Hydrogenation of the inertinite macerals of Bayswater coal

Yields of products from the hydrogenation of the inertinite and vitrinite+exinite macerals of the Bayswater (New South Wales, Australia) coal in a batch autoclave were investigated. Samples were hydrogenated for 1 h at 400 and 450 °C with tetralin as vehicle, hydrogen as charge gas and no added catalyst. The results show that the inertinite macerals contributed significantly to the liquid hydrogenation products, in particular to the oil yield obtained at 450 °C.     

Reaction kinetics of d-xylose in sub- and supercritical water

Reactions of d-xylose were investigated with a flow apparatus in water at high temperatures (350 and 400 °C) and high pressures (40-100 MPa) to elucidate the reaction pathway and reaction kinetics. The products obtained from the reaction of d-xylose were furfural, d-xylulose, glyceraldehyde, glycolaldehyde, dihydroxyacetone, pyruvaldehyde, lactic acid and formaldehyde. Experimental results showed evidence of a dehydration reaction pathway, a retro-aldol reaction pathway and a Lobry de Bruyn-Alberta van Ekenstein (LBET) pathway from d-xylulose. The proposed reaction pathway and kinetic model were in accord with the experimental results. The kinetic constants showed dependence with water density (pressure). At 400 °C and water density of 0.52 g/cm³ at 40 MPa, the reaction from d-xylose to d-xylulose occurred by the LBET pathway with the reverse reaction being negligible. At 400 °C, increasing the water density from 0.52 to 0.69 g/cm³ decreased the kinetic rate constant of the forward LBET pathway and increased that of the reverse LBET pathway. The kinetic rate constant of the dehydration of d-xylulose to furfural increased with increasing water density at constant temperature. The kinetic rate constant of the retro-aldol reaction of d-xylose increased, and the retro-aldol reaction of d-xylulose decreased with increasing water density at 400 °C.     

Catalytic hydrocracking of primary maceral concentrate extracts prepared in a flowing solvent reactor

Differences between the behaviour of coal macerals during liquefaction and catalytic hydrocracking were investigated. The liquefaction experiments were carried out in tetralin, using a flowing solvent reactor. The extracts were catalytically hydrocracked in a micro-bomb reactor, using a commercial catalyst. Extracts and hydrocracked products were characterised by size exclusion chromatography (SEC), UV-fluorescence spectroscopy (UV-F), probe-mass spectrometry and thermogravimetric analysis. Conversions of the vitrinite and the liptinite concentrates during liquefaction were high (∼89%), while inertinite samples yielded a little over 20% extract. For inertinites, the emerging picture was consistent with high cross-link density. Liptinite was extracted less completely at lower temperatures and more slowly at high temperatures compared to corresponding vitrinites and vitrinitic coals. Long chain aliphatics released from the liptinite concentrate between 340 and 390°C appeared likely to have originated in lower-molecular mass material occluded in the sample matrix and dissolving in tetralin prior to the onset of massive covalent bond scission. SEC chromatograms showed material of larger MMs in liptinite and vitrinite extracts than in the inertinite extract. The molecular mass distributions broadened with increasing extraction temperature. Catalytic hydrocracking experiments were carried out in a micro-bomb reactor for 10 and 120 min at 440°C, under 190 bar of hydrogen. In hydrocracking, the liptinite was the slowest extract to react at short reaction times (∼10 min). However, at longer reaction times, its products showed the smallest MM-distribution. Smaller differences were observed between the chromatograms of the 10 and 120 min hydrocracked products of the inertinite extract. Differences between spectra of the three extracts would strongly suggest the presence of larger (and apparently irreducible) polycyclic aromatic ring systems, in the hydrocracked products of the inertinite extract.     

