Heavy media separation of SRC-II feedstocks: 1. Effect on coal properties

The objectives of this investigation were to determine the effects of coal preparation on the properties of Run-of-Mine (ROM) and washed Powhatan and Ireland Mine coals and to assess the potential effects on SRC-II liquefaction yields. The effect of washing on the two coals was found to be quite similar. For both coals, the properties were altered more significantly by changes in separation media gravity than by changes in the coal size. The elemental composition of the Powhatan and Ireland washed coals was correlated with carbon content. It was shown that both the hydrogen and oxygen levels increased linearly with the carbon content of the coal samples. However, the $\text{H}\text{C}$ and $\text{O}\text{C}$ ratios were not changed significantly by coal cleaning. Only small variations in the nitrogen and organic sulphur levels were observed while the sulphate sulphur and chlorine levels were not affected by coal cleaning. The major impact of the coal cleaning was to reduce the pyritic sulphur (and hence the total sulphur) content of the coals. Most of the pyritic sulphur was shifted into the middling coal and refuse fractions while the clean coals had much lower contents and the pyritic sulphur level decreased with increasing carbon content. Coal cleaning did not significantly alter the maceral contents of vitrinite, exinite, total reactive macerals (TRM), or the reflectance of vitrinite; all these parameters varied over a very narrow range, probably within the precision of the measurement technique.     

Mechanisms leading to process improvements in lignite liquefaction using CO and H2S

Optimum distillate yields from US lignites can be as high on a dry, ash-free basis as those obtained from bituminous coals, but only if the vacuum bottoms are recycled. Lignites are more readily liquefied if the reducing gas contains some carbon monoxide and water, which together with bottoms recycle has proven to yield the highest conversions and the best bench-unit operability. The recycle solvent in the reported tests consisted of unseparated product slurry, including coal mineral constituents. Variability in coal minerals among nine widely representative US low-rank coals did not appear to correlate with liquefaction behaviour. Addition of iron pyrite did, however, improve yields and product quality, as measured by hydrogen-to-carbon ratio. Future improvements in liquefaction processes for lignite must maintain high liquid yields at reduced levels of temperature, pressure, and reaction time whilst using less reductant, preferably in the form of synthesis gas (CO + H₂) and water instead of the more expensive pure hydrogen. Understanding the process chemistry of carbon monoxide and sulphur (including H₂S) during lignite liquefaction is a key factor in accomplishing these improvements. This Paper reviews proposed mechanisms for such reactions from the viewpoint of their relative importance in affecting process improvements. The alkali formate mechanism first proposed to explain the reduction by CO does not adequately explain its role in lignite liquefaction. Other possible mechanisms include an isoformate intermediate, a formic acid intermediate, a carbon monoxide radical anion, direct reaction with lignite, and the activation of CO by alkali and alkaline earth cations and by hydrogen sulphide. Hydrogen sulphide reacts with model compounds which represent key bond types in low-rank coal in the following ways: (1) hydrocracking; (2) hydrogen donor; (3) insertion reactions in aromatic rings; (4) hydrogen abstraction, with elemental sulphur as a reaction intermediate; and (5) catalysis of the water-gas shift reaction. It appears that all of these reaction pathways may be operative when catalytic amounts of H₂S are added during liquefaction of lignite. In bench recycle tests, the addition of H₂S as a homogeneous catalyst reduced reductant consumption as much as three-fold whilst maintaining high yield levels when the reaction temperature was reduced by 60°C. Attainment of the high distillate yield at 400°C was accompanied by a marked decrease in the production of hydrocarbon gases, which normally is a major cause of unproductive hydrogen consumption and solvent degradation via hydrocracking. Processing with synthesis gas and inherent coal moisture using bottoms recycle and H₂S as a catalyst appears to be the most promising alternative combination of conditions for producing liquids from lignite at reduced cost.     

