Additive effect of tyre constituents on the hydrogenolyses of coal liquefaction residue

A numerous amount of waste tyre is landfilled or dumped all over the world, which causes environmental problems. The coal liquefaction residue (CLR) produced in 30% yield through the process supporting unit of the NEDOL coal liquefaction process. As one of the effective method for processing both CLR and waste tyre, simultaneous hydrogenolyses of these materials was carried out. The synergistic effects to upgrading, such as the increase of oil yield and the decrease of asphaltene yield, were appeared on the hydrogenolyses. However, the interaction between tyre and CLR to synergistic effects was not clarified. In this study, the effects of hydrogen donatable solvent (tetralin) and pressurized gas on the hydrogenolyses of CLR and tyre constituents are discussed. As a result, it was clarified that both tetralin and the pressurized H₂ gas were necessary for the simultaneous hydrogenolyses of CLR and tyre. The hydrogen shuttling from H₂ gas and tetralin was enhanced by the aromatic compounds derived from tyre rubber constituents (styrene-butadiene rubber and natural rubber). The hydrogenation of the heavy oil constituent in CLR was enhanced by carbon black and the inorganic constituents in tyre, such as zinc oxide and sulfur. Accordingly, the synergistic effects on the simultaneous hydrogenolyses of CLR and tyre were appeared because the hydrogen shuttling occurred by the aromatics from tyre rubber constituents, and the hydrogenation was enhanced by carbon black and the inorganic constituents in tyre.     

The upgrading of petroleum residuum and coal in catalytic coprocessing

The combined catalytic reactions using different types of petroleum residuum and coal were performed at 425°C and 60 minutes in the presence of hydrogen to upgrade both materials to high quality synthetic fuels. In order to improve this coprocessing technology, the effect of the chemical and physical properties of both materials on the coprocessing product yields was investigated through a parametric study. In all reaction combinations, substantial increase in maltene production and high coal conversions of over 84% were observed regardless of petroleum residuum type and coal rank. The petroleum residuum properties of specific gravity and conradson carbon residue had effects on asphaltene production and coal conversion. The results of quantitative analysis for the amount of coal upgraded during coprocessing lead to conclude thata large amount of coal converted to maltene fraction due to high catalytic activity and reactive hydrogen donor richness of coprocessing system. However, most of the heavier fractions were formed primarily from coal regardless of the type of residuum used.     

Hydrothermal dewatering of lower rank coals. 2. Effects of coal characteristics for a range of Australian and international coals

A range of lower rank coals from Australia, Indonesia, and the USA have been dried under hydrothermal dewatering conditions at 320 °C for 30 min in a 500 ml autoclave using a 1:3 dry coal/water mixture. The hydrothermally dewatered (HTD) products were characterised by elemental analysis (both organic and inorganic components), volatile matter determinations, moisture holding capacity, calorific value and mercury porosimetry. The total organic carbon (TOC) and the concentrations of inorganics in the waste waters were also determined. The coals fell into two broad groups, the lower rank Australian brown coals with gross calorific values in the range 10-16 MJ/kg (afm) and the higher rank Indonesian and US coals with gross calorific values in the range 18-25.5 MJ/kg (afm). Rank was the major factor influencing the properties of the HTD products but lithotype was also important. TOC values of the waste water from drying of the low rank Australian coals were much higher than those of the waste water from the higher rank coals. Important variations in the amount of leached calcium, magnesium, and iron were noted.     

Influence of additives of various origins on thermoplastic properties of coal

Two coking coals of different rank were chosen in order to assess the influence of various additives on their thermoplastic properties. Six additives of different origin and characteristics were selected: two non-coking coals, together with a commercial coal tar pitch, a residue from the bottom of the benzol distillation tower and two residues from the tyre recycling industry. The effect of the additives on coal thermoplastic properties was assessed by means of the Gieseler test. The additives were pyrolyzed to a final temperature of 550 °C and the tar characterized by means of Fourier transform infrared spectroscopy (FTIR) and gas chromatography (GC). The influence of the additives on coal thermoplasticity is related to the volatile matter content of the additive, its evolution profile with temperature and the composition of the tar obtained during the pyrolysis of the additives.     

The use of coal liquefaction catalysts for coal/oil coprocessing and heavy oil upgrading

The catalytic hydrogenation of heavy oil and mixed coal-heavy oil (coprocessing) systems has been the focus of a recent study at the Federal Energy Technology Center (FETC). The intent of this effort was to extend the use of coal liquefaction technologies to heavy oil upgrading and coprocessing systems. Specifically, new dispersed molybdenum-based catalysts developed at FETC and a novel silica-doped hydrous titanium oxide (HTO : Si)-supported NiMo catalyst developed at Sandia National Laboratories (SNL) were tested in these systems. The results indicate the potential of coal liquefaction catalysts for use in coprocessing and heavy oil upgrading. High conversions of coal–oil mixtures were observed with dispersed catalyst loadings as low as 100 ppm Mo. Similar results were observed in heavy oil systems. Also, the novel NiMo/HTO : Si catalyst was at least as effective as commercially-available supported catalysts (e.g. Amocat 1C) for conversion of high boiling point material to distillable products and aromatics removal.     