Model for the coal hydrogenation process and its applications

A coal hydrogenation model has been formulated which incorporates both chemical and microscopic experimental data. In this generalized model, carbonization and hydrogenation are viewed as concurrent processes in the liquefaction of coal. Insufficient hydrogen availability, rapid heating rates and long reaction times at elevated temperatures can promote carbonization reactions. The model describes in detail the reaction pathways involved in the hydrogenation of both inertinite and vitrinite. When vitrinite is hydrogenated in the presence of a hydrogen donor solvent, a plastic material called vitroplast is formed. The vitroplast is either converted to liquid and gaseous products when hydrogen availability is high or becomes mesophase and then semicoke when hydrogen availability is low. Even under favourable hydrogenation conditions, the major reaction pathway in the hydrogenation of inertinite is one of initial mild carbonization followed by hydrogenation. It is evident that the difference in hydrogenation behaviour between vitrinite and inertinite is due, in part, to the ability of the hydrogen donor solvent to penetrate vitrinite but not inertinite particles. The hydrogenation model is useful for explaining various phenomena that occur during hydrogenation, such as the formation of mesophase and semicoke, and the blockage of reactors and preheaters.     

煤中显微组分液化反应性研究进展

煤炭液化是目前可大规模采用的缓解我国石油资源供应紧张的有效方法.综述了国内外关于煤岩显微组分液化特性和机理的研究现状,讨论了显微组分性质对液化反应性的影响,提出了今后深化研究的方向,认为低煤级煤中惰质组的转化率和油收率不可忽视,只是反应条件与其他显微组分并不一致,且影响惰质组反应性的因素较为复杂.所以建议,不同显微组分的最佳液化条件与差异、煤中活性显微组分与惰性成分在液化过程中的相互关系、显微组分在液化反应过程中的协同效应及其表征等是值得今后深化研究的方向.     

Pyrolysis behavior of vitrinite and inertinite from Chinese Pingshuo coal by TG-MS and in a fixed bed reactor

The pyrolysis behaviors of vitrinite and inertinite from Chinese Pingshuo coal were investigated by using the thermogravimetry coupled with mass spectrometry (TG-MS) and in a fixed bed reactor, respectively. The results showed that inertinite has lower pyrolysis reactivity, lower tar and gas yields, but higher water yield than vitrinite. At 650 °C, the tar and gas yield of vitrinite is 22.4% and 14.4%, respectively, obviously higher than 13.4% and 10.2% of inertinite. The TG-MS analysis also showed much difference of vitrinite and inertinite in gas evolution profile. The ultimate and XRD analyses of chars indicated that the difference in element composition of vitrinite char and inertinite char decreases with the increase of temperature, and have similar element composition and structure characteristic at 650 °C. The total sulfur removal of both vitrinite and inertinite increases with the pyrolysis temperature, and reaches to 60% at 650 °C, but the organic sulfur in inertinite seems more stable than that in vitrinite.     

Microscopic observations of the swelling of a high-volatile bituminous coal in response to organic solvent

The swelling behaviour of individual coal macerals in response to solvents is thought to be important since it represents an early stage in the disintegration of the coal, which is, in turn, of fundamental importance to coal hydrogenation at elevated temperatures. Therefore, a detailed incident-light microscope study of solvent-treated, polished coal surfaces, involving a new edge-on mode of observation, was undertaken in order to observe the way in which solvents interact with the different coal macerals. This study was carried out on blocks of Bayswater Seam coal, using tetralin, pyridine, and 1:3 maleic anhydride-xylene solutions at temperatures near their respective boiling points. The degree of swelling of the polished coal surface depends on the nature of the organic solvent and the individual coal macerals. Vitrinite and, in some instances, low-reflectance semifusinite exhibit varying degrees of swelling in response to the solvent treatment; whereas exinite and the majority of the inertinite macerals appear to be unaffected by the solvents. Within the vitrinite group the lower-reflectance sub-macerals exhibit the greater degree of swelling. At temperatures of less than 200 °C the ability of the solvents to produce swelling in the coal decreases in the order pyridine → 1:3 maleic anhydride-xylene → tetralin.     

