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.     

Iron/sulfur-catalyzed coal liquefaction in the presence of alcohol and carbon monoxide

The activities of several iron-based catalyst precursors towards the liquefaction of various kinds of coals, ranging from brown to bituminous, were examined in alcohol–carbon monoxide systems. Pentacarbonyliron (Fe(CO)₅) with or without sulfur, or synthetic pyrite were found to be excellent catalyst precursors. Primary alcohols (ethanol and 1-propanol)–CO acted as an effective hydrogen source, whereas branched alcohols were less effective. In the Fe(CO)₅/sulfur catalyzed liquefaction of Yallourn coal at 375°C for 120 min, a high conversion (99.5%) was achieved in the presence of ethanol and CO (7.0 MPa/cold). The two-staged reaction (375°C, 60 min+425°C, 60 min) further improved the oil yield to 59.1% with a slight decrease in the coal conversion. The uptake of alcohol into asphaltene and preasphaltene fractions was distinctly observed, especially for Illinois No. 6 coal. The infrared analyses of the asphaltene fractions from each coal showed absorption at around 1705 cm⁻¹, characteristic for those obtained in the linear alcohol–CO systems. According to the characterization of the products by NMR and the preliminary study using a model compound, alkylation as well as the hydrogenolysis seem to contribute to the dissolution of coals.     

Coal liquefaction with in situ impregnated Fe2(MoS4)3 bimetallic catalyst

Daliuta subbituminous coal (DL), loaded with Fe₂(MoS₄)₃ bimetallic catalyst, was liquefied in a 50 ml micro-autoclave with tetralin as solvent at 440 °C, initial hydrogen of 6.0 MPa, soaking time of 30 min in attempt to produce one to four ring aromatic chemicals. The catalytic effects of in situ impregnated Fe₂(MoS₄)₃ in water solution with and without surfactant were investigated in terms of coal conversion, oil+gas yield and the yields of aromatic, aliphatic and polar compound fractions in the oil. The conversion, oil+gas, aromatics and polar compound yields of DL coal, loaded with 1 wt% daf FeMo of Fe₂(MoS₄)₃ bimetallic catalyst, were 78.2, 70.5, 20.8 and 16.7 wt% daf, respectively, which were higher than those with 1.0 wt% Fe (based on daf coal) of Fe₂S₃ (62.6, 54.2, 13.4, 13.2 wt% daf, respectively) or 1.0 wt% Mo of ammonium tetrathiomolybdate (70.8, 63.2, 16.7, 14.1 wt% daf, respectively) alone under the same conditions. When the catalyst was impregnated on coal in surfactant solution, the coal conversion and product yields were further increased.     

Differences in the behaviour of US bituminous and subbituminous coals during short contact time liquefaction

The short contact time (SCT) liquefaction of Belle Ayr subbituminous coal has been compared with that of Illinois No. 6 and Pittsburgh seam bituminous coals. Each bituminous coal was highly solubilized (90 wt%, daf coal) in 3–4 min at 450 °C and 13–16 MPa hydrogen pressure. More than 80 wt% of each coal was converted to solvent-refined coal (SRC, pyridine-soluble residuum), with only small quantities of distillate oil and C₁–C₄ gas being formed. A longer reaction (up to 30 min) gave only a small increase in total conversion, but gas and distillate yields increased significantly. Iron sulphides did not appear to catalyse coal solubilization. By contrast, only 65 wt% of the Belle Ayr coal dissolved rapidly in SCT liquefaction and pyrite addition catalysed the conversion of the remaining insoluble organic matter (IOM). With an equivalent amount of pyrite present the Belle Ayr coal also gave more C₁–C₄ gas and substantially more distillate in SCT liquefaction than the bituminous coals. These differences in product distributions obtained from bituminous and subbituminous coals in SCT liquefaction can be rationalized on the basis of differences in the structures of the starting coals. However, the origin of high IOM yields with the Belle Ayr coal remains unclear.     