Submicron ash formation from coal combustion

In recent years, fine particles have been found to be the cause of various harmful effects on health, and many countries have imposed restrictions on emission of these particles. Fine ash particles are formed during coal combustion in power stations and, if not collected in the air pollution control devices, are emitted into the atmosphere. The fine ash particles can remain airborne for long periods and can result in deleterious health effects when inhaled and deposited in the lungs.Previous studies have shown that combustion of coals of different rank can result in differences in the amount and chemistry of the submicron ash particles. This study examines the variability occurring between the submicron ashes formed from coals of similar rank. Five Australian bituminous coals were burned in a laminar flow drop tube furnace in two different oxygen environments to determine the amount and composition of submicron ash formed. The experimental setup is described and the repeatability of the experiments is discussed. The variability in the submicron ash yield as a percentage of the total ash collected and the submicron ash composition are presented and discussed. This paper presents experimental results rather than a detailed discussion on its interpretation. However, the results indicate that the condensation of evaporated species is responsible for the formation of ash particles smaller than 0.3 μm.     

Relationship between properties and conversions of North Bohemian coals during coal/oil coprocessing

Eleven low rank coals from North Bohemian mines were comprehensively characterized by using a number of analytical methods. Along with common proximate and ultimate analysis, spectroscopic techniques, porosity measurement, extractability and swelling in organic solvents were used. Although coals were of similar geological origin, some of their characteristics largely differed from one coal to another. Coals were coprocessed with petroleum vacuum residue at 440°C for 1 h and yields of reaction products and coal conversions were determined. Despite the differences in composition and properties, the coals provided similar conversions and yields of distillable reaction products. A small positive effect on coal conversion was found for ash content and microporosity of coals. However, a small negative effect was found for carbon content, optical reflectance and solvent extractability of coals.     

XRD evaluation of KOH activation process and influence of coal rank

Three Japanese coals with different rank (Ohmine, Miike and Taiheiyo coals) were activated with KOH from 300 to 850 °C. Higher rank coal with lower oxygen content showed a high yield and also a large specific surface area determined by N₂ adsorption isotherms. X-ray diffraction (XRD) patterns of the activated carbons were measured to characterize stacking structure of aromatic layers by standardized analysis of coal by XRD method, considering the presence of slit-shaped micropores among the stacking structure. Structural parameters obtained by this method were related to the yield and the surface area in order to discuss the feature of micropores developed during the activation.     

Ignition characteristics of coal blends in an entrained flow furnace

Ignition tests were carried out on blends of three coals of different rank - subbituminous, high volatile and low volatile bituminous - in two entrained flow reactors. The ignition temperatures were determined from the gas evolution profiles (CO, CO₂, NO, O₂), while the mechanism of ignition was elucidated from these profiles and corroborated by high-speed video recording. Under the experimental conditions of high carbon loading, clear interactive effects were observed for all the blends. Ignition of the lower rank coals (subbituminous, high volatile bituminous) enhanced the ignition of the higher rank coal (low volatile bituminous) in the blends. The ignition temperatures of the blends of the low rank coals (subbituminous-high volatile bituminous) were additive. However, for the rest of the blends the ignition temperatures were always closer to the lower rank coal in the blend.     

Influence of coal thermoplastic properties on coking pressure generation: Part 2 - A study of binary coal blends and specific additives

A number of coal blends and pitch/coal blends were evaluated using rheometry, thermogravimetric analysis and microscopy to confirm and further elucidate the coking pressure mechanism previously proposed by Duffy et al. (2007) [1]. We confirm that blending a low rank, high fluidity, low coking pressure coal, with a high rank, low fluidity, high coking pressure coal can significantly reduce the coking pressure associated with the latter. Interestingly, blending does not necessarily result in a fluidity that is midway between that of the two coals; sometimes the fluidity of the blend is less than that of the low fluidity coal, especially when the coals are significantly different in rank. This occurs because the increase in complex viscosity (η*) through resolidification of the low rank, high fluidity coal counteracts the reduction in η* resulting from softening of the high rank, low fluidity coal. It has also been confirmed that the η* of the resultant blend can be estimated from the η* of each component coal using a logarithmic additivity rule commonly employed for polymer blends.Polarised light microscopy has indicated that the degree of mixing between coals of different rank is minimal, with fusion restricted to the particle surface. It is therefore inappropriate to think of such a coal blend in the same way as a single coal, since each component coal behaves relatively independently. This limited fusion is important for understanding the coking pressure mechanism for blends. It is proposed here that the lower rank coal, which softens at lower temperature, is able to expand into the interparticle voids between the high rank coal that is yet to soften, and these voids can create channels for volatiles to traverse. Then, and importantly, when the high rank coal begins to expand, the pore structure developed in the resolidified structures of the low rank coal can facilitate removal of volatiles, while the resolidified material may also act as a suitable sorbent for volatile matter. This is considered to be the primary mechanism by which coal blending is able to alleviate coking pressure, and applies to addition of inert material also.Addition of a coal tar pitch was found to increase fluidity but also to extend the thermoplastic range to lower temperatures. This caused an increase in the swelling range, which was accompanied by a long plateau in η*, a feature which has previously been observed for certain high fluidity, high pressure coals. Elasticity and η* at the onset of expansion were also higher for both the pitch impregnated coals and the high pressure blends, which supports previous findings for singly charged high pressure coals, and confirms the potential use of such criteria for identifying potentially dangerous coals/blends.     

