Regulation of radicals by hydrogen-donor solvent in direct coal liquefaction

Radicals are important intermediates in direct coal liquefaction. Certain radicals can cause the cleavage of chemical bonds. At high temperatures, radical fragments can be produced by the splitting of large organic molecules, which can break strong chemical bonds through the induction pyrolysis of radicals. The reaction between the formation and annihilation of coal radical fragments and the effect of hydrogen-donor solvents on the radical fragments are discussed in lignite hydrogenolysis. Using the hydroxyl and ether bonds as indicators, the effects of different radicals on the cleavage of chemical bond were investigated employing density functional theory calculations and lignite hydrogenolysis experiments. Results showed that the adjustment of the coal radical fragments could be made by the addition of hydrogen-donor solvents. Results showed that the transition from coal radical fragment to H radical leads to the variation of product distribution. The synergistic mechanism of hydrogen supply and hydrogenolysis of hydrogen-donor solvent was proposed.     

Composition and reactivity of coal from the Khoot deposit in Mongolia

The composition and reactivity characteristics of Khoot coal from Mongolia in the processes of pyrolysis, gasification, thermal dissolution, and the production of porous materials were determined. It was established that the coal is characterized by high activity in the reactions of destruction. In the process of semicoking, the yield of liquid tar was as high as 10%. Highly porous activated carbons with specific surface areas to 900 m²/g and high sorption capacities were obtained by the steam activation of carbonizates. To 60.8% liquid products at low gas formation can be obtained from the Khoot coal in the process of thermal dissolution in a hydrogen-donor solvent at 450°C without the use of hydrogen.     

Co-carbonization of hard coals and coal extracts 2. The co-carbonization of medium- and high-rank coals with extracts

Studies on the influence of anthracene coal extracts on the carbonization process of medium- and high-rank coals were undertaken. Extracts from flame coal (Int. Class. 900) and gas-coking coal (Int. Class. 632) were used as additives. The blends prepared from the examined coals and the extracts exhibited better coking properties than the parent coals. The addition of extract to the coals gave an increase in the microstrength of the resultant cokes. The effects of co-carbonization of coking coals with extracts were increases in the size of the optical texture as well as in the degree of structural ordering of cokes. In the co-carbonization of semicoking coal with addition of coal extracts, a reduction in the size of the anisotropic units and a decrease in the crystallite height of cokes were observed. No modification of the basic anisotropy of coke from anthracite by coal extract was observed. With increasing extract content in anthracite/extract blends there was an increase in the degree of structural ordering of co-carbonization products. Extract addition was unable to modify the behaviour of fusinite. Based on the results of investigation of the influence of coal extracts on the carbonization of different-rank coals, a division of coals according to the modification of the optical texture of coke is given.     

Hydrogenation of brown coal. 3. Roles of hydrogen and hydrogen-donor solvents in systems catalysed by iron and tin compounds

The role of hydrogen and hydrogen-donor solvents in the liquefaction of a Victorian brown coal without added catalyst and in the presence of iron-and tin-based catalysts has been studied. Results of an investigation of the effect of temperature and pressure on the conversion parameters, of independent studies of asphaltene hydrogenation, and of work with model ethers are described. A mechanism is tentatively proposed to describe the role of iron, tin and iron-tin catalyst systems based upon these results.     

Performance indices for coal liquefaction solvents

Most coal liquefaction processes are based on the thermal cleavage of activated bonds giving reactive carbon and oxygen radicals which abstract hydrogen atoms from the donor solvent. The role of oil is approximated in this study by using a simple standard reaction. A series of five representative solvents react with phenyl and phenyloxy radicals generated by thermolysis of benzoyl peroxide at 87 °C in tetrachloroethylene. The n.m.r. analysis of the reacting mixture defines four performance indices, i.e. the hydrogen-donor, the efficiency, the recycle and the scavenger indices, which characterize the ability of these solvents as efficient recycle oils in coal liquefaction processes. 9,10-dihydrophenanthrene proves to be by far the most appropriate solvent for this purpose.     