The use of various metal carbonyls as catalyst precursors for coal hydroliquefaction

The catalytic activity of metal carbonyl complexes of chromium, molybdenum, tungsten, manganese, iron, cobalt, and nickel in the liquefaction of coal (Illinois No. 6, Wandoan and Mi-ike) was investigated. The carbonyl compounds of molybdenum, tungsten, iron, cobalt, and nickel acted as highly active catalysts for the liquefaction of Illinois No. 6 coal, resulting in high coal conversion (>90%) and high oil yield (>32%), under hydrogen pressure of 50 kg cm^?1 in a nonhydrogen-donating solvent at 425°C for 60 min. Among the catalysts surveyed, Mo(CO)₆ gave the highest oil yield (57.7%) and the largest amount of hydrogen transferred to coal (3.1 wt.% of d.a.f. coal). However, the molybdenum and tungsten carbonyls did not exhibit high catalytic activity for low sulfur Wandoan coal in the absence of added sulfur. On the other hand, cobalt and nickel carbonyls showed high catalytic activity irrespective of the amount of sulfur in the reaction system. Fe(CO)₅Mo(CO)₆ binary catalyst promoted hydroliquefaction of Wandoan coal, resulting in increases in oil yield and transfer of hydrogen to coal in the presence of sulfur.     

Coal hydroliquefaction using iron pentacarbonyl as a catalyst precursor

Hydroliquefaction of several coals, Taiheiyo (Japanese), Mi-ike (Japanese), Wandoan (Australian), and Illinois No.6 (American), was carried out using iron pentacarbonyl(Fe(CO)₅) at 425–460°C under a hydrogen pressure of 4.9MPa in a non-hydrogen donating solvent, 1-methylnaphthalene. With the addition of iron pentacarbonyl coal conversion increased substantially for all of the coals used. Lighter fraction (oil) also increased, by ≈ 10–17 wt%, in the presence of the catalyst. The addition of Fe(CO)₅ suppressed coking, resulting in high values of coal conversion and oil fraction even at 460°C. The amounts of hydrogen transferred from the gas phase increased by 2–4 times with Fe(CO)₅. A process involving direct hydrogen transfer to coal fragment radicals is proposed.     

Products from rapid heating of a brown coal in the temperature range 400–2300 °C

The devolatilisation behaviour of Yallourn brown coal was investigated under rapid heating conditions using two different flash pyrolysers: a fluid-bed reactor giving coal particle heating rates of 10⁴ °Cs^?1 with a gas residence time of about 0.5 s and a shock tube which generated heating rates of the order of 10⁷ °Cs^?1 and a 1 ms reaction time. Yields of products are reported covering pyrolysis temperatures in the range 400–2300 °C. Hydrocarbon gas yields reached maximum values which were remarkably similar for both reactors although occurring at different temperatures. Carbon oxide production was also similar for both reactors with CO yields reaching 30% wt/wt daf coal. These high yields of CO are very different from those reported for slow heating conditions. It appears that on flash heating, coal decomposition pathways change in a manner which increases CO yields at the expense of H₂0 and to a lesser extent C0₂, resulting in the volatilisation of additional carbon from the coal.     

Synthesis and Investigation of the Catalytic Activity of Nanostructured Potassium Titanates Doped by Ni,Mg, Al,Fe, and Cr

This work presents the results of investigating the catalytic activity of potassium titanate nanomaterials doped by different metals (Ni, Mg, Al, Fe, and Cr) in oxidation reactions of hydrogen and carbon monoxide. It is shown that the best characteristics of the oxidation of the investigated gases have nanotubes doped by aluminium (0.3 × 10^–5 mol H₂/(g s) at 250°C and 10^–5mol CO/(g s) at 350°C).     

Catalytic effects of MoCl3- and NiCl2-containing molten salts in hydroliquefaction of Akabira bituminous coal with and without hydrogen-donor vehicle

Catalytic effects of MoCl₃-LiCl-KCl and NiCl₂-LiCl-KCl molten salts in hydroliquefaction of Akabira bituminous coal were studied. In the absence of solvent, both catalysts showed high coal conversion activity and high selectivity for the formation of hexane-soluble oil product. Oil yields from the catalytic runs were 3.4–3.0 times that from a non-catalytic run. Addition of hydrogen-donor tetralin considerably increased the oil yield and conversion and reduced the total hydrogen consumption. About 95 and 91 wt% daf coal was converted into pyridine-solubles and 59 and 54 wt% into oil with relatively low total hydrogen consumption (3.5 and 3.1 wt% daf coal) with the MoCl₃ and NiCl₂ catalysts respectively, in the presence of tetralin. Thermogravimetric analysis indicated that these catalysts enhanced the depolymerization of the coal organic matrix. Analysis of the liquefaction products suggested that the catalysts effectively catalysed the hydrocracking of polyaromatic structures contained in heavy products to hydroaromatics with relatively small ring sizes, explaining the high oil selectivity.     

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.     