Enantioselective hydrogenation of trifluoroacetophenone over cinchonidine-modified platinum

The enantioselective hydrogenation of 2,2,2-trifluoroacetophenone to (R)-1-phenyl-2,2,2-trifluoroethanol represents a new application of supported Pt catalysts modified with cinchona alkaloids. Heat treatment of a 5 wt% Pt/alumina catalyst at 400°C in flowing hydrogen, followed by an air-treatment of the reaction mixture before the hydrogenation reaction improved the enantiomeric excess by a factor of 2.5. Traces of water in apolar medium, high trifluoroacetophenone and moderate cinchonidine concentrations were also advantageous for enantiodifferentiation. Both reaction rate and enantiomeric excess increased during the initial transient period of the reaction, below 10% conversion.     

Coal microlithotype response to froth flotation in selected Western Kentucky coals

Seven coals representing four western Kentucky coal seams and the coal rank range from high volatile C to high volatile A bituminous were selected for bench-scale froth flotation processing. Each coal was represented by two splits of the run-of-mine coal: a 12.7 mm × 0 fraction (crushed to 28 mesh × 0) and a 28 mesh × 0 fraction. The original 28 mesh × 0 split was found to be higher in the inertinite macerals fusinite and semifusinite than the coarser fraction. The separation of the inertinite macerals, expressed as the microlithotype inertite, from the vitrinite-rich vitrite and clarite microlithotypes proved to be markedly rank dependent. In the higher rank coals vitrite and clarite were concentrated in the clean coal while inertite was concentrated in the clean product in the high volatile C coals. Whereas in gravity-based coal cleaning only the finest pyrite usually remains in the clean coal, in this study no consistent trend in pyrite-size or pyrite-quantity partitioning was noted.     

Continuous synthesis of metal nanoparticles in supercritical methanol

Metal nanoparticles were synthesized continuously in supercritical methanol (scMeOH) without using reducing agents at a pressure of 30 MPa and at various reaction temperatures ranging 150-400 °C. Wide angle X-ray diffraction (WAXD) analysis revealed that metallic nickel (Ni) nanoparticles were synthesized at a reaction temperature of 400 °C while mixtures of nickel hydroxide (α-Ni(OH)₂) and metallic Ni were produced at lower reaction temperatures of 250-350 °C. In contrast, metallic silver (Ag) nanoparticles were produced at reaction temperatures above 150 °C while metallic cupper (Cu) nanoparticles were produced at reaction temperatures above 300 °C. Mixtures of copper oxide (CuO and Cu₂O) and metallic Cu were produced at lower reaction temperatures of 250 °C. Scanning electron microscopy (SEM) showed that the particles size and morphology changed drastically as the reaction temperature increased. The average diameters of Ni, Cu and Ag particles synthesized at 400 °C were 119 ± 19 nm, 240 ± 44 nm, and 148 ± 32 nm, respectively. The scMeOH acted both as a reaction medium and a reducing agent. A possible reduction mechanism in scMeOH is also presented.     

Coal flash pyrolysis: 4. Polymethylene moieties in coal macerals

An analysis for polymethylene moieties in purified coal macerals has shown the (CH₂)_n (wheren?5) content, by a liquefaction—¹ H n.m.r. method, to be highest in exinite macerals and lower in vitrinite and inertinite macerals. From any particular coal, the (CH₂)_n content of the vitrinite was higher than the inertinite but lower than the exinite. Pyrolysis of these macerals gave ethylene yields proportional to the (CH₂)_n content.     

The random pore model with intraparticle diffusion for the description of combustion of char particles derived from mineral- and inertinite rich coal

An investigation was undertaken to determine the applicability of the random pore model with intraparticle diffusion for the determination of the reaction kinetics for the combustion of chars particles derived from coals rich in minerals and inertinites. The char particles which were pyrolysed at 900 °C consisted of a dense carbon-containing fraction originating from the inert macerals (mainly inertinites), a high concentration of minerals and carbominerites, pores generated by the devolatilisation of the reactive macerals and cracks as a result of the presence of minerals. Combustion experimentation was carried out with a thermogravimetric analyser using 1 mm particles with 20% (mole) oxygen in nitrogen at 287.5 kPa and low temperatures (450-600 °C) and with high gas flow rates. The random pore model with intraparticle diffusion (pores and cracks) was solved numerically according to a method consisting of a step-wise regression procedure. This was achieved by using carbon conversion and reduced time relationships to calculate the structural parameter and the initial Thiele modulus followed by determination of an initial lumped reaction rate and validation with conversion versus real time results. The model is characterised by a decreasing Thiele modulus (increasing porosity) occurring during the reaction period which gives rise to a transition to a chemically controlled reaction system. It was found that the initial overall reaction rate was controlled by intraparticle diffusion with an increasing influence with increasing temperature.     

