The characterization of asphaltenes and preasphaltenes obtained under various coal liquefaction conditions

A CP-MAS ¹³C NMR study of asphaltenes and preasphaltenes obtained under various coal liquefaction conditions is reported. The carbon aromaticity, f_a, of the solid extracts from the reaction products has a close relation with the reaction conditions. By plotting f_a against the atomatic $\text{H}\text{C}$ ratio for these solid products on the characterization chart for model polycyclic aromatic compounds, the molecular structures with relation to the liquefaction pathway from coal to oil can be proposed.     

Flash pyrolysis of coals: comparison of results from 1 g h−1 and 20 kg h−1 reactors

The performances of 1 g h^?1 and 20 kg h^?1 flash pyrolysers are compared for three Australian coals: Loy Yang brown coal (Victoria), Liddell bituminous coal (New South Wales), and Millmerran sub-bituminous coal (Queensland). The two reactors gave comparable yields of tar, char and C₁–C₃ hydrocarbon gases over a range of operating conditions for each particular coal. The yield of total volatile matter from Millmerran coal was similar from both reactors, as were the compositions of chars from Loy Yang coal and tars from the Liddell and Millmerran coals. For Millmerran coal, the yields of tar, C₁–C₃ gases and volatiles from the large reactor below 650 °C, were slightly lower than for the small reactor, possibly owing to a shorter retention time of Millmerran coal particles in the large-scale reactor. At a temperature near 600 °C tar yields were independent of tar concentration in the effluent gas, over a range 0.0025–0.1 kg m^?3 for Liddell coal, 0.005–0.26 kg m^?3 for Millmerran coal and 0.0045–0.09 kg m^?3 for Loy Yang coal. The tar yields from Millmerran and Liddell coals at 600 °C in the large reactor, correlate directly with the atomic $\text{H}\text{C}$ ratio of the parent coal, in the same manner as that found for a wider range of bituminous coals in the small-scale reactor.     

Flash pyrolysis of coals: behaviour of three coals in a 20 kg h−1 fluidized-bed pyrolyser

Flash pyrolysis of Loy Yang brown coal, and Liddell and Millmerran bituminous coals has been studied using a fluidized-bed reactor with a nominal throughput of 20 kg h^?1. The apparatus and its performance are described. The yields of tar and hydrocarbon gases are reported for each coal in relation to pyrolysis temperature, as also are analytical data on the pyrolysis products. The peak tar yields for the dry, ash-free Loy Yang and Millmerran coals were respectively 23% wt/wt (at ≈ 580 °C) and 35% wt/wt (at $\text{\$}\text{?}$600 °C). The tar yield from Liddell coal was 31% wt/wt at ≈ 580 °C. Hydro-carbon gases were produced in notable quantities during flash pyrolysis; e.g. Millmerran coal at 810 °C gave 6% wt/wt (daf) methane, 0.9% wt/wt ethane, 6% wt/wt ethylene, and 2.5% wt/wt propylene. The atomic $\text{H}\text{C}$ ratios and the absolute levels of hydrogen in product tars and chars decreased steadily with increasing pyrolysis temperature.     

Constitution of tars from the flash pyrolysis of Australian coals: 2. Structural study of Millmerran coal-tar resins by hydrogenolysis

The structures of the acid, base, polyfunctional and neutral resin fractions of Millmerran coal tar have been studied by high-pressure catalytic hydrogenolysis followed by g.c.-m.s. analysis of the volatile products. n-Alkanes from C₉ to C₃₂ constitute 4–24% of the organic products. Each fraction shows a characteristic n-alkane distribution. The alkanes are considered to be an integral part of the coal-tar resin structure. The results show that 40–70% of the coal-tar resin fractions consist of 1- or 2-ring aromatic units substituted or linked by long methylene chains.     