Evaluation of several methods of extraction of oil from a Jordanian oil shale

A Jordanian oil shale from the El Lajjun deposit has been reacted with N₂, H₂ and CO in the presence and absence of water in the temperature range 300–425 °C. The effect of adding Fe, Cu, Ni, Sn and NaAlO₂ as potential catalysts to some of these reactions has been studied but none led to improved oil yields. Most of the organic material in the oil shale was converted to asphaltene at 355 °C, but the oil yield was low at this temperature. At 425 °C nearly all the organic product was in the form of oil.     

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.     

On “partial” coal conversion by extraction with supercritical H2O

This paper presents the results of an exploratory study in which two Western Canadian coals — both furnishing unusually low tar yields by Fischer assays — were extracted with supercritical water at 400–425°C/14–24.5 MPa. In some experiments, CO was used to generate “external” hydrogen for stabilization of coal radicals by the shift reaction; and in others, the effect of a disposable iron catalyst on conversion was examined. Also reported are some observations on the effect of coal pretreatment — specifically: acid leaching, ion exchange against Na⁺, and preheating — on conversion.Data for a Saskatchewan lignite and an Alberta high-volatile bituminous (hvb) coal show that total conversion (to toluene-soluble primary liquids, co-produced water and gas) can range as high as 50 and 35 wt%, respectively, of the d.a.f. coal; that extraction proceeds to virtual completion within 10 min; and that conversion yields can be substantially enhanced by Fe-based catalysts which also allow operation at lower system-pressures than would otherwise required.     

Average structure of coal: Structural analysis of pyridine extract of zinc-water-coal reaction product

Six coals, of 67.5–91.5 wt%C (daf), were hydrogenated with zinc and water under 8 MPa of nitrogen for 30–60 min at 445 °C. This reaction utilizes the hydrogen generated in situ by the reaction Zn+H₂0 = ZnO + 2H₂. The influence of reaction time was examined using the lowest-rank coal and 30 min was found to be the optimum for this coal. The conversion of the various coals was 80.7–100% with the exception of the highest-rank coal, which gave only 36.5% conversion. Structural analysis, carried out for the pyridine-soluble fractions using the Brown—Ladner equations, showed that the aromatic ring size increased from 1 for the lower-rank coals to 4 for the higher-rank coals.     

Hydrogen sorption characteristics of Zonguldak region coal activated by physical and chemical methods

Hydrogen sorption characteristics of activated carbons (ACs) produced by physical and chemical activations from two coal mines (Kilimli and Armutcuk) in the Zonguldak region, Turkey were investigated by a volumetric technique at 77 K. H₂ adsorption isotherms were obtained on the samples exposed to pyrolytic thermal treatments in a temperature range of 600–900 °C under N₂ flow and chemical activation using different chemical agents such as KOH, NH₄Cl, ZnCl₂ from the two mines. Experimental hydrogen adsorption isotherm data at 77 K were used for the evaluation of the adsorption isotherm constants of the Brunauer-Emmett-Teller (BET) and the Langmuir models, and also the amount of hydrogen adsorbed on the various samples was evaluated by using the adsorption isotherm data. Higher hydrogen adsorption capacity values were obtained for all the heat and the chemically treated activated carbon samples from the Kilimli coal samples than Armutcuk. The amount of H₂ adsorbed on the original Kilimli coal samples was 0.020 wt%, and it was increased to 0.89 wt% on the samples pyrolyzed at 800 °C. The highest value of hydrogen adsorption obtained was 1.2 wt% for the samples treated with KOH+NH₄Cl mixture at 750 °C followed by oxidation with ZnCl₂. It was shown that chemical activations were much more effective than physical activations in increasing the surface area, pore volume and the hydrogen sorption capacities of the samples.     

Oxy-ammoniation of Elbistan lignite to produce a nitrogenous fertilizer

Elbistan lignite has been found to contain 50.1 wt% (daf) humic acid. The i.r. spectrum of this lignite, however, indicates the absence of free carboxyl groups. Treatment with mineral acids, however, regenerates the carboxyl groups. A product containing 18.8 wt% N (daf) has been obtained by treatment of HN0₃-treated Elbistan lignite in aqueous ammonia for 4 h at 165 °C and under oxygen pressure. Water-soluble and active nitrogen tests indicate that such products may have the properties of slowrelease nitrogenous fertilizers.     