New method for elucidating the structures of coal

A mixture of 30% aqueous hydrogen peroxide (H₂O₂) and trifluoroacetic acid (TFA) dissolves coals to give colourless solutions. Depending on the nature of the coal, 9–55% of the hydrogen in the original coal is converted to simple aliphatic products. The aliphatic products preserve most of the original aliphatic structure of the coal. This technique of oxidative degradation is a powerful method of elucidating the structure of coal. It is particularly applicable to the aliphatic components of coal structure.     

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.     

Non-isothermal liquefaction of liptobiolith coal in supercritical water flow and effect of zinc additives

The liquefaction of liptobiolith coal in water vapor and supercritical water (SCW) flow at uniform increase in temperature from 300 up to 470 °C and in SCW flow at 400 °C (30 MPa) with addition of zinc shavings to coal has been investigated. Temperature dependences of the yield of liquid and volatile products and kinetic parameters of the process have been obtained. The yields of oil, resin, asphaltene and volatile products in relation to the coal organic matter (COM) are 23.2, 16.1, 5.1 and 14.1%, respectively. CO₂, CO, H₂S and C₁–C₄ alkanes prevail in the composition of volatile products. The generation of oil, resin and asphaltene are found to have occurred in terms of the simultaneous chemical reactions of cleavage of the COM aliphatic CC bonds, while the volatile products result from the consecutive transformations of the COM components in the bulk and SCW solution. Participation of H₂O molecules in thermochemical transformations of COM leads to increase in the oxygen amount in the conversion products and residue by 13.2%. Hydrogen and heat evolution during zinc oxidation by SCW provides for the hydrogenation of COM in situ. Addition of zinc to coal results in increase in the volatile products yield up to 48.6% and decrease in the conversion residue yield up to 20.8%. Under these conditions the yield of resin does not change, while the yields of oil and asphaltene decrease up to 21.2 and 2.5%, respectively. Based on the sulfur balance it is revealed that ≈40% of sulfur atoms pass into ZnS owing to the reactions of H₂S with Zn and ZnO resulting in the removal of H₂S from the volatile conversion products.     

Effect of hydrothermal treatment on the extraction of coal in the CS2/NMP mixed solvent

The extraction of four Chinese different rank bituminous coals with the carbon disulfide/N-2-pyrrolidinone (CS₂/NMP) mixed solvent (1:1 by volume) was carried out in room temperature. It was found that one of middle bituminous raw coal of the four coals gave more than 74% (daf) extraction yield, suggesting an associative structural model for the coal. The four coals were hydrothermal treated under different conditions, and it was found that the extraction yields of the treated coals obviously increased. This will have great significance for coal liquefaction. FTIR measurements show the removal of minerals after the hydrothermal treatment of coals suggesting the dissociation of the coal aggregation structure due to ionic interactions and/or hydrogen bonds broken because of the removal of oxygen and hydroxyl oxygen proceeded through ionic pathways, resulting in the extraction yields of the treated coals increase. However, breaking of π-cation interactions by hydrothermal treatment may be one of possible mechanisms for the enhancement of extraction yield of higher rank of treated coal. The mechanism of hydrothermal treatment of coal was discussed in the paper.     

Mössbauer study of transformations of pyrite under conditions of coal liquefaction

The Mössbauer effect is used to study in-situ transformations of pyrite under conditions of coal liquefaction based on Illinois No. 6 coal from St. Clair County. A marked reduction is observed at high temperatures in the isomer shift of the iron sulphides during coal liquefactions. By contrast the pure sulphides do not show such a strong effect in the presence of solvent and hydrogen. This reduction in the isomer shift may result from covalent bonding between the iron on the pyrrhotite surfaces and the coalderived liquid and gases. Marked broadening of the linewidth of Fe_{1 ? x}S occurs above 300 °C in the presence of solvent and hydrogen. The stoichiometries of the pyrrhotites formed in the different runs were determined and a correlation was observed between the total amount of sulphur in the coal and the iron deficiency in Fe_{1 ? x}S. Coal-derived liquids are more active in enhancing pyrite decomposition than tetralin. Both H₂S and Fe_{1 ? x}S seem to be actively involved in the liquefaction process.     

