Relative reactivity of hydrogen donor solvent in coal liquefaction

Hydrogen transfer from donor solvent to coal must involve reactions such as hydrogen donation to free radicals and hydrogenation of aromatic structures. The relative reactivities of five typical hydrogen donor solvents, more reactive than tetralin, were determined using a competing elimination reaction in the liquefaction of a bituminous coal at 400 °C and a brown coal at 350 °C. 9,10-Dihydroanthracene, 9,10-dihydrophenanthrene and 1,2,3,4-tetrahydroquinoline exhibited outstanding hydrogen donating ability. Further, the relative reactivities of five mild hydrogen donor solvents such as acenaphthene and indan were determined by a similar elimination reaction using a bituminous coal at 450 °C.     

Short contact time liquefaction of coal using hydrogen donor solvent

Liquefaction of coals to form benzene-soluble materials was studied at 400 °C under autogenous pressure conditions using tetrahydroquinoline (THQ), tetrahydroisoquinoline (THIQ) and tetralin (TL) as the hydrogen donating solvents. THQ was the best solvent with a conversion rate of 90% within 15 min for low rank coals (< 80% C). In contrast, it took 50 min to achieve a conversion of 80% when TL was used as the solvent, although both solvents could achieve almost complete conversion of coals into quinoline-soluble material within 10 min. THQ also showed excellent activity with blended coals. Some binary solvents exhibited activities which varied with the THQ content. A 1:3 by weight mixture of THQ and petroleum pitch produced the highest conversion of 100%.     

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。     

Coal liquefaction in nitrogen compounds

Model compound studies have shown that 1,2,3,4-tetrahydroquinoline is an exceptionally good coal solvent. In the pure compound, subbituminous coal conversion to THF-soluble products approaches 100% under relatively mild reaction conditions. The effectiveness of tetrahydroquinoline for coal conversion appears to be related to its concentration relative to coal. The unique behaviour of tetrahydroquinoline is ascribed to its being a highly active H-donor; the fact that it is regenerable under reaction conditions by the reaction of hydrogen and quinoline; and that its polarity allows penetration of the coal structure and aids in dispersion of the dissolved coal. It has been found that, during reaction with coal, tetrahydroquinoline and other nitrogen compounds undergo extensive condensation reactions which result in an increase in the nitrogen content of the high boiling and non-distillable liquefaction products.     

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.     

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。     

神府煤液化油石脑油馏分重整生产芳烃的研究

由于煤液化油石脑油馏分(200℃)中芳烃潜含量较高,利用煤液化油石脑油馏分为原料,进行加氢精制,将原料中的硫氮含量降至1 mg/kg左右,满足重整进料要求,然后在小型固定床连续反应器上进行加氢重整生产芳烃试验。着重考察重整反应前、后族组成的变化及主要芳烃化合物的产率。结果表明,加氢重整过程中发生正构烷烃异构化反应;环烷烃主要发生脱氢芳构化反应转化为芳香烃;煤液化油石脑油馏分适宜进行催化重整,C_1~C_4烃气产率6.03%,氢气产率3.60%;重整后,芳烃含量达83.20%,其中C_6~C_8芳烃含量61.03%,是提取BTX的良好原料。石脑油的馏程对芳烃的组成和产率有一定影响,适宜的馏程为60~160℃。     

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。     

Changes in hydrogen utilization with temperature during direct coal liquefaction

A method for quantitative measurement of the hydrogen utilized in different modes of reaction has been applied to hydroliquefaction reactions at temperatures ranging from 375 to 450 °C. The analytical approach is capable of differentiating hydrogen utilized in hydrogenation reactions from that used in bond scission chemistry (hydrogenolysis). The hydrogenolysis reactions result in breakdown of the coal matrix, formation of light hydrocarbon gas and elimination of organic heteroatoms. The results indicate that in this small continuous reactor, operated at 13.8 MPa (2000 psig) H₂, little net chemical activity of hydrogen occurs at 375 °C. However, at 400 °C, the slurry has been hydrogenated significantly with little net hydrogen incorporation. At 450 °C comparable amounts of hydrogen are consumed in gas generation, heteroatom removal, hydrogenation and matrix breakdown, with large net hydrogen incorporation. These results indicate that at temperatures below the thermolysis threshold of 400 °C, significant internal hydrogen redistribution occurs in the slurry. At higher temperatures, a more conventional hydroliquefaction chemistry involving significant bond cleavage and aromatization is indicated. This approach to analysis of hydrogen utilization requires integration of a variety of analytical data. The uncertainties in these data and their impact on the resultant utilization profile are discussed.     