Definition of fossil fuel-derived asphaltenes in terms of average structural properties

Molecular mass and polarity alone do not adequately explain the benzene solubility of all fossil fuel-derived asphaltenes. To account for the solubilities of a wide selection of asphaltenes in terms of average structural properties, it has been necessary to consider also the nature of the aromatic structures by deducing the proportion of internal (bridgehead) aromatic carbon to total carbon ($\text{C}{}_{\mathrm{INT}}\text{C}$). This takes account of both the amount and degree of condensation of aromatic nuclei. Three-dimensional plots of number average molecular mass, the % acidic OH (measure of polarity) and $\text{C}{}_{\mathrm{INT}}\text{C}$ give boundaries between benzene insolubles, asphaltenes and n-pentane solubles. An empirical solubility parameter has been defined which gives values for asphaltenes in the range 0.85-1.2, compared with ? 0.6 for n-pentane solubles and ? 1.25 for benzene insolubles.     

Internal rearrangement of hydrogen during heating of coals with phenol

Heating either Bruceton or Wyodak coal with phenol results in the thermal depolymerization of the coal yielding pyridine-soluble products and an insoluble residue. The depolymerization is accompanied by extensive rearrangements of hydrogen within the coals producing a soluble material enriched in hydrogen and a residue which is hydrogen poor. The hydrogen shuttle in Wyodak coal has a different temperature dependence than does the depolymerization, being favoured at higher temperatures. The $\text{H}\text{C}$ ratio of the soluble products increased with increasing conversion. Relatively small amounts (ca. 5%) of the products at high conversion are derived from phenol.     

Comparison of the chemical structure of coal hydrogenation products,athabasca tar sand bitumen and Green River shale oil

Coal hydrogenation products, Athabasca tar sand bitumen, and Green River shale oil produced by retorting were analyzed by the Brown—Ladner method and the Takeya et al. method on the basis of elemental analysis and ¹H-NMR data, by ¹³C-NMR spectroscopy and by FT-IR spectroscopy. Structural characteristics were compared.The results show that the chemical structure of oils from Green River shale oil and Athabasca tar sand bitumen, and the oils produced in the initial stage of hydrogenation of Taiheiyo coal and Clear Creek, Utah, coal is characterized as monomers consisting of units of one aromatic ring substituted highly with C_3–6 aliphatic chains and heteroatom-containing functional groups. The chemical structure of asphaltenes from Green River shale oil and Athabasca tar sand bitumen is characterized by oligomers consisting of units of 1–2 aromatic rings substituted highly with C_3–5 aliphatic chains and heteroatom-containing functional groups. The chemical structure of asphaltenes from coal hydrogenation is characterized by dimers and/or trimers of unit structures of 2 to 5 condensed aromatic rings, substituted moderately with C_2–5 aliphatic chains and heteroatom-containing functional groups.The close agreement between fa(¹H-NMR) and fa(¹³C-NMR) for Green River shale oil derivatives and Athabasca tar sand derivatives indicates that the assumption of 2 for the atomic H/C ratio of aliphatic structures is reasonable. For coal hydrogenation products, a value of 1.6–1.7 for the H/C ratio of aliphatic structures would be more reasonable.     

Hydroliquefaction of Kentucky 914 coal using bottoms recycle

Kentucky $\text{9}\text{14}$ bituminous coal has been liquefied in a batch reactor using blends of distillates and SRC or SRC fractions as the solvent. The most effective solvents contained either mildly hydrogenated SRC or the cyclohexane-soluble oil fraction of SRC. Approximately 65 wt% of Kentucky $\text{9}\text{14}$ coal was converted to C₄-700K liquids using these solvents. This yield can be compared to a yield of ≈40 wt% C₄-728K produced in the SRC-II process from Kentucky $\text{9}\text{14}$ coal.     

