Anthracene oil solvent

Direct Hydrogenation. Direct hydrogenation of lignitic and other coals has been studied by many investigators. Lignite can be slurried with an anthracene-oil solvent, heated to a temperature of 460—500°C with 1 1 CO H2 synthesis gas at pressures to 28 MPa (280 atm) in a 2 kg/h reactor. The product hquids are separated, and in a commercial process, a suitable hydrogen-donor solvent would be recycled (54). 

In Europe, where an abundant supply of anthracene has usually been available, the preferred method for the manufacture of anthraquinone has been, and stiU is, the catalytic oxidation of anthracene. The main problem has been that of obtaining anthracene, C H q, practically free of such contaminants as carbazole and phenanthrene. Many processes have been developed for the purification of anthracene. Generally these foUow the scheme of taking the cmde anthracene oil, redistilling, and recrystaUizing it from a variety of solvents, such as pyridine (22). The purest anthracene may be obtained by azeotropic distillation with ethylene glycol (23). 

In the SRC work, coal was slurried with a process-derived anthracene oil and heated to 400—455°C at 12.4—13.8 MPa (1800—2000 psi) of hydrogen for 0—1 h. A viscous Hquid was extracted. The product stream contains some hydrocarbon gases, and H2S. The residue is gasified to generate hydrogen for the process. The remaining filtrate is separated into solvent, which is recycled, and SRC, a low ash, tadike boiler fuel. 

A more complex reaction model was proposed from the results of a kinetic study of thermal liquefaction of subbituminous coal. Data were obtained over a temperature range of 673 to 743 K (752 to 878°F) at 13.8 MPa (2000 psia) by using two solvents, hydrogenated anthracene oil (HAO), and hydrogenated phenanthrene oil (HPO), at a coal-solvent ratio of 1 15. Results were correlated with the following model ... 

About one half of the coal samples used in the above study (61) have been investigated by workers in Gulf Research and Development Company, using a continuous flow reactor (63). The throughput was about 1 kg./h of coal/solvent slurry, the solvent was a partly hydrogenated anthracene oil, temperatures of 440 and 455°C were used, and the system was pressurized with hydrogen to 20.69 MPa. 

Solvent s creosote type creosote oil creosote oil anthracene oil... 

A schematic diagram of the liquid solvent extraction process is illustrated in Figure 1. Where the production of liquid hydrocarbons is the main objective an hydrogenated donor process solvent is used, whereas in the production of needle coke this is not necessary and a coal derived high boiling aromatic solvent may be used (e.g. anthracene oil). An essential economic requirement of the process is that a high extraction yield of the coal is obtained and this will depend upon the coal used and the digestion conditions. 

The coals were crushed 80% less than 75 jjlm. The solvents used were anthracene oil (ex British Steel Corporation), hydrogenated process solvent (produced in a continuous coal extract hydrogenation plant) and several pure organic compounds (ex Koch-light). 

Figure 5. Influence of digestion time and temperature on extraction yield. Coal = Beynon solvent = anthracene oil coal solvent ratio = 1 4.

For example, Beynon and Cwm coals when digested in anthracene oil give extraction yields of 68% and 47% respectively. This variation can be explained by reference to the maceral composition of the coals. Beynon coal contains a lower concentration of inertinite than the Cwm coal (Table V). In experiments where relatively pure samples of petrographic species were digested in anthracene oil, exinite and vitrinite were shown to be highly soluble, whilst in comparison the inertinite was almost completely insoluble. Similar variations in reactivity of macerals have been reported from studies of solubility in pure organic solvents (1(3). 

Digestion conditions nominally 400 C with 60 min residence time Solvent anthracene oil... 

Digestion conditions 400°C 60 minute residence time Solvent anthracene oil Coal solvent ratio 1 3... 

A system of classifying coals for solvent extraction, based upon the extent of extraction when using anthracene oil and phenanthrene as solvents has been developed. The reactivity of the coals can be conveniently presented by superimposing the results on Seyler s coal chart. The effects of variations in maceral composition are also discussed. 

Solvent additives to the melt (Table 3) fall into two categories extractive and reactive. The extractive solvents (decane, perchloroethane, o-dichlorobenzene, and pyrrolidine) had negligible effect on solubility, possibly due to the preferential wetting of the coal by the solvent and exclusion of the ZnCl2 melt. Reactive solvents (anthracene oil, indoline, cyclohexanol, and tetralin) all incorporated strongly. Donor solvents, tetralin and indoline, increase the "corrected solubility, whereas anthracene oil and cyclohexanol have negligible effect. 

Primary Conversions and Influence of Mobile Phase Yields for the various H-donor and non-donor solvent extractions of Linby coal at 400% are summarised in Table III the conversions for the THF-extracted coal include the extracted material. Surprisingly, pre-extraction with THF significantly increases primary conversions in the polynuclear aromatic compounds (PACs) investigated. These findings appear to be contrary to those of other liquefaction (16) and pyrolysis (17) studies where prior removal of chloroform-extractable material significantly reduced conversions. However, Rincon and Cruz (18) have reported recently that pre-swelling coals in THF increases conversions for both anthracene oil and tetralin. The fact that Point of Ayr (87% dmmf C) coal yielded over 80% pyridine-solubles in pyrene (C.E. Snape, unpublished data) without pre-extraction is consistent with the earlier results of Qarke et al (19) for anthracene oil extraction where UK coals... 

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). 

Anthracene oil is usually the fraction from 300 to 350°C. It is washed-with various solvents to remove phenanthrene and carbazole the remaining solid is anthracene. 

Obtained by Applying Schemes A, B, and C to Products of Catalytic a Solvent of Anthracene Oil... 

Experience with the development of the solvent-refined coal (SRC) process had suggested that raw anthracene oil was a suitable coal liquid for initial catalyst studies hence some data were obtained using this type of oil. A filtered oil obtained from the COED process developed by FMC Corporation also was used in these studies. The properties of these two oils are given in Table I. The total nitrogen concentration in the raw anthracene feed oil was 0.97 wt % and the FMC oil contained 1.13 wt % nitrogen. Both liquids contained negligible quantities of ash materials. 

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