Coal derivatives

Produced from Co l. Estimates of the cost of producing methanol from coal have been made by the U.S. Department of Energy (DOE) (12,17) and they are more uncertain than those using natural gas. Experience in coal-to-methanol faciUties of the type and size that would offer the most competitive product is limited. The projected costs of coal-derived methanol are considerably higher than those of methanol produced from natural gas. The cost of the production faciUty accounts for most of the increase (11). Coal-derived methanol is not expected to compete with gasoline unless oil prices exceed 0.31/L ( 50/bbl). Successful development of lower cost entrained gasification technologies could reduce the cost so as to make coal-derived methanol competitive at oil prices as low as 0.25/L ( 40/bbl) (17) (see Coal conversion processes). 

The term feedstock in this article refers not only to coal, but also to products and coproducts of coal conversion processes used to meet the raw material needs of the chemical industry. This definition distinguishes between use of coal-derived products for fuels and for chemicals, but this distinction is somewhat arbitrary because the products involved in fuel and chemical appHcations are often identical or related by simple transformations. For example, methanol has been widely promoted and used as a component of motor fuel, but it is also used heavily in the chemical industry. Frequendy, some or all of the chemical products of a coal conversion process are not isolated but used as process fuel. This practice is common in the many coke plants that are now burning coal tar and naphtha in the ovens. 

In 1980, the last year for which a breakdown has been pubUshed, the amount of benzene derived from coal in the United States was 168,000 t or 2.5% of domestic benzene production. Coal-derived toluene was 0.8% of production, and xylenes from coal were only 0.1% of total chemical production (9). The amounts and proportions of BTX components derived from coal in the United States are expected to be nearly the same today as in 1980. Based on information submitted to the International Trade Commission, approximately 25 companies participated in the coal-tar industry in the United States in 1990. 

Although small amounts of hquids are produced during coal pyrolysis, significant amounts of coal-derived hquids did not become available until after the... 

Sasol produces synthetic fuels and chemicals from coal-derived synthesis gas. Two significant variations of this technology have been commercialized, and new process variations are continually under development. Sasol One used both the fixed-bed (Arge) process, operated at about 240°C, as weU as a circulating fluidized-bed (Synthol) system operating at 340°C. Each ET reactor type has a characteristic product distribution that includes coproducts isolated for use in the chemical industry. Paraffin wax is one of the principal coproducts of the low temperature Arge process. Alcohols, ketones, and lower paraffins are among the valuable coproducts obtained from the Synthol process. 

The Eastman acetic anhydride [108-24-7] process provides an extension of carbonylation chemistry to carboxyUc acid esters. The process is based on technology developed independendy in the 1970s by Eastman and Halcon SD. The Eastman acetic anhydride process involves carbonylation of methyl acetate [79-20-9] produced from coal-derived methanol and acetic acid [64-19-7]. 

There are some chemicals that can be made economically from coal or coal-derived substances. Methanol and CO are used to make acetic anhydride and acetic acid. Methanol itself can be made from synthesis gas over a copper-2inc catalyst (see Feedstocks, coal chemicals). 

With regard to coal-derived tar and pitch, the following definitions are appropriate to distinguish them from ostensibly similar materials from other sources and from cmde oil in particular. 

In the European Union, coal-derived complex chemical substances, ie, those contained in the European Inventory of Existing Commercial Chemical Substances, have been classified for carcinogenicity in the twenty-first adaptation to technical progress of the European Commission (EC) Dangerous Substances Directive 1994 67/548/EEC (57). The EC Regulation 793/93 requires data sets to be submitted by producers or importers to the... 

World benzene production rose to 6 x 10 t(1.8 x 10 gallons) in 1988 (63). The United States is the largest producer of benzene and accounts for about 30% of world production. The total annual U.S. production of benzene is shown in Table 4 which gives production figures from both petroleum- and coal-derived benzene. These figures show that benzene obtained from coal is steadily declining, and presendy accounts for less than 5% of the total. Many usehil statistics have been compiled (64). 

The U.S. Department of Energy has funded a research program to develop the Hquid-phase methanol process (LPMEOH) (33). This process utilizes a catalyst such as copper—zinc oxide suspended in a hydrocarbon oil. The Hquid phase is used as a heat-transfer medium and allows the reaction to be conducted at higher conversions than conventional reactor designs. In addition, the use of the LPMEOH process allows the use of a coal-derived, CO-rich synthesis gas. Typical reactor conditions for this process are 3.5—6.3 MPa (35—60 atm) and 473—563 K (see Methanol). 

A chemistry based on the conversion of synthesis gas has been developed and appHed extensively in South Africa to the production of Hquid fuels and many other products. A small-scale production is used in the manufacture of photographic film materials from coal-derived synthesis gas in the Eastman Kodak plant in Kingsport, Tennessee. However, the principal production of chemicals from coal involves the by-products of coke manufacturing. 

The Pott-Broche process (101) was best known as an early industrial use of solvent extraction of coal but was ended owing to war damage. The coal was extracted at about 400°C for 1—1.5 h under a hydrogen pressure of 10—15 MPa (100—150 atm) using a coal-derived solvent. Plant capacity was only 5 t/h with an 80% yield of extract. The product contained less than 0.05% mineral matter and had limited use, mainly in electrodes. 

Processes for hydrogen gasification, hydrogen pyrolysis, or coking of coal usually produce Hquid co-products. The Hygas process produces about 6% Hquids as benzene, toluene, and xylene. Substitution of petroleum residuum for the coal-derived process oil has been used in studies of coal Hquefaction and offers promise as a lower cost technology (104). 

Eor shifting coal-derived gas, conventional iron—chromium catalysts can be used. Because coal gas has a significantly higher concentration of carbon monoxide than is found in gas streams in conventional refineries, the catalyst must be able to withstand high thermal loads. However, potential catalyst poisons such as phenol and other hydrocarbons are not a concern in entrained-bed gasifiers. 

R. P. AHen, R. A. Battista, and T. E. Ekstrom, "Characteristics of an Advanced Gas Turbiue with Coal Derived Fuel Gases," Ninth NnnualEPRJ Conference on Gasification Power Plants, Palo Alto, Calif., Oct. 1990. 

The H-Coal process could operate in one of two modes, depending on the desired product slate. In the "syn-cmde" mode, a fluid-bed coking unit was employed to maximize recovery of distillate from the Hquefaction product (Fig. 7a). When operated in the fuel oil mode (Fig. 7b), no coker was used and the primary product was a coal-derived low sulfur fuel oil. Total hydrogen demand on the process was also reduced in the latter mode of operation. 

Conventional coal-tar fuels from retorting Typical coal-derived fuels with different levels of hydrogenation Synthetic crude oils, by hydrogenation ... 

It IS expected that production of coal-derived pitches, liquids, and chemicals will take on a more important role in the future. This is of some strategic concern to the United States, where the demand for domestic petroleum is greater than the supply. Moreover, the quality of imported petroleum cmdes is declinmg in that they contain increasing amounts of contarmnant metals and sulfur... 

In recent years researchers at West Virginia University have developed coal-derived pitches on a laboratory scale in quantities sufficient to make 1 kg samples of calcined coke for fashioning graphite test specimens. The pitches were derived by uhlizmg solvent extraction with N-methyl pyrrohdone (NMP). This solvent is able to isolate coal-based pitches m high yield and with low mineral matter content [13]. It is this work that will form the basis of the discussion for the later part of this chapter. 

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