Coal fractions separated from

TABLE I. Structural Characteristics of Coal Fractions Separated from Solubilized... 

The observed changes in density are related in a complex way to the chemical structure of the coal or maceral (3). In order to better understand the chemical variations occurring in coal macerals we have examined the ultimate analysis of selected density fractions separated from the same coal. 

As already mentioned, several investigators have pointed out that naphthalene or tetrahydrofuran may be incorporated into the coal product (9, 10, 11), In this work we found that chromatographic procedures could be used to separate unbound naphthalene and its reductive alkylation products from the coal alkylation products. The spectroscopic work indicates that the principal resonances of naphthalene and tetrahydrofuran are absent from the butylated coals. Moreover, the mass balance shows that no important quantity of naphthalene or tetrahydrofuran could be incorporated. We supplemented this negative evidence by a comparison of the reaction products obtained from the same coal in a reaction in liquid ammonia. In the most pertinent case the Illinois No. 6 coal was treated with potassium in liquid ammonia. The polyanion was alkylated with butyl iodide. The product distribution obtained by GPC and the spectroscopic properties of these fractions were very closely related to the properties of the reaction products obtained in the reaction with naphthalene in tetrahydrofuran. Recently Larsen and his group found that neither " C-labeled naphthalene nor tetrahydrofuran was incorporated in chemically significant amounts in the coal products separated from the reaction mixture by chromatography (12). 

Present in coal tar (i%), from which it is separated by fractional distillation. Can be... 

Historical. Pyridines were first isolated by destructive distillation of animal bones in the mid-nineteenth century (2). A more plentifiil source was found in coal tar, the condensate from coking ovens, which served the steel industry. Coal tar contains roughly 0.01% pyridine bases by weight. Although present in minute quantities, any basic organics can be easily extracted as an acid-soluble fraction in water and separated from the acid-insoluble tar. The acidic, aqueous phase can then be neutrali2ed with base to Hberate the pyridines, and distilled into separate compounds. Only a small percentage of worldwide production of pyridine bases can be accounted for by isolation from coal tar. Almost all pyridine bases are made by synthesis. 

The solvent-range product was not separately analysed as it was not able to be separated from the recovered solvent in the distillate. However, GLC examination of the distillate indicated that the solvent-range product was derived mainly from aliphatic side chains in the coal (9). Note that virtually no solvent-range product was derived from fraction D. 

The coal residue was separated into a THF-soluble fraction and a THF-insoluble residue. The wt % yields and atom % 2H compositions are given in Table I. The coal residue was 6 wt % soluble in tetrahydrofuran. The soluble fraction had 23 atom % 2H content. Evaluation of the 2H NMR data showed that 85 wt % of this fraction was derived from the coal and that its deuterium content was 10%. The chemically-bonded naphthalene-d8 content of the THF-soluble fraction, estimated from the 2H NMR data, was about 15 wt % or approximately 1 wt % of the coal. The insoluble residue had 6 atom % 2H content. This indicates that the residue contained approximately 1 wt % chemically-bonded naphthalene which was estimated from the difference in the atom % 2H content of the insoluble residue and recovered naphthalene-d8. This gives a total chemically-bonded naphthalene-d8 content of approximately 2 wt %. Similar results were obtained in extraction experiments made with phenanthrene (30), where it was found that 3-7 wt % of the phenanthrene was chemically linked to the coal product. 

In the United States, germanium is obtained as a by-product of zinc production from zinc blende ores. The ore is concentrated by the flotation process. Concentrated ore is then roasted, converting zinc and the impurity metals to their oxides. Heating the crude oxides with sodium chloride and coal converts germanium and other impurity metal oxides into their volatile chlorides. The chloride vapors are condensed and germanium chloride, GeCh, is separated from the condensate by fractional distillation. 

Horton and Aubrey (34) handpicked pure vitrain samples from coals and separated them into five different specific gravity fractions. They then analyzed these for 16 minor elements. They concluded that for the three vitrains they studied, beryllium, germanium, vanadium, titanium, and boron were contributed almost entirely by the inherent (organically combined) mineral matter and that manganese, phosphorus, and tin were associated with the adventitious (inorganically combined) mineral matter. 

The elemental analyses of the products from the extraction of Bruceton coal are shown in Table III. The mineral matter was separated from the extract quite efficiently as shown by the ash content of the extracts and the insoluble residue. The elemental composition of all fractions was quite similar to that of the original coal. Only the hydrogen content varied to some extent, increasing with increased solubility. The elemental analysis of the products from the extraction of Ireland Mine coal was incomplete. 

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). 

Coal-Tar Process. The largest quantities of naphthalene are obtained from the coal tar that is separated from the coke-oven gases. The coal tar first is processed through a tar-distillation step where ca the first 20 wt% of distillate, i.e., chemical oil, is removed. The chemical oil contains practically all the naphthalene present in the tar. It is processed to remove the tar acids by contacting with dilute sodium hydroxide and, in a few cases, is next treated to remove tar bases by washing with sulfunc acid. Principal U.S. producers obtain their crude naphthalene product by fractional distillation of the tar acid-free chemical oiL... 

N 8.38% col lfts or pltlts(from xylol or by subln), mp 245°, bp 355°, d 1.10 at 18°, vap press 400mm at 323°. Carbazole is one of the principal ingredients of the anthracene fraction of coal tar distilling between 320 and 360° it can be separated from other constituents by various methods, one of which is fusion with KOH and separation of the resulting deriv. Various methods of separating or preparing carbazole are described in Refs 1,5,7,9a,10,11,16 others... 

Separation, Characterization and Analysis of the Distillate Fractions. Results from the analyses of the <200° C coal-liquid distillates (after removal of trace quantities of acids and bases) are summarized in Table IV. Results from the dual silica-gel/alu-mina-gel adsorption chromatography separations of the 200° to 325° C, 325° to 425° C, and 425° to 540° C coal-liquid distillates are summarized in Table V. Data for the acid and base extracts of the polyaromatic-polar adsorption fractions are also included in Table V. Summary data on analysis of the saturate fractions are listed in Table VI. Data in Table VI show a trend toward higher percentages of zero- and one-ring saturates in lower-rank coals. 

Figure 2. GPC separation of SO 2-solubles of SRC from West Virginia subbituminous coal. Fraction 3 and 4 are ...

For many years benzene (benzol) was made from coal tar, but new processes that consist of catalytic reforming of naphtha and hydrodealkylation of toluene are more appropriate. Benzene is a natural component of petroleum, but it cannot be separated from crude oil by simple distillation because of azeotrope formation with various other hydrocarbons. Recovery is more economical if the petroleum fraction is subjected to a thermal or catalytic process that increases the concentration of benzene. 

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