Kinetic studies of coal liquefaction

Isotope Effects in Supercritical Water Kinetic Studies of Coal Liquefaction... 

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 ... 

The type of quantitative analytical data which are needed for modelling and kinetic studies on coal liquefaction process could not be obtained by using general analytical techniques. We have developed a new analytical approach for obtaining qualitative information as well as quantitative data on coal liquid species. Coal liquefaction produces smaller molecules from coal which is composed of larger molecular species or a matrix of larger molecular species in which smaller species are entrapped. 

Kinetic studies ( ) of such systems Indicate that the Initial stages of liquefaction Involve conversion of the coal Into a more or less completely pyrldlne-soluble solid and thereafter Into a benzene-soluble material which Is gradually transformed Into a viscous liquid as increasing amounts of hydrogen combine with It. This process can be catalyzed by, e.g., cobalt molybdate, but proceeds rapidly even in the absence of catalysts. At 775 F (A00°C), total py-solubi1ity (and vSO per cent solubility In benzene) can be attained within less than 10 minutes. 

At the present time, few, if any, details of chemical reaction mechanisms in coal conversion are known with certainty. This situation is particularly distressing in the areas of coal liquefaction and pyrolysis where chemical kinetics may strongly influence process efficiency and product quality. To improve this situation, in recent years a number of research groups have been performing chemical studies of coal and "model" compound reactions. 

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. 

The primary purpose of this paper is to describe the kinetics of coal liquefaction derived from a pilot-scale unit. The specific coal studied was Big Horn subbituminous coal. The experimental data were obtained in a pilot-scale Gulf patented (13) reactor. The data illustrate the effects of reactor space time and temperature on the product distribution. Since the reactor behaves as a bubble column, the intrinsic kinetics of the liquefaction process can be extracted by means of a kinematic model of the reactor. The experimental data were found to be... 

Most studies on the mechanism and kinetics of solvent extraction have necessarily used only a limited selection of coals. In a commercial environment where coals with widely varying properties are available, it is necessary to develop a generalised system of grading the coals with respect to their suitability for liquefaction. 

Many studies on direct liquefaction of coal have been carried out since the 1910 s, and the effects of kinds of coal, pasting oil and catalyst, moisture, ash, temperature, hydrogen pressure, stirring and heating-up rate of paste on coal conversion, asphaltene and oil yields have been also investigated by many workers. However, few kinetic studies on their effects to reaction rate have been reported. 

The dialin donor solvents were also used directly in coal liquefaction studies. Inasmuch as details of coal structure are unknown, the present theory can only be tested in a qualitative way, as follows. First, if the liquefaction of coal occurs under kinetic control with hydrogen-transfer from the donor solvent involved in the rate-determining step, then we should expect the dialin donors to be more effective than the control solvent T.et-ralin (and also Dfecalin). This is suggested by the theory because the dialins possess higher energy HOMOs than Tetralin and... 

If the mobile phase is present in a significant concentration, as suggested by the results of solvent extraction studies (1,8), the practical meaning of the mobile phase to coal conversion processes may be profound. In coal liquefaction, two stage processes emphasizing the mobile phase and the macromolecular structure separately could well be most economical. In devolatilization kinetics, at least two sets of kinetic parameters are necessary to model the devolatilization phenomena associated with the mobile phase and the macromolecular structure respectively since the mobile phase components devolatilize at much lower temperatures than the macromolecular structure components 0. In addition, the mobile phase appears to have a significant influence on the thermoplastic properties of coal (0 and thereby on coke quality. 

Amestica and Wolf (12) in a study closely related to the one described herein, measured the conversion of Illinois No. 6 coal in toluene and ethanol. Their results clearly showed that conversions increased with temperature and solvent density but were not detailed enough to show the time dependence of the conversion. However, a result important to this study was that toluene converts coal to liquids without significantly reacting itself. After reaction, 98% of the toluene used was recovered versus only 73 -85% of the ethanol in runs using it. Ethanol is a hydrogen donor and reacts extensively with the coal. While toluene probably reacts with coal to a small extent, its effect was primarily physical in nature. As such, it is a good candidate for studying the effects of a supercritical solvent on coal liquefaction kinetics since the enhancement effect of supercritical conditions is physical in nature. 

The specific role of pyrite (FeS2) as a catalyst has been under investigation since pyrite was identified as the most active inherent mineral for coal liquefaction. Under liquefaction conditions, FeS2 is transformed into a nonstoichiometric iron sulfide, Fei-x (0 X 0.125). Thomas et al. (15) studied the kinetics of this decomposition under coal liquefaction conditions, and concluded that the catalytic activity of FeS2 is associated with radical initiation resulting from the... 

Diffuse reflectance infrared Fourier transform (DRIFT) spectroscopy has been proven to be an excellent means of characterizing coals and related materials. This report is devoted to the evaluation of the technique as a method for situ monitoring of the chemical structural changes wrought in reactions of coal with fluid phases. This technique does not require a supporting medium (matrix) which can contain chemical artifacts which inherently serve as a barrier for access to the solid coal. The rapid response of the Fourier transform infrared technique is further beneficial for kinetic studies related to combustion, liquefaction, gasification, pyrolyses, etc. Experimental equipment and techniques are described for studies over wide ranges of pressure (10 5 Pa to ca 1.5 x 10 kPa) and temperature (298 K to 800 K). 

Kinetic studies using tetrahydronaphthalene (tetralin) as the hydrogen donor have shown that sufficient hydrogen is available for liquefaction of coal when the proportions of vehicle coal are of the order of 2 1 and that the conversion is quite rapid at temperatures on the order of 400°C (750°F). Thus, under these particnlar conditions (Fignres 12.6 and 12.7), coal becomes almost 100% solnble in pyridine within 10 min without any massive increase in hydrogen content of the product relative to the original coal. 

Coal is a nonhomogeneous material and its liquefaction produces a very large number of products. A completely detailed kinetic analysis involving all chemical species is therefore impossible. All the studies reported in the literature evaluate kinetic models using different types of lumped reacting species. 

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