神华上湾煤恒温阶段直接液化反应动力学

为考察神华上湾煤的直接液化性能及反应动力学,以加氢蒽油-洗油混合油作为溶剂、负载型FeOOH作为催化剂,在0.01 t·d^-1煤直接液化连续实验装置上考察了不同反应温度（435~465℃）、不同停留时间（7~110 min）下液化产品组成的演变规律。研究发现,随着煤的裂解及加氢反应的进行,煤及沥青类物质（PAA）收率不断减小,重质液化产物逐步向轻质液化产物转化。当反应温度为455℃、停留时间为90 min时,煤转化率为90.41%（质量分数（,油收率为61.28%（质量分数（。随着反应条件进一步苛刻,油收率下降。基于上湾煤直接液化反应特性及其产物收率变化规律建立了11集总煤直接液化反应动力学候选模型,以BFGS优化算法对实验数据搜索、选优,确定了动力学模型参数。检验结果表明所建立的动力学模型可用于恒温阶段直接液化行为的模拟计算。     

高碱低阶煤热解及热解半焦研究进展

我国碱金属、碱土金属(AAEM)含量高的低阶煤储量丰富。高碱含量造成锅炉受热面结渣沾污及气化炉结块腐蚀等难题,低阶煤内水高、氧含量高、挥发分高、发热量低以及易氧化自燃等特性为其储、运、用带来极大的难题。热解可生产优质燃料和高附加值化工原料,也是燃烧、气化、直接液化等过程的起始阶段和/或伴随反应,煤在热解阶段发生的反应、经历的变化,对煤转化利用的效率和清洁程度起重要、甚至决定性作用。笔者对煤热解与热解半焦研究及进展进行综述性评价,着重探讨煤中AAEM对热解过程及半焦的影响。结果表明,热解研究装置模拟的工况与现代煤化工过程中煤热解所处环境相差甚远,半焦样的代表性不强使热解研究成果的指导意义不大;对煤中不同赋存形态AAEM的分离方法有待完善,还需筛选、尝试新的萃取试剂;基本掌握了煤热解过程中AAEM的变迁行为,但尚缺乏控制煤中AAEM危害的有效方法。高碱低阶煤的安全高效洁净转化利用技术仍待突破。     

低阶煤预处理技术的研究进展

简述了低阶煤的利用现状及热转换过程中存在的问题,总结了水热预处理、酸预处理、溶剂溶胀、热预处理、氧烷基化及加氢预处理等预处理技术对低阶煤的结构、热解反应性和焦油品质及收率的影响。提出了合适的预处理技术可以降低煤的液化条件,提高煤的热转换效率,改善焦油品质,实现低阶煤的清洁高效利用。     

Upgrading of low rank coal with solvent

In this study, thermal upgrading of low-rank coal with solvent at 380–440 °C under an initial nitrogen pressure of 2 MPa was studied as a possible method for producing clean solid fuel with a high heating value and less spontaneous ignition behavior. Upgrading of Buckskin coal (USA, subbituminous coal) in the presence of t-decalin (non hydrogen-donor solvent) at 440 °C gave 11.4 wt.% of gas, 5.3 wt.% of oil and 74.1 wt.% of upgraded solid product with a small amount of water. The gaseous product consisted mainly of carbon dioxide (67 wt.%), methane, carbon monoxide, hydrogen and a trace of C₂ and C₃ hydrocarbon gases. The oil product from coal contained BTX, phenol, and their alkyl-derivatives. The heating value of the upgraded solid product from the Buckskin coal increased to 31.0 MJ/kg in dry base as compared to the heating value of wet base of the untreated raw coal, which was 19.3 MJ/kg. Spontaneous ignition behavior was greatly reduced by the upgrading. The effect of catalyst and additives on the upgrading was investigated in terms of product distribution and the quality of the solid product. Taiheiyo (Japan, subbituminous) and Yallourn (Australia, brown) coals were also studied.     

Pyrolysis of coal liquids

The pyrolysis of process recycle solvent derived from Western Kentucky coal via the SRC-II coal liquefaction process was investigated to ascertain the effect of residence time and temperature on the production of olefins. The study was made using an alonized transfer line reactor operating at temperatures of 650 and 730 °C, essentially atmospheric pressure, and residence times up to 0.13 s. A comparison is made with previously published results for the pyrolysis of hydrotreated COED light and heavy coal liquids (subsequently referred to as COED light and heavy oils, respectively) derived from Western Kentucky coal and steam pyrolysis of a hydrogenated fraction of SYNTHOIL derived from Western Kentucky coal. Results indicate that in each case the preferential pyrolysis of the saturate fraction occurs under convential pyrolysis conditions. Ethylene, propylene, and methane were the dominant gas products in all cases. The liquid pyrolysates from the COED oils and SRC-II recycle solvent had lower $\text{H}\text{C}$ ratios and heating values than their respective feedstocks. Mass spectroscopic analysis of the liquid pyrolysates in each case revealed the presence of polycyclic aromatics that were not present in the individual feedstocks. This trend which increased with temperature is indicative of cyclization and/or recombination of free radicals during pyrolysis. It is therefore surmized that the yields of light olefins from primary coal liquefaction products can be improved by partially hydrogenating them prior to pyrolysis. Alternatively, sufficient hydrogen can be provided in the vicinity of cracking to suppress retrogressive reactions which lead to the formation of coke. The pyrolysis of COED oils and SRC-II recycle solvent was found to follow first-order irreversible kinetics. The activation energy for the pyrolysis of the COED light and heavy oil was found to be 76.1 and 70.85 kJ g-mol^?1, respectively.     