Spontaneous combustion of carbonaceous stockpiles. Part I: the relative importance of various intrinsic coal properties and properties of the reaction system

The likelihood of a coal stockpile or carbonaceous waste dump undergoing spontaneous combustion is strongly influenced by factors that relate to both the intrinsic properties of the material itself, as well as the properties of the reaction system. An understanding of these material properties is a pre-requisite for the simulation of the large-scale reaction system with the aim of preventing or containing this phenomenon.The first part of this paper investigates a range of coal properties that were considered to be the most critical in terms of heat ‘generation’ in a bulk coal medium. Certain properties, such as the heat capacity, the heat of reaction with oxygen and the activation energy for this reaction, were found to vary to a relatively minor degree for coals of varying rank and geological origin. However, rates of reaction with oxygen were found to vary by orders of magnitude for different coals. The reaction kinetics is consistent with a diffusion-limited shrinking-core model. A study of the coal properties that most strongly influence these rates of reaction is the subject of part two of this paper.     

Floatability and desulfurization of a low-rank (Turkish) coal by low-temperature heat treatment

It is well known that higher rank coals are inherently hydrophobic whereas lower rank coals are more hydrophilic. Because of the hydrophilic character of low-rank coals, they are difficult to float even at high dosages of oily collectors. In the present study, the floatability behavior of a hydrophilic lignitic coal was investigated with and without low-temperature heat treatment using a column flotation and a Denver flotation cell. The floatability and hydrophobicity of the coal were investigated upon heating the coal at 105 °C. After heating it was found that the floatability, hydrophobicity, and separation efficiency of lignite increased dramatically. A change in the hydrophobicity of lignite before and after the low-temperature heating was determined by FTIR spectroscopy. On the other hand, reverse flotation experiments applied in natural, alkaline, and acidic conditions yielded rather good results. A concentrate assaying 1.52% total sulfur was obtained at natural pH from a feed of 2.50% sulfur.     

Hydrogen production by methane cracking over different coal chars

Hydrogen production by methane cracking over a bed of different coal chars has been studied using a fixed bed reactor system operating at atmospheric pressure and 1123 K. The chars were prepared by pyrolysing four parent coals of different ranks, namely, Jincheng anthracite, Binxian bituminous coal, Xiaolongtan lignite and Shengli lignite, in nitrogen in the same fixed bed reactor operating at different pyrolysis temperatures and times. Hydrogen was the only gas-phase product detected with a GC during methane cracking. Both methane conversion and hydrogen yield decreased with increasing time on stream and pyrolysis temperature. The lower the coal rank, the greater the catalytic effect of the char. While the Shengli lignite char achieved the highest methane conversion and hydrogen yield in methane cracking amongst all chars prepared at pyrolysis temperature of 1173 K for 30 min, a higher catalytic activity was observed for the Xiaolongtan lignite char prepared at 973 K, indicating the importance of the nature of char surfaces. The catalytic activity of the coal chars were reduced by the carbon deposition. The coal chars had legible faces and sharp apertures before being subjected to methane cracking. The surfaces and pores of coal chars were covered with carbon deposits produced by methane cracking as evident in the SEM images. The results of BET surfaces areas of the coal chars revealed that the presence of micropores in the chars was not an exclusive reason for the catalytic effect of the chars in methane cracking.     

