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.     

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.     

Effects of solvent and iron-compounds on the liquefaction of brown coal

Hydrogen-donor solvents such as hydrophenanthrene are the most effective aromatic solvents for the liquefaction of brown coal. The hydrogen-donating ability of the solvent is more important for brown coals than for bituminous coals, because the thermal decomposition and subsequent recombination of the structure of the brown coals occurs rapidly. Three-ring aromatic hydrocarbons are more effective solvents than two-ring aromatics, and polar compounds are less effective solvents with brown coals than with bituminous coals. The thermal treatment of brown coal, accompanied by carbon dioxide evolution at temperatures > 300°C, in the presence of hydrogen-donating solvent did not affect the subsequent liquefaction reaction. However, thermal treatment in the absence of solvent strongly suppressed the liquefaction reaction, suggesting that the carbonization reaction occurred after the decarboxylation reaction in the absence of hydrogen donor. To study the effect of various iron compounds, brown coal and its THF-soluble fraction were hydrogenated at 450°C in the presence of ferrocene or iron oxide. The conversion of coal and the yield of degradation products are increased by the addition of the iron compounds, particularly ferrocene, and the yield of carbonaceous materials is decreased.     

Reaction mechanism of coal hydrogenation: 2. Three rings solvent system

Taiheiyo coal was hydrogenated in phenanthrene, 9,10-dihydrophenanthrene, 1,2,3,4,5,6,7,8-octahydrophenanthrene and perhydrophenanthrene under 10 MPa (initial pressure) of hydrogen or nitrogen with or without stabilized nickel as catalyst at 400 °C for 15 min. Preasphaltene, asphaltene and oil conversions and the conversion of solvents were measured, and the amounts of hydrogen absorbed by coal from molecular hydrogen and from donor solvent were calculated. The main route of reaction appears to be the direct hydrogenation of coal by molecular hydrogen and the contribution of hydrogenation via the solvent was greater than in the case of the two rings solvent system.     

Reaction mechanism of coal hydrogenation: 1. Two-ring solvent system

Taiheiyo coal was hydrogenated in naphthalene, tetralin and decalin under 10 MPa (initial pressure) of hydrogen or nitrogen with stabilized nickel as catalyst at 400 °C for 15 min. Preasphaltene, asphaltene and oil conversions and the conversion of the solvents were measured. The hydrogen absorbed by coal from molecular hydrogen and from the donor solvent was calculated. The main reaction route appears to be the direct hydrogenation of coal by molecular hydrogen, with the side reaction via solvent by molecular hydrogen occurring only slightly, when an active catalyst such as stabilized nickel is present.     

Catalytic liquefaction of various coals using a mixture of carbon monoxide and water

In a batch-autoclave, twenty coals were liquefied using a cobalt-molybdenum oxide catalyst with a mixture of CO and H₂0 at 400 °C with or without vehicle oil. Furthermore, lignite and peat were liquefied on tungsten oxide catalyst at 300 °C in the absence of CO. The reactivity of coal in this liquefaction is found to depend strongly on its rank. The vehicle oil significantly influences the extent of the water-gas shift reaction, especially when bituminous coals are liquefied, by dissolving such coals. Liquefaction of coal by this process is considered to take place via three routes: hydrogenolysis by the nascent hydrogen produced from the shift reaction; dissolution of coal into the vehicle oil which is an initial stage of hydrogenolysis; and a solvolytic reaction with H₂O, such as hydrolysis.     

Solubilization of bituminous coal in aromatic and hydroaromatic solvents

The Solubilization of a bituminous coal (Ruhr District) in aromatic and the corresponding hydroaromatic compounds was compared at temperatures from 250–450°C. The solvent pair naphthalene and tetralin exhibit marked differences in solvent power as only tetralin is a ‘true’ hydrogen donor and, thus, an excellent solvent for coal. In the series of quinolines, however, the difference in solvent efficiency became significant only at temperatures ?350°C. The high solvent power of anthracene oil is explained on the basis of transferable hydrogen and the presence of N-heterocyclic compounds. Inference is drawn as to the optimum constitution of a vehicle oil.     

