Effect of the ozonization of brown coal from the Kansk-Achinsk Basin on its pyrolysis in a mixture with polyethylene

It was found that the treatment of brown coal from the Kansk-Achinsk Basin with an ozone-oxygen mixture at 25–100°C for 1–8 h was accompanied by the formation of oxygen-containing structural groups in the organic matter of coal; the thermal stability of these groups was comparatively low. The preliminary ozonization of coal resulted in an increase in the degree of conversion and the yield of liquid distillation products in the course of coprocessing of coal with polyethylene.     

Flash pyrolysis of coals. 1. Devolatilization of a Victorian brown coal in a small fluidized-bed reactor

The devolatilization behaviour of finely-ground (< 0.2 mm) Loy Yang brown coal was investigated under rapid heating conditions using a small-scale fluidized-bed pyrolyser. The pyrolyser operated continuously, coal being fed at rates of 1–3 g/h directly into a bed of sand fluidized by nitrogen. Particle heating rates probably exceeded 10⁴ °C/s. The yields of tar, C₁-C₃ hydrocarbons and total volatile matter are reported for a pyrolyser-temperature range of 435 to 900 °C. A maximum tar yield of 23% w/w (dry ash-free coal), 60% more than the Fischer assay, was obtained at 580 °C. Yields of C₁-C₃ hydrocarbons increased with increasing temperature, reaching 8% at 900 °C. Elemental analyses showed that the composition of the tar and char products was strongly dependent on pyrolysis temperature. The effects on the devolatilization behaviour of the coal produced by the moisture associated with the coal, by hydrogen, and by the replacement of the sand by a fluidized bed of petroleum coke were investigated.     

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.     

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.     

Catalytic cracking of the semicoking tar of coal from the Shubarkol deposit

The results of studies on the application of a catalytic composition synthesized based on finely dispersed silicon-containing natural clay from the Narynkol deposit (Republic Kazakhstan) and a water-soluble silicon salt (Ba–Al–Si) to the process of the catalytic cracking of the semicocking tar of coal from the Shubarkol deposit are reported. It was established that, in the presence of this composition, the yield of a gasoline fraction at a temperature of 420°C and an argon pressure of 3.0 MPa was 34%, and the yield of a diesel fraction was 50%; this fact makes it possible to consider coal tar as a potential raw material for the production of motor fuel components.     

Influence of carrier gas flow and heating rates in fixed bed hydropyrolysis of coal

Fixed bed hydropyrolysis experiments on a UK bituminous coal (82% dmmf C) at 580–650 °C and pressures up to 300 bar have indicated that tar yields depend strongly on the velocity of the hydrogen carrier gas relative to the static coal particles. Tar yields increase with increasing pressure provided that the superficial gas velocity is not reduced. Otherwise, tar yields can actually decrease because the beneficial hydrocracking reactions that occur are no longer sufficient to counter the increased char formation resulting from the slower rates of intra-particle diffusion and devolatilization of tar molecules. While raising the heating rate from 1 to 20 °C s⁻¹ had little effect on overall conversions, hydrocarbon gas yields increased significantly at the expense of tar. Moreover, the higher heating rate gave more aromatic tars, and the available evidence strongly suggests that the primary volatiles are hydrocracked before escaping from the coal particles as well as in the vapour phase.     

Hydrogenation of the semicoking tar of coal from the Shubarkol deposit

The results of the hydrogenation processing of the semicoking tar (AO Sary Arka Spetskoks, Karaganda, Republic of Kazakhstan) of coal from the Shubarkol deposit in the presence of Mo- and Ni-containing pseudohomogeneous catalytic systems for the production of motor fuel components and chemical substances are reported. It was established that the yield of a gasoline fraction at a temperature of 400°C (5.0 MPa, a 0.015% S additive) was 18.7% with the use of a molybdenum catalyst or 10.6% with a nickel catalyst; therefore, the coal tar can be considered as a potential raw material for obtaining motor fuel components.     