Highly active and selective Cu/SiO2 catalysts prepared by the urea hydrolysis method in dimethyl oxalate hydrogenation

Cu/SiO₂ catalysts have been successfully prepared via urea hydrolysis method. The catalysts have been systematically characterized by X-ray diffraction, high-resolution transmission electron microscopy, N₂-physisorption and H₂ temperature-programmed reduction. The results demonstrated the presence of copper nanoparticles and their high dispersion on the SiO₂ support. Catalysts with different copper loadings were prepared, and their performances in the hydrogenation of dimethyl oxalate to ethylene glycol were studied. A 100% conversion of dimethyl oxalate and maximum 98% selectivity of ethylene glycol were reached with 15.6 wt.% copper loading at 200 °C and 2 MPa. Furthermore, under the same reaction conditions, the catalyst can maintain the selectivity of 90% when the reduction temperature reduced from 350 °C to 200 °C. The high activity and selectivity over the catalyst may be ascribed to the homogenously distribution of copper nanoparticles on the large surface.     

States of surface hydrogen under reaction conditions of the Fischer-Tropsch synthesis

The reaction of hydrogen with Fe surfaces was observed by the ellipsometric method at 77 K to 500 ° C under H₂ pressures of 10^–3 Torr (0.1 Pa) to 500 Torr (7×10⁴ Pa). The ellipsometric analysis reveals no existence of adsorbed hydrogen on the surface above 400 °C; hydrogen seems to be alternatively absorbed into the subsurface region of two to three atomic layers. It is concluded that the subsurface hydrogen is specific to the high temperature and the high pressure owing to strained and roughened Fe surfaces as well as the equilibrium with gas phase hydrogen. Absence of adsorbed hydrogen is indicated as well in the ellipsometric response to the hydrogenation reaction of surface carbon species on Fe surfaces.     

Micrinite and exudatinite in some Australian coals,and their relation to the generation of petroleum

The occurrence and microscopic features of micrinite and exudatinite in some Australian coals are reported. The origin of these macerals and also the significance of their occurrence are discussed in connection with hydrocarbon genesis. In Australia, micrinite occurs in bituminous and sub-bituminous coals which are very rich in inertinite, and also in brown coal rich in inertinite. One of the possible progenitors of micrinite is oxidized porigelinite. There is little reason to conclude that micrinite was formed from resinite and other macerals at an early stage of coalification and that liquid hydrocarbons were formed during this process. Exudatinite occurs in sub-bituminous and high-volatile bituminous coals in the Gippsland Basin. There is no positive evidence of a genetic relation between liquid hydrocarbons, exudatinite, micrinite and liptinite macerals. The formation of liquid hydrocarbons from solid liptinite etc. may take place just before and during Teichmüller's so-called ‘2nd coalification jump’.     

Reaction Coupling of Ethylbenzene Dehydrogenation with Nitrobenzene Hydrogenation

The chemical equilibrium for the coupling of ethylbenzene dehydrogenation with nitrobenzene hydrogenation, to produce styrene and aniline simultaneously, has been calculated on the basis of the Soave–Redlich–Kwong equation of state. The dehydrogenation of ethylbenzene in the presence of nitrobenzene over the catalysts -Al₂O₃, ZSM-5, activated carbon and platinum supported on activated carbon has been carried out at 400 °C. The effects of Pt loading and the pretreatment of the catalysts have been investigated. It has been revealed that the conversion of ethylbenzene can be greatly improved by the reaction coupling due to the elimination of the hydrogen produced in the reaction by the hydrogenation of nitrobenzene. Platinum supported on the activated carbon has been suggested as a suitable catalyst. The best results with ethylbenzene conversion of 33.8% and styrene selectivity of 99.2% were obtained over Pt(0.02 wt%)/AC at 400 °C. Moreover, such process is also energetically favored since the necessary process heat to drive the ethylbenzene dehydrogenation can be provided by the coupling with the exothermic nitrobenzene hydrogenation reaction.     