Aspects of the chemistry of donor solvent coal dissolution. The role of phenol in the reaction

The relative reactivity of phenol in exchange reaction with tetralin-d₁₂ and naphthalene-d₈ indicates that hydrogen exchange occurs by a free radical process rather than by an electrophilic substitution reaction at 427 °C. Substances such as benzyl phenyl ether that initiate free radical reactions increase the rate of the exchange reaction between phenol and tetralin-d₁₂ whereas weak acids have only a modest influence on the exchange. Phenol and 1 -naphthol accelerate the rates of decomposition of some ethers and amines in tetralin. These results suggest that phenolic compounds enhance thermal coal dissolution reactions in donor solvents via their influences on the rates of the homolytic cleavage of carbon-oxygen and carbon-nitrogen bonds.     

Carbonylation studies with Illinois No. 6 bituminous coal

Sodium metal and carbon dioxide were used to carbonylate Illinois No. 6 coal in a 1 l, high-pressure, autoclave in anhydrous tetrahydrofuran from 150 to 350 °C. Solubility of the reaction products in tetrahydrofuran and water, and the sodium uptake in the insoluble residue were determined. The reduction and subsequent carbonylation of coal produced a limited amount of solubility in these solvents, and the uptake of sodium in the insoluble residue reached a maximum of 6.29% at 250 °C with no carbon dioxide added. This corresponded to a ratio of sodium atoms per 1000 carbon atoms of 62.9, a 69-fold increase over the unreacted dried coal. Total acidity and carboxyl group content were calculated for the insoluble residues and unreacted bituminous coal. The per cent increase of carboxyl groups reached a maximum of 1.37 meq g^?1 at 2000 °C which represents a 174% increase over the unreacted coal.     

Comparative reactivities of coal asphaltenes during hydropyrolysis

Comparisons have been drawn in the relative reactivities of three coal asphaltenes during hydropyrolysis. All were derived from hydrogen donor-solvent extracts of bituminous coal, but had different hydrotreatment histories and different carbon contents (87.1, 91.9 and 90.8 wt% for asphaltenes 1, 2 and 3, respectively). The hydropyrolyses were carried out in the presence of CoO–MoO₃ catalyst and gaseous hydrogen at 8.7 MPa. For two of the asphaltenes (1 and 2) systematic comparisons were made for different reaction times at 425°C; for all three asphaltenes comparisons were made for l h of hydropyrolysis at 425°C. The general pattern of asphaltenes conversion indicated that more pentane-soluble product was produced from asphaltene isolated from straight coal extract (asphaltene 1). For the asphaltenes isolated from hydrotreated extracts, the extent of conversion to liquids was limited when the carbon content was high (asphaltene 2) although the pattern of conversion was similar in the other hydrotreated asphaltene (asphaltene 3). The aliphatic content of the liquid products formed was low, and the distribution of hydrogenated species in the highly aromatic liquid products indicated that complete hydrogenation of the polyaromatics produced in pyrolysis is difficult. Altogether the aliphatics made up ≈ 10 wt% of the asphaltene 1 hydropyrolysate. Aromatic hydrocarbons made up 90% of the liquid product. Phenanthrene, pyrene and anthracene were prominent, and the largest component in the mixture was phenanthrene which, together with other polyaromatics such as fluoroanthene, dominated the liquid product.     

Catalytic activity of coal minerals in water vapour gasification of coal

Possible catalytic influences of coal minerals during water vapour gasification of coal have been studied by kinetic measurements and microanalytical methods. A bituminous coal without and with various pretreatments and also model chars synthesized from PVC and PVC-sulphur mixtures were used as raw materials. Kinetic measurements were performed in a fixed-bed flow reactor at pressures between 0.2 and 2 MPa and temperatures from 880 to 1010 °C using hydrogen/water vapour mixtures as gasification agents. It was found that coal gasification at and beyond 880 °C can be decisively catalysed by the iron as constituent of mineral matter. Preconditions are elimination of inorganic sulphur and reducing atmosphere to stabilize elemental iron. The optimum pressure is in the range of 0.5 to 1 MPa. Scanning electron microscopy and electron probe microanalysis confirm that catalytic gasification starts as soon as the iron is free of sulphur. The organic sulphur of coal does not prevent but lowers the catalytic activity of iron.     

Kinetics of thermal liquefaction of coal

A model is presented for the kinetic study of the thermal liquefaction of Belle Ayr subbituminous and Burning Star bituminous coals with anthracene oil, hydrogenated anthracene oil and hydrogenated phenanthrene. All experiments were performed in a continuous-feed, stirred tank reactor, at a temperature of 450 °C and a space time of approximately 5 to 55 min. A kinetic model which includes a reaction: coal + oil→more reactive coal, correlates the data reasonably well. This reaction explains the net consumption of anthracene oil during the initial stages of liquefaction. Such a reaction may account for a portion of the swelling of coal at low space times and the sizable increase of viscosity of reaction slurry during these initial stages of liquefaction. It is also observed that the yield of oil increases when solvents of increasing hydrogen donor capacity are used.     