Effect of pre-swelling of coal on its solvent extraction and liquefaction properties

Effects of pre-swelling of coal on solvent extraction and liquefaction properties were studied with Shenhua coal. It was found that pre-swelling treatments of the coal in three solvents, i.e., toluene (TOL), N-methyl-2-pyrrolidinone (NMP) and tetralin (THN) increased its extraction yield and liquefaction conversion, and differed the liquefied product distributions. The pre-swollen coals after removing the swelling solvents showed increased conversion in liquefaction compared with that of the swollen coals in the presence of swelling solvents. It was also found that the yields of (oil + gas) in liquefaction of the pre-swollen coals with NMP and TOL dramatically decreased in the presence of swelling solvent. TG and FTIR analyses of the raw coal, the swollen coals and the liquefied products were carried out in order to investigate the mechanism governing the effects of pre-swelling treatment on coal extraction and liquefaction. The results showed that the swelling pre-treatment could disrupt some non-covalent interactions of the coal molecules, relax its network structure and loosened the coal structure. It would thus benefit diffusion of a hydrogen donor solvent into the coal structure during liquefaction, and also enhance the hydrogen donating ability of the hydrogen-rich species derived from the coal.     

Hydroliquefaction of low-sulfur coals using iron carbonyl complexes—Sulfur as catalysts

Hydroliquefaction of low-sulfur Australian coals (Wandoan and Yallourn) was studied using iron carbonyl complexes as catalyst. The addition of Fe(CO)₅ (2.8 wt% Fe of coal) increased coal conversion from 48.6 to 85.2% for Wandoan coal, and from 36.7 to 69.7% for Yallourn coal in 1-methylnaphthalene at 425°C under an initial hydrogen pressure of 50 kg cm^?2. When molecular sulfur was added to iron carbonyls (Fe(CO)₅, Fe₂(CO)₉ and Fe₃(CO)₁₂), higher coal converions ( > 92%) and higher oil yields (>46%) were obtained, along with an increase in the amount of hydrogen transferred to coal from the gas phase (0.2 to 2.8%, d.a.f. coal basis). In the liquefaction studies using a hydrogen donor solvent, tetralin, Fe(CO)₅S catalyst increased the amount of hydrogen absorbed from the gaseous phase and decreased the amount of naphthalene dehydrogenated from tetralin. The direct hydrogen transfer reaction from molecular hydrogen to coal fragment radicals seems to be a major reaction pathway. Organic sulfur compounds, dimethyldisulfide and benzothiophene, and inorganic FeS₂ and NiS were found to be good sulfur sources to Fe(CO)₅. From X-ray diffraction analyses of liquefaction residues, it is concluded that Fe(CO)₅ was converted into pyrrhotite (Fe_1?xS) when sulfur was present, but into Fe₃O₄ in the absence of sulfur.     

Heavy media separation of SRC-II feedstocks: 2. Effect on liquefaction yields

The objective of this investigation was to assess the potential effects of coal preparation on SRC-II liquefaction yields. Liquefaction yields were estimated from coal properties at standard SRC-II conditions using mathematical models. For Powhatan and Ireland Mine coals, the yields were most sensitive to changes in the total sulphur level and were not significantly affected by the small changes in total reactive macerals, H/C ratio or volatile matter. The fractions from both coals were ranked in order of decreasing liquid yields (or increasing organic vacuum bottoms yields) on a dry, ash-free basis as follows: middling > cleaned > ROM (run-of-mine) > deep cleaned. On a dry basis, all the washed fractions from each coal were superior to the ROM coal, giving higher liquid yields.     