提高洗苯效率的有效途径

介绍了焦化厂焦油洗油吸收煤气中苯的工艺流程,分析了造成粗苯产量低的主要原因是循环洗油270℃前馏程偏低。在统计分析的基础上找出造成循环洗油270℃前馏程偏低的主要因素,认为控制洗油270℃前馏程≥70%,是提高粗苯收率的有效途径。     

Effect of pressure on the hydropyrolysis of Manvers coal

Manvers weakly-coking coal was pyrolysed to 500 °C in a stirred autoclave under varying pressures of hydrogen and nitrogen. As expected the major changes produced by increase in nitrogen pressure were a decrease in tar yield accompanied by increases in gas and, to a smaller extent, in coke yields. Total pressures and hydrogen :coal ratios were altered to obtain maximum yields of tar, gases and liquor. All products were investigated. Tar fractions, separated into neutral, phenolic and basic components, were analysed by g.c.-m.s. Short-chain hydrocarbons were detected in the gas sample. Methanol densities and micropore surface areas the cokes were related to the conditions of pyrolysis. At the relatively low rates of heating employed, pressure had effects on tar composition similar to increasing the temperature of pyrolysis.     

Thermal Dissolution of Coking Coals in the Anthracene Fraction of Coal Tar

The thermal dissolution of two samples of 1GZhR and ZhR coal in the anthracene fraction of coal tar is studied. The yield of quinoline-soluble products increases considerably in the temperature range of coal softening. Optimal thermal-dissolution conditions are determined for selective production of quinoline-soluble pitch-like products. At 350–380°C, the yield of quinoline-soluble products is 70–73% after 1–2 h. The yields of the distillate fraction and the gas are 0.9% and 0.2%, respectively. The ash-free pitch-like product is a plastic mass with a softening temperature of 76–81°C. It consists mainly of polycyclic aromatic hydrocarbons with a few short alkyl substituents in the aromatic rings. The spatial structure mainly includes poorly structured polycyclic aromatic molecules of the γ component. The proportion of relatively ordered graphitelike packets is 31–37%. Each packet contains five stacked polycyclic aromatic molecules of diameter 17 Å. In terms of its composition and plasticity, the product is suitable as a source of alternatives to coal pitch.     

Unusual effects of catechol upon the hydroliquefaction of coal

The effect of catechol on coal hydrogenolysis was studied using tetralin as a solvent vehicle. A constant high liquefaction yield was observed when the amount of catechol added was reduced from 10 to 0.1 % based on the weight of coal. Under the same hydrogenolysis conditions, identical conversion yields were observed even when no catechol was added. Separate experiments were carried out, using a new internal vessel and the original stirrer, to examine the effect of the stirrer on liquefaction yield. Improved liquefaction yields were achieved in these experiments (an increase from 31 to 64% at 400 °C and from 46 to 78% at 420 °C for Miike coal; from 26 to 48% at 400 °C and from 36 to 73% at 420 °C for Wandowan coal; and from 16 to 34% at 400 °C and 21 to 55% at 420 °C for Lithgow coal). This suggests that an active catalytic species is formed on the surface of the stirrer and the internal surface of the autocalve.     

Pyrolysis of a ZnCI2-impregnated coal in an inert atmosphere

Untreated and ZnCI₂-impregnated samples of Linby bituminous coal were pyrolysed at atmospheric pressure in a Gray—King retort and a quartz fluidized bed. It was confirmed in the Gray-King retort that in the absence of externally added hydrogen, and at slow heating rates (several degrees per minute), the effect of impregnating ZnCI₂ is to increase the char yield and to suppress tar production. It was found that this trend can be reversed by flash-pyrolysing the ZnCI₂-impregnated samples. Tar yields as high as 35% (at 10% ZnCI₂ loading) were observed at 582 °C, compared to 22% tar from the untreated coal. This reversal of the product distribution trend is seen to be caused solely by the increase in heating rates, and not by the difference between the geometries of the equipment.     

