Coal liquefaction dissolution

A question then arises as to whether the CSD recovery is being limited by the preasphaltene content produced from direct products of coal liquefaction or whether by low liquefaction severity a more thermally sensitive product is produced resulting in retrogressive reactions of liquefaction products to "post-asphaltenes." There is some indication that "virgin" preasphaltenes, primary products of coal dissolution, are more easily recovered via CSD as shown in Table VII however, "postasphaltenes" made from thermal regressive reactions are not. 

The important elementary reactions of coal liquefaction are the decomposition of coal structure with low bond dissociation energy, the stabilization of fragments by the solvent and the dissolution of coal units into the solution. 

Previously we have shown that phenolic compounds have a remarkable positive effect (4) on the coal liquefaction in the presence of Tetralin, depending strongly on the character of coal as well as on the concentration of phenols. The effect of phenols on the decomposition of diaryl ethers will give a good explanation for the previous results, because aliphatic ether structures of some young coals will be decomposed rapidly at relatively low temperatures and so the rate of coal dissolution will not be affected by the addition of phenols, on the other hand, the polycondensed aromatic ether structures will be decomposed effectively by the addition of phenols in the course of coal liquefaction. 

It is generally recognized that vitrain is the most soluble constituent of any particular coal, whereas fusain is the least soluble. Indeed, early work on the liquefaction of coal by dissolution in a solvent showed that even at temperatures on the order of 400°C (750°F), fusain is, to all intents and purposes, insoluble. Under these aforementioned conditions, durain did show some response to the solvent but still did not match the solubility of vitrain. 

Likewise, Orr et al.29,30 have explored the possible use of tyre pyrolysis oil as a solvent for coal liquefaction. The potential of this alternative was demonstrated by the fact that coal-TPO mixtures were transformed with higher conversion than when coal was reacted directly with ground waste rubber tyres. It is proposed that the polyaromatic compounds present in the TPO favour coal dissolution during liquefaction. Treatment of coal-TPO mixtures (50/50%) at 430 °C under 68 atm of cold-hydrogen pressure in the presence of a Mo catalyst led to a high coal conversion in just 10 min of reaction. From electron probe microanalysis of the coal particles after the reaction, the authors conclude that TPO favours the catalyst dispersion and its contact with coal, which results in enhanced coal conversion. 

Weber, W.H. and A. Basu. "Coal Dissolution Studies Utilizing the Slurry Preheater at the Wilsonville SRC Pilot Plant." (Coal Liquefaction Preheater Studies, ORNL, 1979). 

Data for the kinetics of coal liquefaction have been published in the literature (1-11). A review of the reported studies has recently been given by Oblad (12). The reported data were mostly obtained in bench-scale reactors. Guin et al. (7) studied the mechanism of coal particle dissolution, whereas Neavel (7), Kang et al. (8), and Gleim (10) examined the role of solvent on coal liquefaction. Tarrer et al. (9) examined the effects of coal minerals on reaction rates during coal liquefaction, whereas Whitehurst and Mitchell (11) studied the short contact time coal liquefaction process. It is believed that hydrogen donor solvent plays an important role in the coal liquefaction process. The reaction paths in a donor solvent coal liquefaction process have been reviewed by Squires (6). The reported studies examined both thermal and catalytic liquefaction processes. So far, however, very little effort has been made to present a detailed kinetic model for the intrinsic kinetics of coal liquefaction. 

Direct-Liquefaction Kinetics All direct-liquefac tion processes consist of three basic steps (1) coal slurrying in a vehicle solvent, (2) coal dissolution under high pressure and temperature, and (3) transfer of hydrogen to the dissolved coal. However, the specific reac tion pathways and associated kinetics are not known in detail. Overall reaction schemes and semiempirical relationships have been generated by the individual process developers, but apphcations are process specific and limited to the range of the specific data bases. More extensive research into liquefaction kinetics has been conducted on the laboratory scale, and these results are discussed below. 

The reactive role of liptinite macerals in liquefaction has been partially documented (50,68). However, recent work has shown that unaltered sporinite often is encountered in the residues from both batch and continuous liquefaction runs. For example, sporinite was a common component in the residues of a high volatile A bituminous coal after hydrogen-transfer runs at 400° for 30 minutes (70). In spite of the relative unreactivity of the sporinite in this instance, the vitrinite clearly had reacted extensively because vitroplast was the predominant residue component. The dissolution rate of sporinite from some coals, even at 400°C, may be somewhat less than that of vitrinite. 

In this paper, a number of low-severity liquefaction regimes are considered. The influence of different H-donor and non-donor solvents on primary conversions without a hydrogen overpressure is discussed in the light of other recent work (10-131. Also, it is demonstrated that oil yields broadly increase with decreasing coal rank in both H-donor extraction and dry catalytic hydrogenation provided that retrogressive reactions are avoided in the initial stages of coal dissolution. 

As reaction severity approaches zero the Monterey coal conversion is about 70 percent and the Wyodak is about 40 percent. Liquefaction appears to occur very rapidly to these levels and then slower to the maximum conversion. The initial liquefaction may be a physical dissolution while the slower rate represents a reaction in which chemical bonds are broken, although other explanations are possible. (10)... 

The purpose of this paper is to describe some of our findings which examine the liquefaction behavior of Western sub-bituminous coal to determine which components of the solvent are most critical in the short contact time dissolution stage. The work will be presented from two points of view ... 

For example, preheating coal at ca. 200°C (ca. 390°F) tends to have an adverse effect on the caking properties but may also increase ease of, say, gasification (insofar as caking coals can be difficult to gasify efficiently) (Chapters 20 and 21) and may also increase the ease of dissolution by organic solvents during liquefaction processes (Chapters 18 and 19). 

---