Liquefaction direct

Ed9ar B. Klunder, Ph.D., Project Manager, Federal Energy Technology Center (Pittsburgh), U.S. Department of Energy. (Direct 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. 

Direct-Liquefaction Processes Figure 27-8 presents a simph-fied process flow diagram of a typical direct coal liquefaction plant. Specific processes are described in the following paragraphs. 

TABLE 27-14 Direct Liquefaction Process Conditions and Product Yields... 

The conversion of coal into hquid materials can be accomphshed by pyrolysis or by direct liquefaction— heating coal in the presence of a hydrogen source. Neither of these routes is yet economically feasible. 

In direct liquefaction, coal is heated in the presence of hydrogen and a catalyst such as cobalt-molybdenum or nickel-molybdenum on alumina to give a greater yield of high-quality hydrocarbons than that produced by pyrolysis. This hydrogenation process has been demonstrated in several 50- to 250-ton-per-day plants. 

Kinetics of Direct Liquefaction of Coal in the Presence of Molybdenum—Iron Catalyst... 

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. 

Fan (1989) provided a detailed historical development of three-phase fluidization systems in reactor applications. Only a brief review of the significant accomplishments and the economic factors affecting the development of three-phase reactors will be provided here. Table 1 provides the important contributions in the application of three-phase fluidization systems for the past several decades. The direct liquefaction of coal to produce liquid fuels was the first commercial reactor application of three-phase fluidization systems, with development having occurred from the mid-1920 s throughout the 1940 s. A large effort was put forth at this time in Europe for the production of liquid fuels from coal as a direct... 

Direct hydration, of ethylene, 10 538 Direct hydrogenation, 6 827 Direct immunosensors, 14 154 Direct ingot (dingot) method, 25 409 Direct initiation, 14 270 Direct injection (DI) diesel engines, 12 421 Direct inlet injection, gas chromatography, 6 383, 415-416 Directional couplers, 17 446 Directional drilling techniques, in sulfur extraction, 23 572 Directive 89/107/EEC (EU), 12 36 Direct liquefaction, 6 827 Direct marketing, technical service personnel and, 24 343 Direct metal nitridation, 17 211-213 aerosol flow reactor, 17 211-212 Direct methanol fuel cells (DMFC),... 

Direct Liquefaction Kinetics Hydrogenation of coal in a slurry is a complex process, the mechanism of which is not fully understood. It is generaly believed that coal first decomposes in the solvent to form free raclicals which are then stabilized by extraction of hydrogen from hydroaromatic solvent molecules, such as tetralin. If the solvent does not possess sufficient hydrogen transfer capability, the free radicals can recombine (undergo retrograde reactions) to form heavy, nonliquid molecules. A greatly simplified model of the liquefaction process is shown below. 

Derbyshire, FJ., Catalytic Coal Liquefaction by Temperature-Staged Reaction, presented at Direct Liquefaction Contractor s Review Meeting, Pittsburgh, PA (Oct. 20-22, 1986). 

After World War II, direct liquefaction of coal became uneconomical as the use of lower-cost petroleum products became more widespread. However, the German process of indirect coal liquefaction, the Fischer-Tropsch process, continued to hold some interest. The Fischer-Tropsch process first involved production of a carbon monoxide and hydrogen-rich synthesis gas by the controlled gasification of coal followed by a catalytic reaction process to yield a valuable mixture of hydrocarbon products. Simplified Fischer-Tropsch reactions are shown by the following equations ... 

A direct liquefaction technique, the SRC process involves mixing dried and finely pulverized coal with a hydrogen donor solvent, such as tetralin, to form a coal-solvent slurry. The slurry is pumped together with hydrogen into a pressurized, vertical flow reactor. The reactor temperature is about 825°F (440°C) and pressures range from 1,450 to 2,000 psi. A residence time in the reactor of about 30 minutes is required for the carbonaceous material to dissolve into solution. From the reactor, the product passes through a vapor/liquid separation system. The slurry solids remaining in the reactor are then removed and filtered. Various filtration techniques have been developed to remove solids from recoverable oil. 

We will examine three synthetic fuel scenarios and compare their implications regarding sulfur availability with the current and projected market for sulfur to the year 2000. The analysis will consider three production levels of synthetic fuels from coal and oil shale. A low sulfur Western coal will be utilized as a feedstock for indirect liquefaction producing both synthetic natural gas and refined liquid fuels. A high sulfur Eastern coal will be converted to naphtha and syncrude via the H-Coal direct liquefaction process. Standard retorting of a Colorado shale, followed by refining of the crude shale oil, will round out the analysis. Insights will be developed from the displacement of imported oil by synthetic liquid fuels from coal and shale. 

In route 2, the direct liquefaction approach, coal is slurried with a process solvent and the slurry is pumped into a pre-heater/reactor and heated to temperatures of 750-850°F at a pressure of 1500-3000 psi of hydrogen. A catalyst can be used either in the reactor itself or external to the reactor to hydrogenate the process solvent. Almost all the organic constituents of the... 

We will consider three processes in more detail to show how the sulfur in the original feedstock material (coal or oil shale) is recovered as elemental by-product sulfur. In this way yields of sulfur per barrel of product can be computed. The three processes will illustrate examples of coal gasification for production of SNG, methanol or indirect liquids, direct liquefaction for production of naphtha and synthetic crude oil and finally, oil shale retorting for production of hydrotreated shale oil. 

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