Production of isotropic coke by thermocracking of the anthracene fraction of coal tar

The properties of coke obtained by heat treatment of the anthracene fraction of coal tar under pressure (by thermocracking) are investigated. Pressures up to 5 MPa are used; the temperature is 500 or 550°C. For comparison, pitch coke is obtained from oxidized pitch with softening temperatures of 166.2 and 190.2°C. The coke yield from thermocracking is 70–75%. The following properties of the coke are determined: the actual density, the ash content, the yield of volatiles, the optical microstructure, the elementary composition, the change in volume on heating to 2400°C, the impurity composition, and the X-ray structural characteristics. High temperatures (at least 550°C) and heating rate of the anthracene fraction facilitate the formation of a large quantity of active radicals, which instantaneously form the three-dimensional coke structure, preventing the growth and coalescence of mesophase particles; isotropic coke is formed, with a microstructure score of 2.2. At 500°C, anisotropic coke is formed, with a microstructure score of 4.3. Despite the high softening temperature and the content of the α1 fraction, the high-temperature pitch does not form isotropic coke on carbonization. The macrostructure of the coke obtained by thermocracking is monolithic, with fine pores. The thermocracking conditions (temperature, pressure, presence of H₂) facilitate partial destruction and hydrogenation of the heterocyclic compounds. As a result, the coke has a reduced N, S, and O content. For pitch coke, the nitrogen content is 20–40% higher. The lack of ash in the anthracene fraction of coal tar results in ash- and metal-free coke. The coke obtained by thermocracking also has satisfactory X-ray structural characteristics and undergoes practically no expansion on graphitization, in contrast to pitch coke. In view of the technological convenience (absence of liquid products, high coke yield) and the quality of the coke, the production of isotropic coke by thermocracking may be regarded as a promising means of supplying the raw material used to produce artificial graphite.     

Flash pyrolysis of coals. Devolatilization of bituminous coals in a small fluidized-bed reactor

The devolatilization behaviour of ten bituminous coals was investigated under rapid heating conditions using a small-scale fluidized-bed pyrolyser. The pyrolyser operated continuously, coal particles being injected at a rate of 1–3 g h^?1 directly into a heated bed of sand fluidized by nitrogen. Yields of tar, C₁–C₃ hydrocarbon gases, and total volatile-matter and an agglomeration index are reported for all coals. Maximum tar yields were obtained at about 600 °C and were always substantially higher than those from the Gray-King assay. Total volatile-matter yields were also substantially higher than the proximate analysis values. The maximum tar yields appear to be directly proportional to the coal atomic $\text{H}\text{C}$ ratio. The elemental analysis of the tar is strongly dependent on pyrolysis temperature. The tar atomic $\text{H}\text{C}$ ratio is proportional to that of the parent coal. The effect on the devolatilization behaviour of two coals produced by changes in the pyrolyser atmosphere and the nature of the fluidized-bed material were also investigated. Substituting an atmosphere of hydrogen, helium, carbon dioxide or steam for nitrogen, has no effect on tar yield and, with one exception, little effect on the hydrocarbon gas yields. In the presence of hydrogen the yield of methane was increased at temperatures above 600 °C. Tar yields were significantly reduced on substituting petroleum coke for sand as the fluid-bed material. A fluidized bed of active char virtually eliminated the tar yield.     

Temperature Effect on the Thermal Dissolution of Coal

The main process characteristics of the thermal dissolution of grade Zh coal in the anthracene fraction of coking tar depending on temperature and reaction time were determined. It was established that the effective extraction of quinoline-soluble products occurred in a temperature range of coal conversion into a plastic state. The process proceeded selectively; at 350–380°C, the yield of the quinoline-soluble products was 71–75%. In this case, the yield of toluene-soluble products did not exceed 10%, and the yield of gas was 0.5%. At a higher temperature and a long reaction time (>2 h), a sharp decrease in the characteristics of thermal dissolution occurred.     