铁镍复合助剂对煤热解过程中氮迁移规律的影响

为了减少煤炭燃烧过程中NO_x的排放,在管式炉中进行了煤与金属助剂（FeCl₃、NiCl₂）的热解实验,研究了助剂负载量、热解温度、助剂添加方式对氮迁移及N₂产率的影响并且对复合助剂作用机理进行了探讨。结果表明：随着助剂负载量的增加,氮脱除率及N₂产率呈现先增加后趋于稳定的趋势,且负载量以0.8%Fe复合1.0%Ni为最佳。在700~1000℃的热解温度范围内氮脱除率及N₂产率随热解温度的增加而增加。对煤进行溶胀处理添加复合助剂后,氮脱除率及N₂产率要优于未经处理的煤样。铁基助剂与镍基助剂在催化煤热解氮迁移过程中形成互补,铁基助剂的添加增加了镍基助剂的活性,弥补了单助剂的劣势,且复合助剂相比于单助剂有更强的氮脱除效果并且N₂产率达到最高39%。铁镍复合助剂对煤中N-5转化为N₂的催化效果更加明显,因为复合助剂对吡咯的内氢转移和开环有更强的催化作用。本研究能够为煤炭洁净化利用提供理论和实验依据。     

煤直接液化残渣的性质及利用现状

为了高效地利用煤直接液化残渣,从液化残渣的组成、结构特性、热解特性、溶解特性4个方面论述了液化残渣的物理化学性质的研究现状。研究发现:残渣在组成和结构特性上都保留了原煤的部分特性。在对直接液化残渣热解特性的研究中,论述了各种不同研究手段,例如热重分析仪、实验室移动床、小型焦炉、高压釜等对液化残渣的热解过程的研究进展及热解机理的解析现状。在对液化残渣的溶解性进行研究时,讨论了残渣溶解性研究的意义及其在各种溶剂中表现出的不同特征。最后论述了煤直接液化残渣的利用研究现状、分析了其潜在的高附加值利用方式、发展前景和存在的问题。     

Effects of solvent pretreatment and solvent incorporation on coal liquefaction

Yields of short-contact-time liquefaction product can be increased by pretreating the coal-solvent slurry at below normal liquefaction temperatures to permit solvent incorporation and/or swelling of the coal before liquefaction. An external pretreatment and an in situ pretreatment produce similar results. A coal-vehicle adduct was isolated from the pretreated coal and had liquefaction characteristics similar to the original coal. The beneficial effect of the solvent pretreatment is therefore believed to be the result of physical solvent incorporation with the coal, which causes solvent-aided liquefaction, in contrast with the thermal decomposition that can occur if some of the coal reaches liquefaction temperatures before it is contacted by vehicle. Pretreatment allows vehicle to be present (in contact with coal) at the reactive site in order to react with, and cap, coal free radicals.     

贫煤与煤沥青共炭化研究

进行了不同配比的煤沥青和贫煤的共炭化研究,研究表明,煤沥青与贫煤共炭化时的相互作用是物理融合和化学相互作用的共同作用。其中物理融合表现在使焦炭界面结合状态改善,化学相互作用表现在煤沥青使贫煤的炭化性能发生变化。随煤沥青配比的增加,配煤黏结性有较大改善,焦炭OTI值增大,ISO值减小。煤沥青通过增大焦炭光学组织各向异性程度,使焦炭的反应性降低,反应后强度提高。     

An update of german non-isothermal coal pyrolysis work

Pyrolysis is an essential and inseparable process in all aspects of coal conversion and utilization, the most common product of coal pyrolysis being coke. It is part of combustion and plays an important role in coal gasification and liquefaction. Over the last fifteen years Bergbau-Forschung GmbH has sponsored research in the basic processes and fundamentals of pyrolysis to optimize the properties and/or yield of the coke, gas and liquids produced. The work is summarized and the theoretical framework used for the analysis is described. Results with heating rates from degrees per day to degrees per micro second in inert and reactive gases are presented. Emphasis is placed on the kinetics of gas formation. Further work in the area of pressurized pyrolysis is planned.     