Oxidation of ash-free coal from sub-bituminous and bituminous coals in a direct carbon fuel cell

The present study proposes the production of ash-free coal (AFC) and its oxidation as a primary fuel in direct carbon fuel cells (DCFCs). The AFC was produced by the extraction of Arutmin sub-bituminous coal (AFC1) and Berau bituminous coal (AFC2) using polar solvents such as N-methyl-2-pyrrolidone (NMP), N,N-dimethylacetamide (DMA), N,N-dimethylformamide (DMF) and dimethyl sulfoxide (DMSO). It was carried out at a temperature of around 202 °C under atmospheric conditions and using a microwave irradiation method. Using NMP as the solvent showed the highest extraction yield, and the values of 23.53% for Arutmin coal and 33.80% for Berau coal were obtained. When NMP was added to DMSO, DMA and DMF, the extraction yield in the solvents was greatly increased. The yield of AFC from a sub-bituminous coal was slightly lower than that from a bituminous coal. The AFC was evaluated in a coin-type DCFC with a mixture of AFC and carbonate electrolyte (3 g/3 g) at 850 °C. The AFC and gaseous H₂ fuels were compared using the electrochemical methods of steady-state polarisation and step chronopotentiometry. The DCFC ran successfully with the AFCs at 850 °C. The open-circuit voltages were about 1.35 V (AFC1) and 1.27 V (AFC2), and the voltages at 150 mA cm^?2 were 0.61 V (AFC1) and 0.74 V (AFC2).     

Ambient-pressure thermogravimetric characterization of four different coals and their chars

Ambient-pressure thermogravimetric characterization of four different coals and their chars was performed to obtain fundamental information on pyrolysis and coal and char reactivity for these materials. Using a Perkin-Elmer TGS-1 thermobalance, weight loss as a function of temperature was systematically determined for each coal heated in helium at 40 and 160 °C/min under various experimental conditions, and for its derived char heated in air over a temperature range of 20 to 1000 °C. The results indicate that the temperature of maximum rate of devolatilization increases with increasing heating rate for all four coals. However, heating rate does not have a significant effect on the ultimate yield of total volatiles upon heating in helium to 1000 °C; furthermore, coupled with previous data⁹ for identical coal samples, this conclusion extends over a wide range of heating rate from 0.7 to 1.5 × 10⁴ °C/s. Using the temperature of maximum rate of devolatilization as an indication of relative reactivity, the devolatilization reactivity differences among the four coals tested that were suggested by this criterion are not large. For combustion in air, the overall coal/char reactivity sequence as determined by comparison of sample ignition temperature is: N. Dakota lignite coal ≈ Montana lignite coal > North Dakota lignite char > III. No. 6 bituminous coal ≈ Pittsburgh Seam bituminous coal > Montana lignite char > III. No. 6 bituminous char > Pittsburgh Seam bituminous char. The reactivity differences are significantly larger than those for devolatilization. The reactivity results obtained suggest that coal type appears to be the most important determinant of coal and char reactivity in air. The weight loss data were fitted to a distributed-activation-energy model for coal pyrolysis; the kinetic parameters so computed are consistent with the view that coal pyrolysis involves numerous parallel first-order organic decomposition reactions.     

Laboratory-scale coal reactivity testing for entrained gasification

A relatively simple and rapid micro-gasification test has been developed for measuring gasification reactivities of carbonaceous materials under conditions which are more or less representative of an entrained gasification process, such as the Shell coal gasification process. Coal particles of < 100 μm are heated within a few seconds to a predetermined temperature level of 1000–2000 °C, which is subsequently maintained. Gasification is carried out with either CO₂ or H₂O. It is shown that gasification reactivity increases with decreasing coal rank. The CO₂ and H₂O gasification reactions of lignite, bituminous coal and fluid petroleum coke are probably controlled by diffusion at temperatures 1300–1400 °C. Below these temperatures, the CO₂ gasification reaction has an activation energy of about 100 kJ mol^?1 for lignite and 220–230 kJ mol^?1 for bituminous coals and fluid petroleum coke. The activation energies for H₂O gasification are about 100 kJ mol^?1 for lignite, 290–360 kJ mol^?1 for bituminous coals and about 200 kJ mol^?1 for fluid petroleum coke. Relative ranking of feedstocks with the micro-gasification test is in general agreement with 6 t/d plant results.     