Release of chloroform-extractable materials from a bituminous coal after mild heating

Samples of Linby coal were heated to ⩽ 400 °C and afterwards extracted with chloroform in a Soxhlet apparatus. Extract yields were observed to pass through a minimum around 350 °C, suggesting loss of potential extract near 350 °C, in contrast to a coking coal for which extract yields increased monotonically with temperature. Between 350 and 400 °C bond rupture produced small amounts of tar and increases in extract yield. Samples impregnated with ZnCl₂ prior to heating yielded less extract and released larger amounts of molecular hydrogen and lower hydrocarbons. At the slow heating rate used (5 °C/min) the catalyst appeared to promote condensation and de-alkylation reactions, the effect becoming more pronounced above 350 °C.     

Mechanism of coal pyrolysis in relation to industrial practice

The validity of our earlier postulates of the mechanism of primary pyrolysis (at and up to 600 °C) is critically examined and it is indicated that the mechanism is strictly followed only under ideal conditions, e.g. in thin beds at rapid rates of carbonization, as in fluidbed and transport reactors. The departure of the Gray-King assay (600 °C) from the ideal path of pyrolysis, e.g. by yielding 20–30% less tar than the yield corresponding to hydroaromatic carbon content, is shown to be due to interaction between the potential tar-forming constituents and the incipient coke-forming substance. This appears to be a function of the thickness of the coal bed, the rate of heating, etc. The greater the thickness, the greater is the degree of interaction and consequent inhibition of tar formation, resulting in a proportionate increase in coke yield. Coke and tar yields are thus partly interconvertible, and the proportions of such interaction have virtually no effect on the proportion of carbon appearing as gas. In industrial high-temperature carbonization, the higher yields of coke and lower yields of tar are due to the same interaction, which occurs to a greater extent primarily because of the greater thickness and/or depth of the coal bed in coke ovens. The fixation of up to 75% of the ‘tar-forming’ carbon (hydroaromatic carbon according to the theory) does not appear to be due to cracking of tar after its formation, but is shown to be foreshadowed well within the primary stage of pyrolysis (below 600 °C), perhaps through condensation-polymerization reactions within the formative coke mass, the mechanism of which is ill-understood at present. The process appears to be very different from the cracking mechanism hitherto believed to explain it. This conclusion is also supported by a study of the distribution of carbon in the gas. Further, such comparative studies between laboratory and industrial conditions do not indicate any significant cracking of methane, hitherto believed to occur in coke ovens. Correspondingly, the reasons for carbon deposition on the exposed hot walls and other regions of coke ovens are discussed and doubt is thrown on the belief that it derives from the cracking of tar and gas.     

Benefits of ultrasound in pitch production from coal tar and its mixtures with styrene distillation residue

Ultrasound treatment of coal tar increases the yield of pitch by a factor of 1.5 in subsequent oxidation by atmospheric oxygen. The yield of pitch may be regulated in terms of its softening temperature by changing the oxidation time. To obtain standard pitch, the following conditions are employed: ultrasound treatment for 3 h; initial oxidation temperature 260–270°C; final oxidation temperature 360–370°C; rate of air supply 63 L/h; oxidation time ~30–70 min, depending on the requirements on the final product. The concentration of aromatic derivatives of benzo[a]pyrene type in the pitch produced and in the liquid fraction (which may be used as a fuel) is considerably less than in the current industrial method. After ultrasound treatment, a 1: 1 mixture of coal tar and rectification residues from styrene yields pitch with satisfactory characteristics on oxidation by atmospheric air. That expands the range of raw materials for pitch production.     

Composition and properties of coal from the Tsaydam Nuur deposit in Mongolia

The composition, thermal characteristics, and reactivity of coal from the new Tsaydam Nuur deposit in Mongolia in the processes of pyrolysis, thermal dissolution, and the production of sorbents were determined. It was established that the coal is low-rank brown coal of the lignite type, which is characterized by high activity in degradation reactions. In the process of thermal dissolution in tetralin at 450°C without the use of hydrogen, the yield of products soluble in chloroform was as high as 80%. The yield of primary tar upon semicoking was 13%. Activated carbons with a sorption capacity of 510 mg/g for iodine were obtained by the steam activation of carbonization products.     

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.