Coking, products from

Heat to raise the coke products from the regenerator dense temperature to flue gas temperature... 

The results of this investigation and particularly of those with butadiene strongly suggest that at least portions of the inactive coke formed during pyrolyses involve the following sequence of events (a) production in the gas phase of unsaturated hydrocarbons, (b) chemical condensation or polymerization of unsaturated hydrocarbons to produce rather heavy hydrocarbons, (c) physical condensation of these heavy hydrocarbons as liquids on the reactor walls or in the transfer line exchangers, and (d) decomposition of the liquids to coke (or tars) and hydrogen. This sequence of events is essentially identical to the one proposed by Lahaye et al. (12) for coke production from cyclohexane, toluene, or n-hexane. 

From the worldwide coke production from hard coal, an estimated (theoretical) 60 billion Nm of hydrogen could be recovered [14]. 

Liquid products from coking are very unstable (high diene contents), very olefinic, and highly contaminated by sulfur and nitrogen. The production of gas is considerable. 

Feedstocks for this very flexible process are usually vacuum distillates, deasphalted oils, residues (hydrotreated or not), as well as by-products from other processes such as extracts, paraffinic slack waxes, distillates from visbreaking and coking, residues from hydrocracking, converted in mixtures with the main feedstock. 

The feedstocks in question are primary distillation streams and some conversion products from catalytic cracking, coking, visbreaking, and residue conversion units. 

Fractions treated by this process are light products from the primary distillation LPG to Kerosene, or light products from thermal and catalytic cracking (visbreaking, coking, FCC). 

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. 

Approximately 50—55% of the product from a coal-tar refinery is pitch and another 30% is creosote. The remaining 15—20% is the chemical oil, about half of which is naphthalene. Creosote is used as a feedstock for production of carbon black and as a wood preservative. Because of modifications to modem coking processes, tar acids such as phenol and cresyUc acids are contained in coal tar in lower quantity than in the past. To achieve economies of scale, these tar acids are removed from cmde coal tar with a caustic wash and sent to a central processing plant where materials from a number of refiners are combined for recovery. 

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. 

When energy alternatives are available, a compromise between cost and quaHty is often realized. Blending of coals can be used to achieve more desirable quaHties. For example, lignite from the former Yugoslavia has been blended with, and even substituted for, the highly caking Rasa coal used for coke production in the iron (qv) and steel (qv) industries. 

Recovering ammonia as a by-product from other processes accounted for less than 1% of the total U.S. ammonia production in 1987. The principal source of by-product ammonia is from the coking of coal. In the coking operation, about 15—20% of the nitrogen present in the coal is Hberated as ammonia and is recovered from the coke oven gas as ammonium sulfate, ammonia Hquor, and ammonium phosphates. The recovery product depends on the scmbbing medium employed, sulfuric acid, milk of lime, and phosphoric acid, respectively. Ammonium sulfate recovery by the so-called semidirect process, is most widely employed. 

Since the 1950s, benzene production from petroleum feedstocks has been very successful and accounts for about 95% of all benzene obtained. Less than 5% of commercial benzene is derived from coke oven light oil. 

Thermal Cracking. Heavy petroleum fractions such as resid are thermally cracked in delayed cokers or flexicokers (44,56,57). The main products from the process are petroleum coke and off-gas which contain light olefins and butylenes. This stream also contains a considerable amount of butane. Process conditions for the flexicoker are more severe than for the delayed coker, about 550°C versus 450°C. Both are operated at low pressures, around 300—600 kPa (43—87 psi). Flexicokers produce much more linear butenes, particularly 2-butene, than delayed cokers and about half the amount of isobutylene (Table 7). This is attributed to high severity of operation for the flexicoker (43). 

Carbon black from oil is the main competition for the product from coal, which is used in filters. Carbon for electrodes is primarily made from petroleum coke, although pitch coke is used in Germany for this product. The pitch binder used for electrodes and other carbon products is almost always a selected coal tar pitch. 

Worldwide demand for blast furnace coke has decreased over the past decade. Although, as shown in Figure 1, blast furnace hot metal production (pig iron) increased by about 4% from 1980 to 1990, coke production decreased by about 2% over the same time period (3). This discrepancy of increased hot metal and decreased coke production is accounted for by steady improvement in the amounts of coke required to produce pig iron. Increased technical capabihties, although not universally implemented, have allowed for about a 10% decrease in coke rate, ie, coke consumed per pig iron produced, because of better specification of coke quaUty and improvements in blast furnace instmmentation, understanding, and operation methods (4). As more blast furnaces implement injection of coal into blast furnaces, additional reduction in coke rate is expected. In some countries that have aggressively adopted coal injection techniques, coke rates have been lowered by 25% (4). 

Some hydrogen cyanide is formed whenever hydrocarbons (qv) are burned in an environment that is deficient in air. Small concentrations are also found in the stratosphere and atmosphere. It is not clear whether most of this hydrogen cyanide comes from biological sources or from high temperature, low oxygen processes such as coke production, but no accumulation has been shown (3). 

Until the mid-1950s the main raw material source for the European plastics industry was coal. On destructive distillation coal yields four products coal tar, coke, coal gas and ammonia. Coal tar was an important source of aromatic chemicals such as benzene, toluene, phenol, naphthalene and related products. From these materials other chemicals such as adipic acid, hexamethylenedia-mine, caprolactam and phthalic anhydride could be produced, leading to such important plastics as the phenolic resins, polystyrene and the nylons. 

In addition to supplying transportation fuels and chemicals, products from coal liquefaction and extraction have been used m the past as pitches for binders and feedstocks for cokes [12]. Indeed, the majority of organic chemicals and carbonaceous materials prior to World War II were based on coal technologies. Unfortunately, this technology was supplanted when inexpensive petroleum became available dunng the 1940s. Nevertheless, despite a steady decline of coal use for non-combustion purposes over the past several decades, coal tars still remain an important commodity in North America. 

Coal-based pitches are predommantly byproducts of metallurgical coke operations in recovery-type coke ovens. The volatile products from the coke oven are recovered and processed, in simplest terms, into gas, light oils, and tar. The quantity and character of the materials are influenced by the type of coal charge, the design of the cokmg equipment, and the temperature and time profile of carboni2ation. Table 1 shows a typical yield of products from the... 

---