Laszlo A. Heredy

Hydrogen incorporation during coal liquefaction

Coal hydrogenation reactions have been investigated using a deuterium tracer method which makes it possible to determine which structural positions in the coal react with hydrogen gas or donor solvent during liquefaction. 2H2 and/or tetralin-d12 were reacted with a Pittsburgh Seam coal at 13.8 to 22.1 MPa and 360 to 425 °C for 0.25 to 1.0 h. Hydrogenation and exchange indices were formulated to indicate the relative contribution of each type of reaction to the total H incorporation. In the coal-deuterium gas system, deuterium incorporation in the solvent-separated products increases in the order oil < asphaltene < preasphaltene < residue. However, in the coal-tetralin-d12-deuterium gas system, deuterium incorporation is similar in each of these four fractions. In both systems, 2H incorporation varies with structural position, with the α-aliphatic positions exhibiting the greatest extent of incorporation. The α-tetralyl radical appears to be an important intermediate in hydrogen transfer to and exchange with the coal. The results indicate that in the donor system the abstraction of hydrogen from the solvent by coal-derived radicals is involved in the rate-determining step of the formation of the soluble products. Evidence indicates that considerable direct interaction of the gas-phase hydrogen with the coal also occurs in the donor solvent system.

Liquefaction of bituminous coal at moderate temperatures

Abstract Coal hydrogenation was investigated in the temperature range 275 to 325 °C in order to minimize the number of thermal side reactions that take place. Gas-phase hydrogen was used in batch experiments without an added donor solvent, to avoid the additional analytical complexities introduced by such a solvent. It was found that significant oil yields (up to 72% of the daf coal) can be obtained from the hydrogenation of bituminous coal at 325 °C. Furthermore, at this temperature, the data indicate that cleavage of certain CO bonds may have an important role in oil formation. The metal surfaces of the liner and impeller of the autoclave had a strong catalytic effect on the liquefaction reactions under these conditions. The oil yield was 48% when the metallic surfaces were exposed and only 19% when these components were coated with glass. Catalysis by nickel, applied as nickel acetate impregnated into the coal, gave higher overall conversion, lower oil yield, and a more saturated oil product than catalysis by the autoclave surfaces.

Investigation of Coal Hydrogenation Using Deuterium as an Isotopic Tracer

Mechanisms of coal hydrogenation were investigated by using a deuterium tracer method. This method makes it possible to determine which structural positions in the coal react with hydrogen during liquefaction. A hydrogenation index (HI) and exchange index (EI) were formulated to measure the amount of deuterium incorporated due to hydrogenation and exchange reactions, respectively. In the coal-deuterium system, deuterium incorporation was found to vary both with product fraction and with structural position. In contrast, the deuterium contents of the fractions from donor solvent experiments were essentially uniform. The donor solvent experiments did, however, show preferential deuterium incorporation with respect to structural position. Important information with regard to the reaction mechanisms in the donor solvent system was obtained by analyzing the spent solvent mixture that was recovered from the reaction products. The results indicate that not only hydrogen donation but also hydrogen exchange involving the α-positions of tetralin can have a significant role in stabilizing the fragments that form during the thermal decomposition of the coal. In addition, evidence was obtained that there is also a direct route for deuterium incorporation into the coal products from the gas phase without the participation of tetralin.