Characteristic diagrams of coal-derived liquids: the correlation between aromaticity and atomic HC ratios

Characteristic diagrams, which are very useful in studies of the reaction pathways in coal liquefaction processes and to characterize coal-derived materials, are presented. Using model compounds, aromatic carbon fraction, f_a, and aromatic proton fraction, f_aH, are plotted against atomic $\text{H}\text{C}$ ratio. The experimental results of an anthracene oil and its hydrogenated oils are plotted on these diagrams, and the usage and the validity of the charts are verified.     

Liquefaction of coal and related materials

Bituminous coal, lignite, peat and more recent biogenic materials were reacted as water slurries at 380 °C for short periods with hydrogen, directly and from the water-gas shift reaction, without organic solvents or catalysts. Conversion increases with $\text{H}\text{C}$ and $\text{O}\text{C}$ ratio of the input material and reaches 90%. For benzene-soluble products $\text{O}\text{C}$ is always lower and $\text{H}\text{C}$ usually higher than for the original material.     

Characterization of liquid product from the reaction of coal with hydrogen atoms

An oily product formed by the reaction of a domestic subbituminous coal (Taiheiyo coal) with hydrogen atoms at 200 °C, has been characterized. The material is essentially composed of C₅-C₂₂ alkanes and cycloalkanes. The $\text{H}\text{C}$ ratio, specific gravity and refractive index were 1.81, 0.855 and 1.447, respectively. The absence of heteroatoms, alkenes and aromatics in the product is the outstanding feature of the coal liquefaction induced by hydrogen atoms.     

A mechanistic study of hydrogenation of coal. 2.

In Part 1 the authors reported that liquefaction of coal by hydrogenation in the presence or absence of vehicle and with or without catalyst progresses with characteristic variations of the reaction order. In the present paper, the roles of temperature, hydrogen, vehicle and catalyst have been studied using a free-radical scavenger such as p-benzoquinone or iodine. Based on these results, a set of characteristic reactions has been identified from which the following overall rate equation has been derived: $\text{d[P}{}_{\mathrm{m}}\text{]}\text{dt}\text{= β}{}_1\text{[C] + β}{}_2\text{[C]}{}^2\text{+ β}{}_3$ where [P_m] denotes gas, and benzene-soluble products, [C] represents the percentages of organic matter in coal and benzene insoluble intermediates, and β₁, β₂ and β₃ are constants. The rate equation thus explains the experimentally observed variation of the reaction order, which depends on the predominance of a particular group of reactions. It has been postulated that pyrolysis is the main driving force, and that hydrogenation of coal either with gaseous hydrogen or by hydrogen-donating vehicle is basically influenced by reactions involving free radicals.     

Electrochemical reduction of polymeric carbon

It was found that the electrochemical reduction of poly (tetrafluoroethylene) with lithium amalgam leading to the mixture of polymeric carbon and lithium fluoride as solid product is followed by a consecutive electrochemical reaction via a polymeric anion radical, [$\text{(}\text{?}$C_n$\text{)}\text{?}$^?]_m. The value of n was determined as 4.75 and was found to be independent of the reaction conditions. The charge of this radical is during the reaction neutralised with Li⁺ ions diffusing through the solid phase to form a chemical compound $\text{(}\text{?}$C_nLi$\text{)}\text{?}$_m whose CLi bonds have a localized character. Therefore, this compound does not evolve hydrogen in contact with water as the intercalation compounds C_nLi, but hydrolyses to a solid hydrocarbon $\text{(}\text{?}$C_nH$\text{)}\text{?}$_m.     