Catalysis of gasification of coal-derived cokes and chars

Calcium is the most important in-situ catalyst for gasification of US coal chars in O₂, CO₂ and H₂O. It is a poor catalyst for gasification of chars by H₂. Potassium and sodium added to low-rank coals by ion exchange and high-rank coals by impregnation are excellent catalysts for char gasification in O₂, CO₂ and H₂O. Carbon monoxide inhibits catalysis of the CH₂O reaction by calcium, potassium and sodium; H₂ inhibits catalysis by calcium. Thus injection of synthesis gas into the gasifier will inhibit the CH₂O reaction. Iron is not an important catalyst for the gasification of chars in O₂, CO₂ and H₂O, because it is invariably in the oxidized state. Carbon monoxide disproportionates to deposit carbon from a dry synthesis gas mixture (3 vol H₂ + 1 vol CO) over potassium-, sodium- and iron-loaded lignite char and a raw bituminous coal char, high in pyrite, at 1123 K and 0.1 MPa pressure. The carbon is highly reactive, with the injection of 2.7 kPa H₂O to the synthesis gas resulting in net carbon gasification. The effect of traces of sulphur in the gas stream on catalysis of gasification or carbon-forming reactions by calcium, potassium, or sodium is not well understood at present. Traces of sulphur do, however, inhibit catalysis by iron.     

Catalytic activity of mineral matter from western Kentucky coals for hydro-desulphurization and hydrodenitrogenation

A pulse reactor was used to study the catalytic activity and selectivity of mineral matter from Kentucky No.9 and No.11 seam coals and a low calorific value gasifier ash in the hydrodesulphurization (HDS) of thiophene and hydrodenitrogenation (HDN) of pyrrole, pyrrolidene and n-butylamine. Mineral matter in its least altered state was obtained by low temperature ashing. Thiophene conversion correlated well with the iron and zirconium contents (R > 0.95) of the catalysts, and at 450 °C all catalysts including a commercial Fe₂O₃/AI₂O₃ gave similar distributions of the butenes and <5% butane. Reactivities of N-compounds catalysed by mineral matter from Kentucky Nos.9 and 11 coals were in the order: n-butylamine > pyrrolidine > pyrrole ≈0. Nickel was found to be the important element n-butylamine conversion and 1-butene was the predominant product species for all the catalysts. Mineral acid treatment of the mineral matter from No.11 coal decreased its HDN activity but increased its HDS activity. Results of this study indicate that hydrogen consumption for removal of sulphur and nitrogen can be reduced by using dehydrogenation-type catalysts.     

A Thermogravimetric Analysis Study of the Kuzbass Coals of Different Ranks

The coals of different ranks from the Kuznetsk Coal Basin were studied by thermogravimetric analysis in inert and oxidizing atmospheres. Correlations between thermal decomposition characteristics [maximum decomposition temperatures (T_max, °C), maximum rates of decomposition (Vmax, %/min), and sample weight losses in different temperature ranges (Δm, %)] and proximate analysis [yields of volatile substances (Vdaf, %)] and petrographic analysis [vitrinite reflectance (R_o)] data and NMR-spectroscopic data [aromaticity factor ( fa)] as the characteristics of the degree of maturity of the test coals were established.     

Flash pyrolysis of coals: influence of cations on the devolatilization behaviour of brown coals

The influence of cations on the pyrolysis behaviour of brown coals under flash heating conditions was investigated by means of a small fluidized-bed pyrolyser. A stream of coal particles in nitrogen was injected at rates of 1–3 g coal/h directly into a heated bed of sand fluidized by nitrogen. Yields of tar, C₁–C₃ hydrocarbons and total volatile matter from four Gelliondale brown coals and a Montana lignite were determined as a function of pyrolysis temperature. With all coals the maximum tar yield was obtained at 600 °C. Removal of cations present in the coals markedly increased the yields of tar and total volatile matter, with little effect on the yields of hydrocarbon gases. The converse was also observed in that the addition of Ca²⁺ to a cation-free coal decreased the yields of tar and total volatile matter. The extent of the reduction in tar yield at 600 °C in the presence of cations was found to be similar for all coals. After acid washing, tar yields appear to correlate with the atomic $\text{H}\text{C}$ ratios of the coals in a manner similar to that observed previously with bituminous coals.     