The variation of structural characteristics of macerals during pyrolysis

Vitrinite and inertinite were separated by DGC from Chinese Shenmu bituminous coal and the structural characteristics of the macerals, before and after pyrolysis, were analyzed by ultimate analysis, FTIR and ¹³C NMR. The results showed that vitrinite chars always had higher H and lower C content than inertinite char at the same pyrolysis temperature. The FTIR and ¹³C NMR indicated that vitrinite had more aliphatic C-H, hydrogen bonding and lower aromaticity. With increasing temperature, the aliphatic C-H decreased, aromatic C-H, aromaticity and H_ar/H_al ratio increased. At the same temperature, inertinite always had higher H_ar/H_al ratio than vitrinite, which is consistent with that inertinite had higher aromaticity than vitrinite. And the H_ar/H_al ratio was also related to the remainder volatile matter. With increasing H_ar/H_al ratio, the remainder volatile matter in vitrinite and inertinite decreased. The higher aromaticity and H_ar/H_al ratio and lower H content of the inertinite in all temperature range were correlated with its higher thermal stability and lower volatile yield than vitrinite.     

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.     

Mechanism of the Direct Hydrodenitrogenation of Naphthylamine on Sulfided NiMo/Al2O3

The hydrodenitrogenation of 1-naphthylamine was studied over a sulfided NiMo/Al₂O₃ catalyst between 300 and 350 °C. 1-Naphthylamine reacted to tetralin, naphthalene, 1,2-dihydronaphthalene and 5,6,7,8-tetrahydro-1-naphthylamine. To elucidate the reaction mechanism, the reactions of the intermediates 1,2,3,4-tetrahydro-1-naphthylamine, 1,2-dihydronaphthalene and 5,6,7,8-tetrahydro-1-naphthylamine were studied as well. The results show that 1-naphthylamine reacts through hydrogenation to 1,2,3,4-tetrahydro-1-naphthylamine, which reacts by NH₃ elimination to 1,2-dihydronaphthalene. The latter molecule subsequently reacts by hydrogenation to tetralin as well as by dehydrogenation to naphthalene. In addition, naphthalene is formed by direct denitrogenation from 1-naphthylamine. This direct denitrogenation may take place by hydrogenation of 1-naphthylamine to 1,2-dihydro-1-naphthylamine, followed by NH₃ elimination or followed by a Bucherer-type NH₂–SH exchange, dehydrogenation and C–S bond hydrogenolysis.     

宁夏庆华煤镜质组和惰质组显微组分的分子结构及对比分析

使用密度梯度离心法对宁夏庆华煤的显微组分进行分离,获得煤的镜质组和惰质组。通过元素分析、X射线光电子能谱（XPS）、固体¹³C核磁共振（¹³C NMR）技术、傅里叶变换红外光谱（FTIR）和X射线衍射（XRD）技术等表征手段对不同显微组分进行物性表征。进一步基于统计平均的分子结构近似结合分子模拟计算,确定庆华煤镜质组和惰质组显微组分的分子结构可分别表示为C₂₆₉H₁₉₆N₄O₁₃S和C₂₅₅H₁₇₉N₃O₁₄S。通过FTIR光谱与¹³C NMR光谱验证,从而实现了不同显微组分的分子结构描述。对两种显微组分的分子模型和结构参数进行了系统对比分析,发现镜质组的芳碳百分数为51.95,惰质组的芳碳百分数为62.16。镜质组模型中芳碳结构数目较少,脂肪碳结构丰富,不饱和度较小,还原度最大。惰质组模型中芳碳结构数量最大,脂肪碳结构数目少,不饱和度最大,煤化程度高。镜质组在原煤中含量高,是原煤的主要组成。惰质组的含量少且大分子结构缩合度高,分布在镜质组构成的基体中。