, several pathways appear to be available for hydrogen transfer for a given coal, the optimal route being dependent upon the solvent composition and the conditions of reaction.     

Coal liquefaction by in-situ hydrogen generation.: 2. Zinc-water model compound reactions

Model compound studies were carried out to elucidate the reaction mechanisms taking place during the liquefaction of coal with the hydrogen produced from the reaction of zinc and water. In compounds of the type Ph-(CH₂)_n-Ph the splitting of the aliphatic bridge was easier with higher n values. Ether type compounds such as diphenylether were unreactive although the C-O bond in dibenzylether was easily cleaved. Condensed ring aromatic compounds gave low conversion with hydrogenation being facilitated by an increase in ring number. Phenolic compounds such as phenol did not react well, but the reactivity increased with increase in aromatic ring size. The cleavage of the aliphatic bridge was accelerated by the OH group, for example, in the case of 4-hydroxydiphenylmethane bond scission was about 15 times higher than that of diphenylmethane. Heterocyclic compounds were unreactive.     

Coal liquefaction using indene-tetralin and indene-decalin mixtures as solvent

Indene-tetralin and indene-decalin mixtures were used as the solvent for coal liquefaction. The effect of mixing on conversion for Yallourn coal was observed under nitrogen pressure at 400 and 440 °C. Conversion to benzene-soluble material in an indene-decalin mixture (50:50, wt) at 440 °C for 1 h was 73.0% and was only 9% lower than that in 100% tetralin. The reaction of indene with tetralin or decalin may provide the active species for coal dissolution. Simultaneously, coal radicals may be scavenged by indene.     

Extents and models of adduction of hydrocarbon and nitrogen-containing solvents in coal liquefaction

Coal liquefaction experiments have been carried out to determine the tendency for adduction of several hydrocarbon- and nitrogen-containing structures typical of coal. Principal conclusions are: that even good hydrogen donors such as tetralin and octahydrophenanthrene are adducted readily; that benzyl radicals adduct primarily by radical-radical reaction, yielding thermally labile products; and that quinoline adducts to coal-derived liquids primarily by hydrogen bonding with little formation of C-C or C-N bonds.     

Coal liquefaction solvents: 1. Methods of separation; characterization by chromatography and spectrometry

N.m.r. spectral assignments were carried out for major component identification in liquefaction solvents. Fractionation, n.m.r. and capillary g.c. were applied to analysis of anthracene oils and an SRC middle distillate. Commercial anthracene oils were found to vary widely in composition. Alkane contents ranged from 2–3%, greatly influencing solvent stability, performance and liquefaction yields at 460 °C.     

Coal liquefaction model: microscopic examination of solids from metal halide catalysed coal hydrogenation experiments

Coal undergoes changes during the hydrogenation process which depend on the balance between carbonization and hydrogenation reactions, which in turn depend on various experimental conditions, i.e. hydrogen availability, heating rate etc. If carbonization conditions prevail, semicoke is formed, whereas liquid hydrocarbons are formed under hydrogenation conditions. This model is applicable to hydrogenation reactions carried out under a wide range of experimental conditions.