Chemistry of solvents in coal liquefaction: Quantification of transferable hydrogen in coal-derived solvents

Hydrogen was evolved as hydrogen sulphide when coal-derived solvents for liquefaction were heated with sulphur (dehydrogenation method) and their naphthene contents were quantified by titration and ¹³C n.m.r. analysis to estimate the amount of transferable hydrogen from hydroaromatics present in the solvent. Examination of synthetic solvents consisting of model compounds confirmed the validity of both approaches. The content of transferable hydrogen, thus measured, in the various solvents correlated well with their liquefaction activities using Morwell brown coal. This suggests that the sufficient stabilization of radical fragments derived thermally from the coal at the initial stage of its liquefaction leads to high conversion. It was also shown that the dehydrogenation method was applicable to non-distillable heavy fractions of coal-derived liquids such as SRC which are difficult to measure by n.m.r. because of their limited solubility.     

Interrelationship of chemical characterization and rheological behaviour of coal liquefaction bottoms

In the development of the Exxon Donor Solvent (EDS) process, bituminous and subbituminous coals have been processed in a one ton-per-day coal liquefaction pilot plant using the feed coal slurried with solvent and with or without bottoms recycle. The liquefaction bottoms from both once-through and bottoms recycle operation exhibit non-Newtonian viscometric behaviour. The recycled bottoms, however, are more viscosity/shear dependent, less viscosity/temperature dependent and more thermally stable than the once-through bottoms. Chemical characterization of these bottoms reveals that alkyl and phenoxy groups are important functional groups responsible for the viscometric behaviour of bottoms. The increase of bottoms viscosity is postulated to involve the elimination/condensation of methylene units are phenolic functional groups to form the crosslinkages of large aromatic clusters.     

煤直接液化溶剂油的平均结构

对一种褐煤的直接液化加氢前、后溶剂油进行了1H核磁共振波谱、元素组成和分子量等性质的分析和平均结构参数的计算,研究了加氢前、后溶剂油分子的平均结构。结果显示：加氢处理前、后溶剂油的平均分子式为C17H23S0.004N0.09O0.12和C16H24S0.003N0.03O0.03,加氢前溶剂平均分子的芳碳率fa为0.46,平均分子结构含有2～3个环,其中芳香环为1～2个,环烷环为1个。经过加氢处理后溶剂油分子的平均结构发生较大的变化,溶剂平均分子芳碳率fa为0.37,平均分子结构中含有2个环,其中芳香环1个,环烷环1个,经加氢处理后,溶剂具备了较好的供氢性能。     

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.     

Catalytic activity of iron compounds for coal liquefaction

The catalytic activity of pyrite and synthesized -FeOOH in coal liquefaction was investigated using batch autoclaves with the aim of developing an industrial iron catalyst. The results indicate that the presence of H₂S helps gaseous hydrogen transferring and prevents deactivation so that the catalyst promotes hydrocracking of coal and hydrogenation of the products. The activity converges with excess H₂S and sulfur addition equivalent to an S/Fe molar ratio of 2.0 being reasonable for the activation. The active site is located on the outer surface, with finely divided catalysts exhibiting high activity. Both pulverized pyrite and synthesized -FeOOH are sufficiently fine as to exhibit high activity in the process. Pulverized pyrite is an industrially feasible iron catalyst for coal liquefaction process, because it is inexpensive and does not require sulfur addition.     

Two-stage liquefaction of a subbituminous coal

The two-stage conversion of a subbituminous coal has been investigated using an autoclave reactor system. The overall performance of the reaction is found to be determined by the effectiveness of the first-stage operation and by the method of sequencing of the stages. The initial thermal products can undergo condensation reactions which render them unresponsive to subsequent catalytic conversion and which increase the light gas yield. This can occur during the first stage reaction, if there is limited capacity for free-radical stabilization, and upon storage and/or thermal cycling between stages. The latter effects are circumvented by operating the two stages in immediate sequence. Condensation is also reduced by increasing the solvent quality and the solvent:coal ratio. The presence of a catalyst during thermal decomposition of coal can greatly improve conversion and product stability even at short reaction time and can reduce constraints on solvent quality. The more feasible approaches to improving first-stage operation appear to be in controlling the solvent composition and in employing hydrogenation catalysts.     