煤与各种添加物共碳化的研究进展

综述了近年来世界各国钢铁公司焦化厂和实验室中煤与各种添加物如石油焦、石油沥青、煤焦油沥青、加氢残渣等共碳化炼焦技术的进展,指出煤与各种添加物的共碳化技术是有效节约炼焦煤资源、降低炼焦成本和提高焦炭质量的一种有效手段。     

Development of anisotropic texture in co-carbonization of low rank coal with pitch-evaluation from hydrogen donor and acceptor abilities of coal and pitch

The extent of development of anisotropic texture in cokes prepared from various coals or blended coals in co-carbonization systems was assessed by using the ratio of hydrogen donor ability to acceptor ability. A parameter D/A, corresponding to the amount of hydrogen transfer during carbonization in the system of blended coal and pitch additive has been proposed to give a measure of the aforesaid development of anisotropic texture in resultant cokes. In pitch A/non-caking coal systems, blending the pitch A with coal to a value of D/A − 0.22, D/A − 0.28 and D/A − 0.40 gives mainly fine-granted mosaics, medium-grained mosaics and coarse-grained mosaics, respectively. The Gieseler plastometry and high-temperature ¹H-NMR were also used to obtain informations about the mobility of the co-carbonization system. A good relation was found between D/A, and the solidification temperature determined by the Gieseler plastometry.Such an approach based on the concept of D/A parameter provides a guideline for selecting pitch as a modifier for low rank coal carbonization.     

矿物质对煤中硫氮在热解气化过程中迁移变化的催化作用

从煤自身所含的矿物质和外加添加剂的观点出发,对煤热解、气化和燃烧过程中存在的催化作用进行了阐述,尤其是煤中N、S有害元素的催化转化作用。煤自身所含的矿物质及部分碱金属、碱土金属和过渡金属添加剂对煤热解、气化和燃烧过程具有一定的催化能力,同时对煤中N、S有害元素的转化也有明显作用。对具有单功能催化作用的金属催化剂进行合理组合、适当改性和优化添加方式,在NOx和SOx污染性气体形成前对其前驱体进行抑制和定向转化,是今后煤炭洁净转化的一个研究方向。     

Carbonization properties of hydrogenated aromatic hydrocarbons—III: Modifying activities of hydrogenated pryene and its oxidized derivatives in the co-carbonization of coals and coal liquids

The modifying activities of hydrogenated pyrene (HP) and its oxidized derivatives were examined in co-carbonization with solvent refined coal, solvent treated coal, a fusible and a non-fusible coal. The present additives all showed a significant activity, with HP oxidized at 150°C exhibiting the highest activity. The activity of the additive is discussed from its structural indices and coke yield in relation to its dissolving and hydrogen donating abilities. The modifying susceptivility of the carbonizing substance is rated in the order described above, being correlated with its single carbonization properties, such as fusibility and potential for anisotropic development. A consecutive treatment of partial hydrogenation and oxidation is emphasized as a useful technique for producing active additive and an excellent coking substance from the pitch material.     

Approach for promoting liquid yield in direct liquefaction of Shenhua coal

Single and multi-stage liquefaction of Shenhua (SH) bituminous coal and re-liquefaction of its liquefaction residue (SHLR) were carried out in an autoclave reactor to investigate the essential approach for promoting oil yield and conversion in SH coal direct liquefaction (SHDL). The multi-stage liquefaction includes pretreatment, keeping the reactor at 250 °C for 40 min before heating up to the reaction temperature, and two-stage liquefaction processes consisting of low temperature stage, 400 °C, and high temperature stage, 460 °C. The results show that the pretreatment has slight effect on oil yield and conversion of SHDL, especially for liquefaction at 460 °C. There is a positive function of two-stage liquefaction in shortening reaction time at high temperature. Increasing ratio of solvent to SHLR can promote the oil yield and abate reaction condition in SHLR re-liquefaction, that is, it can promote the conversion from preasphaltene and asphaltene to oil. The primary factor to inhibit coal liquefaction is the consumption of hydrogen free radical (H·) from solvent or H₂ and condensation of free radicals from coal pyrolysis after a period of reaction. So the essential approach for increasing oil yield and conversion of SHDL is to provide enough H· to stabilize the free radicals from coal pyrolysis.