Gasification reactivities of optical textures of metallurgical cokes

Optical textures of ten typical cokes before and after gasification in CO₂ were quantified by point counting under a polarized microscope to quantify the reactivities of each type of optical texture. Although absolute values of gasification rate for each texture varied considerably from coke to coke, their relative values were constant regardless of the origin of the cokes. The relative reactivities of flow, mosaic, isotropic and inert textures were 1,1.8,2.8 and 3.0, respectively. The relative reactivity of a single coke calculated from a knowledge of optical textures, was monotonicly correlated with the mean maximum reflectance ($\text{R}\text{?}{}_0$) of the parent coal. This indicates that the high reactivity of coke from a high-rank coal ($\text{r}\text{?}{}_0\text{= 1.8\%}$) is due to factors other than its optical texture. The crystallite height, L_c(002)' of the coke correlated with $\text{R}\text{?}{}_0$ of the parent coal, although the values of L_c(002) varied only from 1.5 to 2.1 nm.     

Molecular interaction of quinoline with coal-liquid fractions

A direct calorimetric method has been used to determine simultaneously the molar enthalpy, ΔH^o, and equilibrium constant, K, for the interaction of quinoline (Qu) with coal-derived asphaltenes (A), acid/neutral (AA) and base (BA) components of A, silylated asphaltenes (A(TMS)) and heavy oil (HO) fractions in solvent C₆H₆. Solvent fractionated A and HO fractions were from three centrifuged-liquid product (CLP) samples prepared in the 450 kg ($\text{≈}\text{1}\text{2}$ U.S. ton) per day Process Development Unit at Pittsburgh Energy Research Center, at different process conditions from the same feed coal, Kentucky hvAb. For a given system, Qu-A (AA or BA), Qu-HO, the almost constant value of K and rectilinear variation of ΔH^o with the phenolic oxygen content of coal-liquid fractions have been attributed to the dominance of hydrogen-bonding effects, involving phenolic OH, over other types of molecular interactions in solution. In the Qu-A(TMS) system, ?ΔH^o values increase with decrease in molecular weight of A(TMS), while ?ΔS^o values increase with increase in aromaticity of the A fraction. The degree of complexation, in absence of OH groups, is much smaller than with the Qu-A system.     

Conversion of solvent-refined coal to liquid products in the presence of Lewis acids

The formation of liquid products from a solvent-refined coal (SRC) was studied using Lewis acid catalysts in the presence of either benzene or cyclohexane as an extracting solvent. The soluble products were characterized by elemental analysis, ¹H-n.m.r., and, in some experiments, by gel permeation chromatography. Only ZnCl₂ and SnCl₂, the weakest Lewis acids examined, enhanced the dissolution of SRC over that observed in the absence of a catalyst. Increases in solubility were accompanied by increases in $\text{H}\text{C}$ and aliphatic character and by decreases in average molecular weight. These changes are ascribed to the ability of ZnCl₂ and SnCl₂ to promote depolymerization and hydrogenation of the SRC. Alkylation with isopropanol was also found to enhance the solubility of SRC in benzene and cyclohexane.     

Structural study of hexane-soluble products from hydroliquefaction of three Yallourn brown coal lithotypes over molten salt catalysts

The hexane-soluble fractions of hydroliquefied products from three Yallourn brown coal lithotypes have been separated into five fractions by combined silica-alumina packed column chromatography. Analyses of various fractions by g.c.-m.s. permitted the identification of ≈50 components in the saturate fraction and 40 components in the diaromatic fraction, together with 30 components in the monoaromatics. The components identified were quite similar among hexane-soluble portions of all three lithotypes. A marked predominance of even carbon number alkane (C₂₃-C₂₉) was observed in the hydrocarbon fractions from pale lithotype over $\text{ZnCl}{}_2\text{KCl}$, and medium light lithotype over both pure ZnCl₂ and $\text{ZnCl}{}_2\text{KCl}$. However, medium dark lithotype over both melt catalysts produced a saturate fraction with an odd carbon number(C₂₂-C₂₈) preference. Based on spectral methods, Soxhlet extracts obtained from untreated lithotypes (hexane and benzene solubles) were characterized as complex mixtures of higher molecular weight(300–1000) aliphatic hydrocarbons, which were supposed to be a precursor of the saturates produced from the corresponding lithotype in the catalytic hydroliquefaction.