Bituminous coal, pyrolysis product

Properties. A high volatile western Kentucky bituminous coal, the tar yield of which by Fischer assay was ca 16%, gave a tar yield of ca 26% at a pyrolysis temperature of 537°C (146—148). Tar yield peaked at ca 35% at 577°C and dropped off to 22% at 617°C. The char heating value is essentially equal to that of the starting coal, and the tar has a lower hydrogen content than other pyrolysis tars. The product char is not suitable for direct combustion because of its 2.6% sulfur content. 

The use of pyrolysis for the recycling of mixed plastics is discussed and it is shown that fluidised bed pyrolysis is particularly advantageous. It is demonstrated that 25 to 45% of product gas with a high heating value and 30 to 50% of an oil rich in aromatics can be recovered. The oil is found to be comparable with that of a mixture of light benzene and bituminous coal tar. Up to 60% of ethylene and propylene can be produced by using mixed polyolefins as feedstock. It is suggested that, under appropriate conditions, the pyrolysis process could be successful commercially. 23 refs. 

It is possible to produce some liquid hydrocarbons from most coals during conversion (pyrolysis and hydrogenation/ catalytic and via solvent refining)/ but the yield and hydrogen consumption required to achieve this yield can vary widely from coal to coal. The weight of data in the literature indicate that the liquid hydrocarbons are derived from the so-called reactive maceralS/ i.e. the vitrinites and exinites present (7 8 1 9). Thusf for coals of the same rank the yield of liquids during conversion would be expected to vary with the vitrinite plus exinite contents. This leads to the general question of effect of rank on the response of a vitrinite and on the yield of liquid products and/ in the context of Australian bituminous coals, where semi-fusinite is usually abundant/ of the role of this maceral in conversion. 

Tables 4.4 and 4.5 show the effect of temperature on product yield and composition from the pyrolysis of mixed municipal solid waste (MSW) and bituminous coal. Other data11 show that beyond a certain temperature char yield does...

Table 4.5 Effects of Temperature On Product Yield and Gas Compositions From Pyrolysis of Bituminous Coal...

Naphthalene is produced from coal tar or petroleum. It is made from petroleum by dealkylation of methylnaphthalenes in the presence of hydrogen at high temperature and pressure. Petroleum was a major source of naphthalene until the 1980s, but now most naphthalene is produced from coal tar. The pyrolysis of bituminous coal produces coke and coke oven gases. Naphthalene is condensed by cooling the coke gas and then separated from the gas. Naphthalene production in the United States is slightly greater than 100,000 tons annually. 

Solvent-Refined Coal Process. In the 1920s the anthracene oil fraction recovered from pyrolysis, or coking, of coal was utilized to extract 35—40% of bituminous coals at low pressures for the purpose of manufacturing low cost newspaper inks (113). Tetralin was found to have higher solvent power for coals, and the I. G. Farben Pott-Broche process (114) was developed, wherein a mixture of cresol and tetralin was used to dissolve ca 75% of brown coals at 13.8 MPa (2000 psi) and 427°C. The extract was filtered, and the filtrate vacuum distilled. The overhead was distilled a second time at atmospheric pressure to separate solvent, which was recycled to extraction, and a heavier liquid, which was sent to hydrogenation. The bottoms product from vacuum distillation, or solvent-extracted coal, was carbonized to produce electrode carbon. Filter cake from the filters was coked in rotary kilns for tar and oil recovery. A variety of liquid products were obtained from the solvent extraction-hydrogenation system (113). A similar process was employed in Japan during Wodd War II to produce electrode coke, asphalt (qv), and carbonized fuel briquettes (115). 

The overall pyrolysis behavior of the bituminous coal and lignite under 1 atm helium is summarized in Figures 2 and 3. These data were obtained by heating 53 to 88-fim diameter particles at a nominal rate of 1000°C/sec to the peak temperature indicated on the abscissa and then immediately permitting the sample to cool at a rate of about 200°C/sec. The ordinate of each data point represents the integral yield over the actual experimental time-temperature history. The data are plotted cumulatively up to the total weight loss of the sample, with the vertical separation between successive curves representing the contribution of the indicated products. 

Figure 2. Pyrolysis product distributions from bituminous coal heated to different peak temperatures. (%) H20 and H2S (O) H20, H2S, CO, and C02 (X) H20, H2S, CO, C02, and all hydrocarbon gases (T) total weight loss, i.e., H20, H2S, CO, C02, all HC gases, tar, and liquids. Pressure = 1 atm (helium). Heating rate = 1000°C/sec. (14)...