煤质特性与煤直接液化关系分析

简要讨论了原料煤特性对煤直接液化的影响,在煤的组成和物理性质等与煤液化关系之间建立良好的对应关系并总结了适合直接液化用煤种的一些特性。     

Comparative chemical composition and biological activity of single- and two-stage coal liquefaction process streams

Samples from several integrated two-stage coal liquefaction (ITSL) process streams were collected under both normal and off-normal operating conditions. Selected crude materials were tested for their ability to initiate tumorigenicity in the initiation/promotion assay in mouse skin. Crude materials and their chemical class fractions were assayed for microbial mutagenic activity in the standard Ames test with S. typhimurium TA98, and selected samples were also subjected to the Chinese hamster ovary mammalian cell assay for mutagenicity. Mass spectral and gas chromatographic—mass spectral (g.c.—m.s.) analyses were carried out on these materials. Results were compared with those for analogous materials from solvent refined coal (SRC) single stage liquefaction processes. In general, the ITSL distillates were of higher molecular weight, higher hydroaromatic content, lower nitrogen content and were somewhat less alkylated than the analogous SRC materials. Compared to the SRC coal liquefaction materials, the ITSL distillates and bottoms materials collected under normal run conditions were substantially less active in both the microbial and mammalian cell mutagenicity assays. These same materials were also less active than ITSL samples collected under off-normal conditions. G.c.—m.s. analyses showed that ITSL materials collected under normal operating conditions were substantially reduced in amino polycyclic aromatic hydrocarbon content when compared to both the off-normal ITSL, and SRC materials. Activity of the ITSL materials as initiators of tumorigenesis was greater than expected, based on results from the in vitro assays and not significantly different than that of the SRC materials. The higher initial boiling point of the ITSL distillates probably accounts for much of their greater than expected initiating activity compared to the SRC materials.     

Dependence of coal liquefaction behaviour on coal characteristics. 8. Aspects of the phenomenology of the liquefaction of some coal

Steps are now being taken to define in more detail the phenomenology of coal liquefaction and to provide a scientific basis for empirical correlations previously established between liquefaction conversion and basic compositional characteristics of coals. The rates of production of oils, asphaltenes and preaphaltenes have been determined at four temperatures for three coals, two of Carboniferous and one of Creaceousage. Products are formed more slowly from the younger coal (which is of slightly lower rank) than from the others, but oxygen, partly as OH but probably mostly in a type of ether, is lost more rapidly. It is estimated that the maximum content of O as cleavable ether is 7.7 atoms/100 C atoms for the younger coal (from Wyoming) and 4.1 and 5.1 for the other two (from Oklahoma and Ohio, respectively). Until ≈ 50% of the amount present in the Oklahoma coal is lost, the rates of removal of oxygen and organic sulphur are approximately equal; beyond this level, the removal of S is more rapid. The loss of organic sulphur from the Ohio coal is slightly faster. Even so, the data do not support the idea that cleavage of thioethers is more rapid than that of ethers and that this is the basic reason why a high organic sulphur content tends to promote liquefaction. Conversion of the pyrite in the Ohio coal to pyrrhotite occurs considerably more rapidly than the pyrite in the Oklahoma coal. In preliminary experiments, it is shown that a curve-resolving programme allows two aromatic and five aliphatic C-H stretching vibrations to be distinguished in FTIR spectra of the hexane-insoluble products, and the distribution changes with degree of conversion. In particular, there is evidence that new aryl methyl are generated during liquefaction, in agreement with evidence from oxidation studies.     

煤直接液化技术发展的化学脉络及化学工程挑战

从对煤直接液化的化学本质的分析入手,讨论了煤直接液化技术发展的化学脉络及所面临的化学工程挑战。作者认为,煤直接液化技术的化学本质是煤大分子结构在热场中裂解产生自由基碎片的速率和自由基碎片加氢的速率的匹配,这两个速率的差异决定了煤浆预热、煤液化反应,甚至高温条件下产物分离等过程的特征,决定了油收率、系统中物料结焦、物料输送等行为。     

Simulation of chemical rate processes in short contact time coal liquefaction

Conversions and product distributions from the thermal dissolution of Liddell coal in the presence of tetralin have been simulated by a system of second-order rate equations. Satisfactory correlation with experimental data is obtained over the range of temperatures studied, i.e. 380–420 °C.