Coal, chemicals from

Most coal-tar chemicals are recovered from coproduct coke ovens. Since the primary product of the ovens is metallurgical coke, production of coal chemicals from this source is highly dependent on the level of activity in the steel industry. In past years most large coke producers operated thein own coproduct recovery processes. Because of the decline in the domestic steel industry, the recent trend is for independent refiners to coUect cmde coal tars and light oils from several producers and then separate the marketable products. 

Other Organic Processes. Solvent extraction has found appHcation in the coal-tar industry for many years, as for example in the recovery of phenols from coal-tar distillates by washing with caustic soda solution. Solvent extraction of fatty and resimic acid from tall oil has been reported (250). Dissociation extraction is used to separate y -cresol fromT -cresol (251) and 2,4-x5lenol from 2,5-x5lenol (252). Solvent extraction can play a role in the direct manufacture of chemicals from coal (253) (see Eeedstocks, coal chemicals). 

Coal is used ia industry both as a fuel and ia much lower volume as a source of chemicals. In this respect it is like petroleum and natural gas whose consumption also is heavily dominated by fuel use. Coal was once the principal feedstock for chemical production, but ia the 1950s it became more economical to obtain most industrial chemicals from petroleum and gas. Nevertheless, certain chemicals continue to be obtained from coal by traditional routes, and an interest in coal-based chemicals has been maintained in academic and industrial research laboratories. Much of the recent activity in coal conversion has been focused on production of synthetic fuels, but significant progress also has been made on use of coal as a chemical feedstock (see Coal CONVERSION processes). 

Fig. 1. General pathways for the production of chemicals from coal (4).

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 Chemicals from Coal faciUty is a series of nine complex interrelated plants. These plants include air separation, slurry preparation, gasification, acid gas removal, sulfur recovery, CO /H2 separation, methanol, methyl acetate, and acetic anhydride. A block flow diagram of the process is shown in Eigure 3. The faciUty covers an area of 2.2 x 10 (55 acres) at Eastman s main plant site in Kingsport, Teimessee. The air separation plant is... 

The gasification plant is equipped with two Texaco gasifiers, each capable of producing all of the synthesis gas required for operation of the complex. Eastman chose an entrained-bed gasification process for the Chemicals from Coal project because of three attractive features. The product gas composition using locally available coal is particularly suitable for production of the desired chemicals. Also, the process has excellent environmental performance and generates no Hquids or tars. EinaHy, the process can be operated at the elevated pressure required for the downstream chemical plants. 

R. J. Tedeschi, Acetylene Based Chemicals from Coal and Other Natural Resources, Marcel Dekker, Inc., New York, 1982. 

F.-W. Kampmann and W. Portz, in K. R. Payne, ed.. Chemicals from Coal New Processes, John Wiley Sons, Inc., New York, 1987, Chapt. 2. 

Proof of the existence of benzene in the light oil derived from coal tar (8) first estabHshed coal tar and coal as chemical raw materials (see Eeedstocks, COAL chemicals). Soon thereafter the separation of coal-tar light oil into substantially pure fractions produced a number of the aromatic components now known to be present in significant quantities in petroleum-derived Hquid fuels. Indeed, these separation procedures were for the recovery of benzene—toluene—xylene (BTX) and related substances, ie, benzol or motor benzol, from coke-oven operations (8) (see BTX processing). 

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). 

F. W. Kampmaim and W. Portz, Chemicals from Coal via the Carbide Koute, Hoechst A.G., Heurth-Knap sack D-5030, Germany, 1991 Crit. Rep. Appl. Chem. 14, 32-44 (1987). 

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. 

Most coal chemicals are obtained from high temperature tar with an average yield over 5% of the coal which is carbonized. The yields in coking are about 70% of the weight of feed coal. Tars obtained from vertical gas retorts have a much more uniform chemical composition than those from coke ovens. Two or more coals are usually blended. The conditions of carbonization vary depending on the coals used and affect the tar composition. Coal-tar chemicals include phenols, cresols, xylenols, benzene, toluene, naphthalene, and anthracene. 

Gasification. Gasification of coal is used to provide gaseous fuels by surface and underground appHcations, Hquid fuels by indirect Hquefaction, ie, catalytic conversion of synthesis gas, and chemicals from conversion of synthesis gas. There are also appHcations in steelmaking (see Coal conversion PROCESSES, gasification). 

Nitrogen, unlike pyritic sulfur, is mosdy chemically bound in organic molecules in the coal and therefore not removable by physical cleaning methods. The nitrogen content in most U.S. coals ranges from 0.5—2.0 wt %. 

Whereas near-term appHcation of coal gasification is expected to be in the production of electricity through combined cycle power generation systems, longer term appHcations show considerable potential for producing chemicals from coal using syngas chemistry (45). Products could include ammonia, methanol, synthetic natural gas, and conventional transportation fuels. 

The petroleum industry is now the principal suppHer of ben2ene, toluene, the xylenes, and naphthalene (see BTX processing Feedstocks). Petroleum displaced coal tar as the primary source for these aromatic compounds after World War II because it was relatively cheap and abundantly available. However, the re-emergence of king coal is predicted for the twenty-first century, when oil suppHes are expected to dwindle and the cost of producing chemicals from coal (including new processes based on synthesis gas) will gradually become more competitive (3). 

Wastes from petroleum refining, natural gas purification and pyrolitic treatment of coal Wastes from inorganic chemical processes Wastes from organic chemical processes... 

The Chemistry and Technology of Petroleum, James G. Speight The Desulfurization of Heavy Oils and Residua, James G. Speight Catalysis of Organic Reactions, edited by William R. Moser Acetylene-Based Chemicals from Coal and Other Natural Resources, Robert J. Tedeschi... 

The search for alternative ways to produce monomers and chemicals from sources other than oil, such as coal, has revived working using Fisher Tropseh technology, which produces in addition to fuels, light olefins, sulfur, phenols, etc. These could he used as feedstocks for petrochemicals as indicated in Chapter 4. 

Comparing chemicals that Mansfield obtained from coal tar with chemicals from other sources, Hofmann made a surprising discovery. Some of the constituents of coal tar were similar to a chemical obtained from the... 

To use the Lang factors the engineer must define what type of plant is being built. This is important, since the largest factor is 50% greater than the smallest. It is sometimes difficult, however, because there is a continuum of chemical plants between the two extremes. A coal-briquetting plant is obviously a solids processing plant. Methanol and ammonia plants are fluids plants. Plants that extract chemicals from solids fall between. 

In modern terms, asphaltene is conceptually defined as the normal-pentane-insoluble and benzene-soluble fraction whether it is derived from coal or from petroleum. The generalized concept has been extended to fractions derived from other carbonaceous sources, such as coal and oil shale (8,9). With this extension there has been much effort to define asphaltenes in terms of chemical structure and elemental analysis as well as by the carbonaceous source. It was demonstrated that the elemental compositions of asphaltene fractions precipitated by different solvents from various sources of petroleum vary considerably (see Table I). Figure 1 presents hypothetical structures for asphaltenes derived from oils produced in different regions of the world. Other investigators (10,11) based on a number of analytical methods, such as NMR, GPC, etc., have suggested the hypothetical structure shown in Figure 2. 

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