Other studies on coal were performed using pyrolysis, such as the measurement of the level of sulfur containing compounds in coal [27,28], or evaluation of polynuclear aromatic hydrocarbons (PAH) in coal [29]. The generation of PAH in coal pyrolysis is an important issue, as some of these compounds are known to have carcinogenic properties. A list of PAHs identified in coal pyrolysates is given in Table 14.2.2. The yield of PAH in coal pyrolysate depends to some extent on the coal type but mainly on the pyrolysis temperature. The variation of PAH levels as a function of temperature for several bituminous coals is shown in Figure 14.2.3. The yields of other pyrolysis products of coal were also shown to be temperature dependent [30]. 

The most convenient application for the fuels obtained would be to provide substitute heat for direct use on the producing farm or within short distances requiring a minimum of transportation. The char has a similar heat output to bituminous coal on a mass basis, while the gas has about one-third the value of natural gas. Relatively little capital would be required to modify existing equipment for burning pyrolysis products. The possibility of mixing ground char and fuel oil will be considered in Phase II. 

A large volume of work has been reported on rapid devolatilization of coal (heating rates approximating process conditions (21,22). Recently, the effects of coal minerals on the rapid pyrolysis of a bituminous coal were reported by Franklin, et al ( 23). They found that only the calcium minerals affected the pyrolysis products. Addition of CaCO3 reduced the tar, hydrocarbon gas and liquid yields by 20-30%. The calcium minerals also altered the oxygen release mechanism from the coal. Franklin, et al. attribute these effects to CaCOj reduction to CaO, which acts as a solid base catalyst for a keto-enol isomerization reaction that produces the observed CO and H2O. 

Formation of sub-bituminous coal seems to involve O loss through conversion of dihydroxy phenolic units (catechols) to monohydroxy units (phenols and alkylphenols), as shown in Fig. 4.7, based on the simple distribution of pyrolysis products, which are dominated by phenol, ortho-cresol (2-methylphenol) and 2,4-dimethylphenol (Hatcher 1990). Oxygenated aliphatic structures (alkyl hydroxyls and ethers) seem to be absent. Figure 4.8 shows the types of units present at various stages of biochemical coalification, based on a random hgnin polymer. 

Rosenvold et al. (239) used DSC to study the thermal decomposition of 21 bituminous coal samples from Ohio. Representative DSC curves of the coal samples are illustrated in Figure 7.16. Three regions of endothermic reactions are observed (1) a dehydration peak in the range 25— 150°C (2) a second very broad endothermic peak that spans the range from 150°C to yield a noticeable peak between 400 and 500° C and (3) a narrower endothermic peak at temperatures 3s 550°C. The broad reaction from 150— 500°C probably corresponds to pyrolytic fragmentation of the carbon skeletal structure in coal with the third endothermic peak due to cracking reactions of the products evolved in the pyrolysis process. 

Coals were devolatilized at rates comparable with those encountered in combustion and gasification processes. Rapid pyrolysis was attained with pulse-heating equipment developed for this purpose. This technique permitted control of the heating time and the final temperature of the coal samples. Subbituminous A to low volatile bituminous coals were studied. All bituminous coals exhibited devolatilization curves which were characteristically similar, but devolatilization curves of subbituminous A coal differed markedly. The products of devolatilization were gases, condensable material or tar, and residual char. Mass spectrometric analysis showed the gas to consist principally of H2, CHh, and CO. Higher hydrocarbons, up to C6, were present in small quantities. 

The effect of additives on the asphaltene from the Catalytic Incorporated (Cat. Inc.) coal liquid product was studied. Asphaltene is defined as the pentane insoluble but benzene soluble part of the coal liquid. The fractionation procedure has been described in detail elsewhere(l) and is shown schematically in Figure 1. Some work was also done with A240 petroleum pitch. Elemental analysis for the Wyoming sub-bituminous coal. Cat. Inc. coal liquid product, and Cat. Inc. asphaltene and A240 petroleum pitch are shown in Table I. Measured amounts of the additive compounds to be studied were added to the Cat. Inc. asphaltene and petroleum pitch. The samples were pyrolyzed and the pyrolysis residues examined by cross polarized light microscopy. Elemental analyses of the residues were done. 

The yield of volatile matter in this process is a function of the coal type and ranges from approximately 20% w/w of the coal for a low-volatile bituminous coal to somewhat more than 55% w/w of the coal for a high-volatile C bituminous coal subbituminous coals may not show a volatile matter peak with increasing temperature. In addition to tarry products, the rapid pyrolysis of coal produces gases such as hydrogen, methane, and carbon monoxide as well as lesser amounts of hydrocarbons. Pyrolysis of coal is generally defined as the thermal decomposition of coal in the absence of air or other added substances. 

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