Pyrolysis of coal and iron oxides mixtures. 2. Reduction of iron oxides

The reduction of iron oxides during the pyrolysis of blends of coal and iron oxides on a laboratory scale, has been studied. The pyrolysis of blends of bituminous coal and 30 wt% of magnetite or hematite has been studied by thermogravimetry and analysis of gases, using a heating rate of 3.2 K min^?1. The state of iron in ferrocoke has been established by X-ray diffraction. A primary reduction by hydrogen and carbon monoxide of the hematite has been observed at between 400 °C and 500 °C, but hidden in thermogravimetric measurements by primary volatilization of the coal. At ≈600 °C magnetite is progressively reduced to wustite and then to iron. This reduction starts a little earlier if the heating rate is slow and the coal rank is low and progresses more rapidly when using hematite. Except for higher heating rates in the coal-magnetite blends, the reduction is complete at 1000 °C. The reductants are H₂ and CO, with production of H₂O and CO₂. When the temperature is increased the reduction by CO becomes of increasing importance, being mainly produced from the coke by the Boudouard reaction. The consumption of coke for the reduction of iron oxides is therefore more important at higher temperatures. Lignite is clearly a better reducing agent than the other coals, because of larger quantities of CO produced from the start of its pyrolysis, and the good reactivity of its char towards CO₂ and H₂O.     

Highly active limonite catalysts for direct coal liquefaction

The properties of limonite in Australia and Indonesia were examined by using X-ray diffraction, Mössbauer spectroscopy, Thermal gravimetric analysis (TGA) and TEM–EDX in relation to the catalytic activities in the liquefaction of low-rank coals. The molar ratio of H₂O/Fe in limonite was determined from the weight loss resulting from the dehydration reaction of FeOOH to Fe₂O₃ during heating from 120 to 400 °C in TGA. The H₂O/Fe molar ratio varied from 0.06 for hematite to 0.60 for limonite YY, depending on the hematite content. Results from the pulverization tests showed that the higher value of H₂O/Fe molar ratio resulted in lesser abrasion of medium balls. A unique limonite YY in Australia, containing no hematite, was easily pulverized to sub-micron particle size and showed an excellent oil yield in coal liquefaction. It appeared that H₂O/Fe molar ratio could be one of the most important factors to select the better limonite catalyst for coal liquefaction. Moreover, it was found that Ni containing limonite SO in Indonesia exhibited a higher liquefaction activity than YY catalyst, because of transformation into a smaller crystallite size of pyrrhotite (Fe_1−xS). The agglomeration of pyrrhotites may be suppressed by a strong interaction between FeOOH and Al(OH)₃ such as Fe–O–Al. TEM–EDX analysis suggests that Ni may be located near the Fe_1−xS structure. Oil yield was significantly increased from 43 to 62 wt% daf by CLB addition to the coal slurry in the liquefaction of Banko coal. Finely pulverized limonite catalyst (SO) can be advantageously used in a commercial plant for coal liquefaction in Indonesia due to the low catalyst cost and a high liquefaction activity to obtain a high oil yield.     

Selective oxidation of CO in hydrogen atmosphere on Pt–Fe catalysts supported on zeolite P-based materials

The catalytic properties of Pt supported on zeolite P (ZP)-based materials for the preferential CO oxidation in hydrogen atmosphere under mild conditions (from room temperature to 150 °C), have been investigated. Pt catalysts (1–4 wt%) supported on a zeolitized pumice support (Z-PM) have been prepared. A series of bimetallic Pt–Fe on ZP, having 2 wt% Pt and different Fe loading (0.5–4 wt%), have been also prepared and used as model catalysts. A detailed characterization of the catalysts has been carried out by means of surface area and porosity measurements, X-ray diffraction, scanning electron microscopy and transmission electron microscopy in order to investigate the morphological and microstructural properties of both support and catalytic system. Pt/Z-PM exhibited complete CO conversion with 55 % selectivity at temperatures as low as 50 °C, with no noticeable degradation of the catalytic performances, indicating that the Fe content present as an impurity in the zeolitized pumice support allows to obtain catalysts characterized by high activity and stability. On the basis of the characterization and kinetic tests, hypotheses on the role of Fe promoter have been formulated.     

Coal liquefaction by colloidal iron sulphide catalyst

Taiheiyo coal, which was treated with an aqueous solution of dodecyltrimethylammonium chloride, adsorbed colloidal iron sulphide prepared from FeS0₄ · 7H₂O and Na₂S · 9H₂O in aqueous media. The adsorbed colloidal iron sulphide was much more effective as a catalyst for the liquefaction of the coal itself than the usual powder-type iron sulphide. Thus in differential thermal analysis under hydrogen, the coal with 0.35wt% adsorbed colloidal iron sulphide gave an exothermic peak at 401 °C, which was ≈20 °C lower than when using the powder-type iron sulphide. The coal was smoothly hydrogenated at 450 °C to give a yield of ≈60% liquid products.