Alcohols as H-donor media in coal conversion. 1. Base-promoted H-donation to coal by isopropyl alcohol

Isopropyl alcohol can act as a hydrogen donor to coal, as can tetralin. In contrast to tetralin, however, the transfer of hydrogen by the alcohol can be promoted by the presence of either potassium isopropoxide or KOH. Acetone is formed from the alcohol in quantities that accord with the amounts of hydrogen transferred to the coal. In runs at 335 °C for 90 min, coal was converted with isopropyl alcohol in the presence of either the alkoxide or KOH to a fully pyridine-soluble product with $\text{H}\text{C}$ ratios from 0.88 to 1.13, in contrast to coal (0.79). The organic sulphur content of the coal was reduced from 2.1% to 1%. Model-compound studies with anthracene and diphenyl ether showed that the anthracene was reduced in the system to 9,10-dihydroanthracene, but the ether was recovered unchanged. The coal products from the alcohol/base treatment are very rich in aliphatic hydrogen and have number-average molecular weights in the 450–500 range. The scheme suggested to explain the conversion at 335 °C includes initial hydrogenation of anthracene-like structures in the coal, followed by thermolysis of the dihydro-intermediate.     

Bimolecular and radical hydrogenation of coal studied by field ionization mass spectrometry

Hydrogenation of a low-rank bituminous coal (78 wt% C daf) by decalin (D) and tetralin (T) was carried out at 340–440 °C. Conversion of D and T was determined by g.c. Little conversion of D occurred below 390 °C, indicating little thermal generation of coal radicals. For T, up to 21 H atoms were transferred to 100 C atoms at 380 °C by, it appears, a bimolecular mechanism. F.i.m.s. of samples heated with D and T to 340–440 °C gave ion profiles of seven nominal-mass homologous series of compounds. Results indicated that material with five or more condensed rings was hydrogenated by T between 340 and 380 °C. At 440 °C both donors reacted with some part of the coal by a radical mechanism. The time of exposure of coal to temperatures up to 390 °C could influence coal liquefaction processes.     

Short contact time dissolution of Liddell coal

The thermal dissolution of Liddell coal in tetralin at 400 °C proceeds rapidly. The addition of hydrogen to coal under moderate, uncatalysed conditions is significant and initially proceeds without the elimination of nitrogen, oxygen or sulphur. At extended reaction times, however, oxygen is eliminated via hydrogenolysis reactions. The simulation of product distributions from the thermal dissolution of Liddell coal at 400 °C, and short contact times, has been undertaken using a system of second-order pseudo-kinetic equations. Excellent agreement between the experimental data and the calculated conversions has been obtained.     

Liquefaction of Yallourn brown coal at low pressures and rapid heating rates

Liquefaction of Yallourn brown coal in solvents at high temperature for short contact times and low pressures has been studied. Very high asphaltene yields are achieved with hydrogen-donating solvents (hydrogenated Ashland pitch A240, hydrogenated anthracene oil, and hydrogenated pyrene). For hydrogenated pyrene, yields of almost 90% were obtained during reaction at 450°C for 10 min or at 510°C for 1 min. The average molecular weight of the asphaltene found was 270, with 40 wt% being accounted for by three-and four-ring polynuclear hydrocarbons. The effect of liquefaction temperature, time, and solvents on the asphaltene yield have been examined to clarify the properties required for the solvent under the present conditions used. The behaviour of the asphaltene during pyrolysis and hydrotreatment has also been studied. Some mechanistic aspects of high-temperature, short contact time liquefaction are discussed with regard to the reactivities of the brown coal and the solvents.     

Structural differences in the tars and chars from the pyrolysis of coals of different rank in hydrogen and in nitrogen

Two British coals—Linby high-volatile bituminous and Abernant anthracite — and an Australian brown coal were pyrolysed at 575 °C in hydrogen or nitrogen at 0.1, 5 and 30 MPa in an inclined, single-stage reactor. Hydrogen pressures of ? 5 MPa led to increased yields of tars which were more aromatic than those produced in nitrogen. The high-volatile bituminous coal fused under all conditions, whereas the anthracite and brown coal fused and agglomerated only in hydrogen at 30 MPa.