γ-Radiolytic desulphurisation of some high-sulphur Indian coals catalytically accelerated by MnO2

γ-Radiolysis of acidic aqueous coal slurries is a novel and effective method for the simultaneous oxidative desulphurisation and demineralisation of high-sulphur coals. This method is capable to selectively remove the inorganic and organic forms of sulphur simultaneously through the in situ-generated H₂O₂ and other radiolytic products. In effect, there is neither any appreciable degradation of coal matrix nor any loss in the caking property and volatile matter content of the coals after the removal of sulphur. However, significant removals of sulphur and mineral matter are effected at rather high γ-dose (175×10⁴ Gy or so). Therefore, for the process to be economically viable and commercially adaptable, the applied γ-dose needs to be somehow substantially brought down, at which the same level of desulphurisation could be achieved. Catalytically, accelerating the radiolysis process is one such possibility to effect the desulphurisation step at a low γ-dose.Reported in this paper are the results of investigations on the desulphurisation and demineralisation of high-sulphur (sulphur content in the range 3–5.5%) Churphy, Chalang and Bapung coals of Meghalaya by γ-radiolytic process catalysed by MnO₂. The maximum removal of total sulphur (15.6%, 30.0% and 29.8%) at 30×10⁴ Gy in the presence of MnO₂ and the simultaneous removal of mineral matter (20.0% and 18.5% from Churphy and Chalang coals at 30×10⁴ Gy and 12.0% from Bapung coal at 45×10⁴ Gy) are at par with removals at 175×10⁴ Gy without MnO₂, which has been attributed to MnO₂ catalytically accelerating the radiolytic process via the formation of highly reactive MnO under the action of γ-rays. All the other features of non-catalysed radiolytic desulphurisation such as stabilisation of the slurry and coal not becoming radioactive during irradiation, increase in the heating value, improvement in the caking property, no appreciable degradation of coal matrix after removal of sulphur from the coals remain the same.     

Coal flash pyrolysis: 3. An analytical method for polymethylene moieties in coal

A method of analysis for polymethylene compounds in coal is described, based on liquefaction of the coal in tetrahydroquinoline and running the ¹H n.m.r. spectrum of the liquefaction products in CDCl₃. It is shown that the (CH₂)_n content determined in this way is proportional to the ethylene, propylene and butadiene yields produced on flash pyrolysis of the coals at 850 °C.     

Relation between coal aromatic carbon concentration and proximate analysis fixed carbon

Good agreement has been obtained between measured proximate analysis values for fixed carbon (FC) and the predictions of a thermal decomposition model. The model provides a basis for understanding the relation between FC and coal structure and between FC measured under proximate analysis conditions and coke or char measured in other thermal decomposition experiments. The key parameters in the model are the aromatic carbon concentration (C_ar) and the tar yield. C_ar has been determined for 43 coals using quantitative infrared analysis. The aliphatic hydrogen concentration is measured from the absorption near 2900 cm^?1 and the aliphatic carbon concentration is computed assuming a stoichiometry of CH_1.8 C_ar is then computed by difference. The results verify the good correlation between C_ar and FC discussed by van Krevelen. To explain this correlation, use has been made of a coal thermal decomposition model which has been successful in simulating the quantity and composition of volatile components yielded under vacuum pyrolysis conditions. To apply the model to proximate analysis, it was necessary to estimate the tar yields obtained with thick beds and the amounts of O, N, H, and S which remain with the FC. The tar yields for proximate analysis conditions have been estimated to be $\text{1}\text{3}$ to $\text{1}\text{4}$ the yields for thin beds in vacuum. To determine the composition of the FC, measurements were made on a lignite and a bituminous char produced in a thin bed heated by a wire grid for the time (7 min) and temperature (950 °C) used in the proximate analysis, and on the FC residues from a proximate analysis volatile matter determination. Both residues give similar results, showing that approximately 10% of the ‘fixed carbon’ is not carbon. Values of FC computed with the model adjusted for the above conditions are in good agreement with the measured values.     

