Coal donors

The H-Coal and CFFC Processes are unique In the sense that first-stage liquefaction is achieved by circulating the coal-donor slurry through an "ebullated" (i.e., partly fluidized) bed of uniformly sized catalyst pellets. 

Different types of other coal liquefaction processes have been also developed to convert coals to liqnid hydrocarbon fnels. These include high-temperature solvent extraction processes in which no catalyst is added. The solvent is usually a hydroaromatic hydrogen donor, whereas molecnlar hydrogen is added as a secondary source of hydrogen. Similar but catalytic liquefaction processes use zinc chloride and other catalysts, usually under forceful conditions (375-425°C, 100-200 atm). In our own research, superacidic HF-BFo-induced hydroliquefaction of coals, which involves depolymerization-ionic hydrogenation, was found to be highly effective at relatively modest temperatnres (150-170°C). 

W. R. Eppedy and J. W. Taunton, "Exxon Donor Solvent Coal Liquefaction Process Development," paper presented at Coal Dilemma II ACS Meeting, Colorado Spriags, Colo., Feb. 12, 1979. 

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). 

W. N. Mitchell, K. L. Trachte, md S. Zaczepinski, "Performance of Low-Rank Coals in the Exxon Donor Solvent Process," paper presented at / 0th Biennial Eignite Symposium, Grmd Porks, N.D., May 1979. 

The functional group ia collectors for nonsulfide minerals is characterized by the presence of either a N (amines) or an O (carboxyUc acids, sulfonates, etc) as the donor atoms. In addition to these, straight hydrocarbons, such as fuel oil, diesel, kerosene, etc, are also used extensively either as auxiUary or secondary collectors, or as primary collectors for coal and molybdenite flotation. The chain length of the hydrocarbon group is generally short (2—8 C) for the sulfide collectors, and long (10—20 C) for nonsulfide collectors, because sulfides are generally more hydrophobic than most nonsulfide minerals (10). 

Fig. 17. Schematic diagram of the coal hquefaction section of the Exxon donor solvent (EDS) process. To convert MPa to psi, multiply by 145.

Several processes progressed to demonstration scales but have not been commercialized, primarily because of economic inabiHty to compete with available petroleum products. The H-Coal process developed by Hydrocarbon Research, Inc. was demonstrated at Catiettsburg, Kentucky using a 545 t/d plant and DOE support. The Exxon donor solvent Hquefaction process was not commercialized either. 

Depending on its rank, coal can be dissolved in as little as one minute in the temperature range of 623 to 723 K (662 to S42°F) in suitable solvents, which are assumed to promote thermal cracking of the coal into smaller, more readily dissolved fragments. These fragments may be stabilized through reactions with one another or with hydrogen supplied either by a donor solvent or from a gas phase. 

Magnitudes of /cg, /cp, /c, and indicate the importance of direct reactions with coal, where and are for hydrocracking reactions in the conversion process. Data for and from the experiments with HPO indicate that oil production from coal is increased by the use of a good hydrogen donor solvent. 

Of great concern for air pollution problems resulting from the incident are dioxin-like compounds. In general, dioxin-like compounds can be generated when chlorine donor compounds are present. Depending on the source of the coal tar, chlorine content may range between 1 and 5000 ppm. 

The Role of Ether-Linkages in Solubilization of Low-Rank Carboniferous Coals by H-Donors... 

Detailed discussion of these findings will be presented elsewhere. Here we only wish to point out that responses to a hydrogen donor tend to be critically affected by minor structural differences between the compounds. Thus, while diphenyl ether remains substantially unaffected by the donor, its hydroxy-derivatives (phenoxy phenols) often display fairly high reactivity. Taken in conjunction with the failure of low-rank coals (7) and phenoxy phenols (10) to suffer reductive cleavage when treated with sodium in liquid ammonia, this lends some support for the existence of phenoxy phenol entities in low rank coals. 

The inertness of phenols and phenoxy phenols toward Na/liq. NH3 can be attributed to the fact that phenols are powerful proton-donors in this system, and resistance of the resultant anions toward reduction is believed to result from stabilization by resonance (10). While alkylation of low-rank coals before treatment with Na/liq. NH3 therefore offers means for establishing the presence of phenoxy phenol ethers in them, an alternative is afforded by the observation that some phenols can be reduced by concentrated solutions of lithium (11). If this latter reaction also reduces phenoxy phenols in coal, a second treatment should then cause ether-cleavage. 

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. 

Selection of Solvents. The extraction yield of a low rank coal (Annesley) has been determined after digestion using a selection of solvents (Table II). The results show large variations in solvent power and, in particular, the high extraction yields obtained with hydrogen donor solvents. It is important to differentiate between the ability of a solvent to prevent polymerisation of the dissolved coal by hydrogen transfer, and its ability to retain the dissolved coal in solution. For example, Tetralin is frequently quoted as an... 

Conversion of coal to benzene or hexane soluble form has been shown to consist of a series of very fast reactions followed by slower reactions (2 3). The fast initial reactions have been proposed to involve only the thermal disruption of the coal structure to produce free radical fragments. Solvents which are present interact with these fragments to stabilize them through hydrogen donation. In fact, Wiser showed that there exists a strong similarity between coal pyrolysis and liquefaction (5). Recent studies by Petrakis have shown that suspensions of coals in various solvents when heated to 450°C produce large quantities of free radicals (. 1 molar solutions ) even when subsequently measured at room temperature. The radical concentration was significantly lower in H-donor solvents (Tetralin) then in non-donor solvents (naphthalene) (6). 

The production of such high concentrations of radicals leads to a very unstable situation and if the radicals are not stabilized via H-donation, they undergo a variety of undesired reactions such as condensation, elimination or rearrangement (7). Neavel has shown that at short times ( 5 min) a vitrinite enriched bituminous coal can be converted to 80% pyridine soluble form in even non-donor reaction solvents (naphthalene) (8). But if reaction times are extended, the soluble products revert to an insoluble form via condensation reactions. Such condensation reactions were... 

The classic work of Storch and co-workers showed that essentially all coals below 89% C f can be converted in high yields to acetone soluble materials on extended reaction (12). We have investigated the behavior of coals of varying rank toward short contact time liquefaction. In one series of experiments, coals were admixed with about 5 volumes of a solvent of limited H-donor content (8.5% Tetralin) and heated to 425°C for either 3 or 90 minutes. The solvent also contained 18% p-cresol, 2% y-picolene, and 71.5% 2-methylnaphthalene and represented a synthetic SRC recycle solvent. The conversions of a variety of coals with this... 

It has been proposed (17) that the portion of coal which is mobile under liquefaction conditions, contributes to the stabilization of thermally-generated radicals. Thus, coals which are highly fluid or contain large contents of extractable material might be expected to provide hydrogen and thus promote conversion. Collins has reported that vitrinite is a better donor of hydrogen than is Tetralin (20). Our own measurements of the aromatic content and elemental analyses of the coals (16,21) (or coal products) before and after conversion at short time are insufficient to confirm or deny the supposition that coal acts as its own H-donor even at short times. 

If the initial reactions of coal are purely thermal, one might expect that the H-donor level will be of minor importance if times are kept short. In fact, all coals contain a certain portion of material that is extractable by pyridine. On heating coals to liquefaction temperatures, some additional material also becomes soluble in even non-donor solvents. Thus, there is a portion of all coals which can be solubilized with little dependence on the nature of the solvent. 

We have observed that at short contact times the conversion of bituminous coals is also responsive to the level of H-donor in the solvent. Table IV shows the conversions of an Illinois 6... 

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