Solvolytic liquefaction of coals with a series of solvents

Solvolytic liquefaction of coals of different rank was studied with a variety of solvents at 370–390 °C under nitrogen in order to elucidate the role of solvent in coal liquefaction of this kind and to find a suitable solvent for the highest yields of liquefaction. The yield was found to depend strongly upon the nature of the coal as well as the solvent under these conditions. Pyrene and a SRC-BS pitch were excellent solvents for Miike coal, which was fusible with high fluidity at these temperatures. However, the former was less efficient for Itmann and Taiheiyō coals which were fusible at a higher temperature and non-fusible, respectively. The mechanism of solvolytic liquefaction is discussed, including nature of coal and solvent at reaction temperatures, in order to understand the properties required for high yields with non-fusible coals in solvolytic liquefaction. It is found that for liquefaction with a high yield if the coal is non-fusible, solvolytic reaction should take place between solvent and coal, so giving a liquid phase of low viscosity at the reaction temperature. The solvolytic reaction may be one of hydrogen transfer when SRC-BS is used as the solvent.     

Viscosity changes in coal paste during hydrogenation

Using a viscometer that operates up to a maximum pressure of 29.4 MPa and a maximum temperature of 550 °C, the viscosity of coal paste and its changes with temperature were investigated, and also some effects of: type of vehicle oil, coal to vehicle oil ratio, coal particle size, atmosphere, pressure, catalyst and coal rank. In the viscosity-temperature curve for the paste from high rank bituminous coals, a peak was observed near 300 °C, which is considered to be due to the extractive disintegration of the coal by the vehicle oil. Under hydrogenation with high pressure hydrogen and hydrogenation catalyst, the extractive disintegration of coal was promoted, and the viscosity was higher than that in nitrogen atmosphere. The viscosity behaviour of the coal paste from low rank coals was the same as that of the vehicle oil alone.     

Reaction mechanism of coal hydrogenation. 3. Effect of coal type

Seven coals have been hydrogenated in naphthalene and phenanthrene under 10 MPa (initial pressure) of hydrogen with a stabilized niekel catalyst at 400°C for 15 min. Preasphaltene, asphaltene and oil conversions and solvent conversion were measured. The amounts of hydrogen absorbed by coal and by solvent were calculated. Coal conversion and the amount of hydrogen absorbed by coal decreased, while the amount of hydrogen absorbed by solvent increased, with increase in coal rank. The ratio of the amounts of hydrogen absorbed by coal and by solvent showed a good correlation with conversion to benzene- and n-hexanesoluble materials. Naphthalene and phenanthrene gave similar results, suggesting that the coal was hydrogenated directly by gaseous hydrogen.     

Effects of pressure in coal pyrolysis observed by high pressure TGA

High-pressure thermogravimetric analyzer was employed to investigate the effects of pressure on the thermal decomposition process, which is the very first step in most coal utilizing processes, and pyrolyzates from TGA were analyzed by on-line GC/MS. Results showed that pyrolysis of coal with steam under high-pressure conditions exhibited a slower reaction rate compared to the lower pressure conditions, and the effect is more evident at the high temperature region. Coal rank also exhibited a distinct effect on the pyrolysis rate such that a subbituminous coal showed a bigger effect by steam-addition and pressure than bituminous coals. Weathered coal sample illustrated a slower reaction rate compared to the unoxidized coal. In addition, the implication of pressure effects on pyrolysis has been described.     

Coal liquefaction by in-situ hydrogen generation.: 1. Zinc-water-coal reaction

Liquefaction of coal was carried out in a zinc—water—solvent system to give a product with high concentration of pyridine and benzene solubles. In this system the metal reacts with water to produce the corresponding metal oxide and hydrogen. This hydrogen was used for in-situ hydrogenation of coal. The effects of reaction time, temperature, type of solvent, the quantity of metal used and the rank of coal were investigated. The solvent has a very marked effect on the conversion of coal to benzene-soluble materials, especially at short reaction times. A maximum benzene conversion of 96% for Taiheiyo coal was obtained when it was treated at 445 °C for 1 h using wash oil as solvent. With regard to the influence of coal rank it was found that low rank coals were more reactive than high rank coals. The amount of preasphaltene is only slightly influenced by coal rank but depends on the temperature and the type of solvent used.     

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.     

Minimization of Moisture Readsorption in Dried Coal Samples

Low-rank coals csonstitute a major energy source for the future as reserves of such high-moisture coals around the world are vast. Currently they are considered undesirable since high moisture content entails high transportation costs, potential safety hazards in transportation and storage, and the low thermal efficiency obtained in combustion of such coals. Furthermore, low-moisture-content coal is needed for the various coal pyrolysis, gasification developed. Hence, various upgrading processes have been developed to reduce the moisture content. Moisture readsorption and spontaneous combustion are important issues in coal upgrading processes. This article discusses results of laboratory experiments conducted to study the options for minimization of readsorption of moisture after drying of selected coal samples. Results suggest that there is little benefit in drying low-rank coal at high temperatures. It was found that the higher the amount of bitumen used for coating, the lower is the readsorption of moisture by dried coal. Also, mixing high-temperature-dried coal with wet coal in appropriate proportion can yield reduced moisture content as the sensible heat in the hot coal is utilized for evaporation.