The characterization of coal macerals by diffuse reflectance infrared spectroscopy

Diffuse reflectance Fourier transform infrared (DRIFT) spectroscopy was applied to study the structure of vitrinites, liptinites and fusinites isolated from different rank coals (77.0-91.5%C) using a centrifugal float-sink procedure. Among the macerals separated from a given coal, liptinites are characterized by the highest proportion of aliphatic CH groups, occurring principally as CH₂, and fusinites by the most aromatic structure. Macerals separated from the low rank coals show comparable content of hydroxyl groups that occur as free OH or form similar types of hydrogen bonds. Carbonyl groups appear not only as conjugated ketones and quinones in vitrinites, but also as carboxylic groups in liptinites and low rank fusinites. CH_ar/CH_al ratio does not vary with carbon content in liptinites, but increases in vitrinites and fusinites. In the case of liptinites and vitrinites, a linear relationship between CH_ar/CH_al and reflectance is observed up to vitrinite R₀ value of 1.80%. For all macerals, the ratio CH_ar/CC increases with reflectance, but at different rates. Structural parameters CH_ar/CH_al and CH_ar/CC calculated from DRIFT spectra are very helpful in monitoring the differences among macerals of given coal and following structural rearrangement occurring with rank.     

The chemical nature of asphaltenes from some coal liquefaction processes

Average chemical structures of asphaltenes from three coal liquefaction processes, namely hydroliquefaction (SRC-II), hydrogen-donor solvent extraction (HDS) and supercritical gas extraction (SCG), have been deduced using a structural analysis scheme in which data from ¹H and ¹³C NMR are combined with those from elemental, molecular weight and functional group analyses. Compared with SRC-II and HDS asphaltenes, SCG asphaltenes contain less-condensed aromatic nuclei which can be largely represented by 1- and 2-ring structures. They also contain more oxygen groups and slightly larger aliphatic substituents. CH₃ accounts for between 30 and 40% of the aliphatic carbon in all the asphaltenes investigated. Small amounts of long alkyl chains are present in the SCG asphaltenes but not in the SRC-II and HDS asphaltenes. SCG extraction is chemically less severe than the SRC process and HDS extraction since neither hydrogen nor HDS are employed and, as a result, SCG extracts are considered to be much more representative of the organic matter in the parent coals.     

Formation and destruction of H2S in the short residence time pyrolysis of pulverized coal and model compounds

The evolution of sulphur as H₂S from three US bituminous coals, L-cystine, and thianthrene has been studied in the reflected shock region of a chemical shock tube. With heating rates of approximately 3 × 10⁶Ks^?1, to temperatures in the range 1000–2000K, ultimate yields of sulphur from 7 to 70% as H₂S are observed in as little as 1.5 ms. The most important influence on ultimate yields may be the H/S molar ratio in the fuel which corresponds in the hydrocarbons studied with the H₂S yields. Inherent mineral matter may also influence the evolution, as H₂S formation precedes light hydrocarbon formation from the two model compounds, but occurs nearly simultaneously from the coals. The overall rate of H₂S formation for the three coals is adequately described by a reaction, first order with respect to remaining sulphur, with a rate constant $\text{k=8.1 × 10}{}^7\text{exp}\text{(?}\text{15 960}\text{T}\text{) s}{}^{\mathrm{?1}}$. In the pyrolysis of all five solids, the H₂S yields are decreased to below detectable limits at temperatures >1500K. The path for destruction of the H₂S appears to be by reaction with hydrocarbons such as C₂H₂, the concentration of which becomes similar to the H₂S concentration in the temperature range 1500–1600K.