Coke oven

The composition of coal tar varies with the carbonization method but consists, largely, of mononuclear and polynuclear aromatic compounds and their derivatives. Coke oven tars are relatively low in aliphatic and phenolic content while low-temperature tars have much higher contents of both. 

Coke oven light oil is a by-product of the manufacture of coke for the steel industry. When coal is subjected to high temperature carbonization, it yields 16—25 Hters /tonne of light oil that contains 3—6 vol % of mixed xylenes. 

A breakdown of the mixed xylene supply sources in the United States is summarized in Table 1 (1). As shown in Table 1, the primary source of xylenes in the United States is catalytic reformate. In 1992, over 90% of the isolated xylenes in the United States were derived from this source. Approximately 9% of the recovered xylenes is produced via toluene disproportionation (TDP). In the United States, only negligible amounts of the xylenes are recovered from pyrolysis gasoline and coke oven light oil. In other parts of the world, pyrolysis gasoline is a more important source of xylenes. 

A new countercurrent continuous centrifugal extractor developed in the former USSR (214) has the feature that mechanical seals are replaced by Hquid seals with the result that operation and maintenance are simplified the mechanical seals are an operating weak point in most centrifugal extractors. The operating units range between 400 and 1200 mm in diameter, and a capacity of 70 m /h has been reported in service. The extractors have been appHed in coke-oven refining (see Coal conversion processes), erythromycin production, lube oil refining, etc. 

The Phenox process (254) removes phenol (qv) from the efduent from catalytic cracking in the petroleum industry. Extraction of phenols from ammoniacal coke-oven Hquor may show a small profit. Acetic acid can be recovered by extraction from dilute waste streams (255). Oils are recovered by extraction from oily wastewater from petroleum and petrochemical operations. Solvent extraction is employed commercially for the removal of valuable... 

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. 

Many valuable chemicals can be recovered from the volatile fractions produced in coke ovens. Eor many years coal tar was the primary source for chemicals such as naphthalene [91-20-3] anthracene [120-12-7] and other aromatic and heterocycHc hydrocarbons. The routes to production of important coal-tar derivatives are shown in Eigure 1. Much of the production of these chemicals, especially tar bases such as the pyridines and picolines, is based on synthesis from petroleum feedstocks. Nevertheless, a number of important materials continue to be derived from coal tar. 

In 1990, U.S. coke plants consumed 3.61 x 10 t of coal, or 4.4% of the total U.S. consumption of 8.12 x ICf t (6). Worldwide, roughly 400 coke oven batteries were in operation in 1988, consuming about 4.5 x 10 t of coal and producing 3.5 x 10 t metallurgical coke. Coke production is in a period of decline because of reduced demand for steel and increa sing use of technology for direct injection of coal into blast furnaces (7). The decline in coke production and trend away from recovery of coproducts is reflected in a 70—80% decline in volume of coal-tar chemicals since the 1970s. 

Essentially all the ammonium sulfate fertilizer used in the United States is by-product material. By-product from the acid scmbbing of coke oven gas is one source. A larger source is as by-product ammonium sulfate solution from the production of caprolactam (qv) and acrylonitrile, (qv) which are synthetic fiber intermediates. A third but lesser source is from the ammoniation of spent sulfuric acid from other processes. In the recovery of by-product crystals from each of these sources, the crystallization usually is carried out in steam-heated sa turator—crystallizers. Characteristically, crystallizer product is of a particle size about 90% finer than 16 mesh (ca 1 mm dia), which is too small for satisfactory dry blending with granular fertilizer materials. Crystals of this size are suitable, however, as a feed material to mixed fertilizer granulation plants, and this is the main fertilizer outlet for by-product ammonium sulfate. 

Since 1960, about 95% of the synthetic ammonia made in the United States has been made from natural gas worldwide the proportion is about 85%. Most of the balance is made from naphtha and other petroleum Hquids. Relatively small amounts of ammonia are made from hydrogen recovered from coke oven and refinery gases, from electrolysis of salt solutions, eg, caustic chlorine production, and by electrolysis of water. In addition there are about 20 ammonia plants worldwide that use coal as a hydrogen source. 

The conversion of coal to gas on an industrial scale dates to the early nineteenth century (14). The gas, often referred to as manufactured gas, was produced in coke ovens or similar types of retorts by simply heating coal to vaporize the volatile constituents. Estimates based on modem data indicate that the gas mixture probably contained hydrogen (qv) (ca 50%), methane (ca 30%), carbon monoxide (qv) and carbon dioxide (qv) (ca 15%), and some inert material, such as nitrogen (qv), from which a heating value of approximately 20.5 MJ/m (550 Btu/fT) can be estimated (6). 

Some beehive ovens, having various improvements and additions of waste heat boilers, thereby allowing heat recovery from the combustion products, may stiU be in operation. Generally, however, the beehive oven has been replaced by waH-heated, horizontal chamber, ie, slot, ovens in which higher temperatures can be achieved as well as a better control over the quality of the coke. Modem slot-type coke ovens are approximately 15 m long, approximately 6 m high, and the width is chosen to suit the carbonization behavior of the coal to be processed. For example, the most common widths are ca 0.5 m, but some ovens may be as narrow as 0.3 m, or as wide as 0.6 m. 

Most modem coke ovens operate on a regenerative heating cycle in order to obtain as much surplus gas as possible for use on the works, or for sale. If coke-oven gas is used for heating the ovens, the majority of the gas is surplus to requirements. If producer gas is used for heating, much of the coke-oven gas is surplus. 

The main difference between gas works and coke oven practice is that, in a gas works, maximum gas yield is a primary consideration whereas in the coke works the quality of the coke is the first consideration. These effects are obtained by choice of a coal feedstock that is suitable to the task. For example, use of lower volatile coals in coke ovens, compared to coals used in gas works, produces lower yields of gas when operating at the same temperatures. In addition, the choice of heating (carbonizing) conditions and the type of retort also play a principal role (10,35). 

F. M. Fess, EListory of Coke Oven Technology, Gluckauf Vedag, Essen, Germany, 1957. 

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). 

Large-scale recovery of light oil was commercialized in England, Germany, and the United States toward the end of the nineteenth century (151). Industrial coal-tar production dates from the earliest operation of coal-gas faciUties. The principal bulk commodities derived from coal tar are wood-preserving oils, road tars, industrial pitches, and coke. Naphthalene is obtained from tar oils by crystallization, tar acids are derived by extraction of tar oils with caustic, and tar bases by extraction with sulfuric acid. Coal tars generally contain less than 1% benzene and toluene, and may contain up to 1% xylene. The total U.S. production of BTX from coke-oven operations is insignificant compared to petroleum product consumptions. 

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