Coking oven gas

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. 

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. 

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. 

In the semidirect process, (Fig. 23) the taw coke oven gas is cooled to condense tar and ammonia Hquor. The heavy layer, tar phase, is pumped to storage and the aqueous layer containing free and fixed ammonia is subsequendy processed in a stiH operation. Free ammonia is that which is in a form which readily dissociates by heat. Fixed ammonia is in a form which requites the presence of an alkaH, such as milk of lime, to effect the ammonia release. 

Adsorption Processes. More recendy, pressure swing adsorption (PSA) processes utilizing a high selectivity copper adsorbent have been utilized to effectively separate carbon monoxide from blast furnace gas and coke oven gas (97—101). 

Chlorination of Methane. Methane can be chlorinated thermally, photochemicaHy, or catalyticaHy. Thermal chlorination, the most difficult method, may be carried out in the absence of light or catalysts. It is a free-radical chain reaction limited by the presence of oxygen and other free-radical inhibitors. The first step in the reaction is the thermal dissociation of the chlorine molecules for which the activation energy is about 84 kj/mol (20 kcal/mol), which is 33 kJ (8 kcal) higher than for catalytic chlorination. This dissociation occurs sufficiendy rapidly in the 400 to 500°C temperature range. The chlorine atoms react with methane to form hydrogen chloride and a methyl radical. The methyl radical in turn reacts with a chlorine molecule to form methyl chloride and another chlorine atom that can continue the reaction. The methane raw material may be natural gas, coke oven gas, or gas from petroleum refining. 

In early times hydrogen cyanide was manufactured from beet sugar residues and recovered from coke oven gas. These methods were replaced by the Castner process in which coke and ammonia were combined with Hquid sodium to form sodium cyanide. If hydrogen cyanide was desired, the sodium cyanide was contacted with an acid, usually sulfuric acid, to Hberate hydrogen cyanide gas, which was condensed for use. This process has since been supplanted by large-scale plants, using catalytic synthesis from ammonia and hydrocarbons. 

Coke-oven gas Producer gas Water gas Carbureted water gas Synthetic coal gas... 

The coke oven gas is cooled, and by-products are recovered. Flushing liquor, formed from the cooling of coke oven gas, and liquor from primary coolers contain tar and are sent to a tar decanter. Note that the coke oven gas has a heating value and can be used effectively in the cogeneration of heat or electricity, which can be used by the plant, or if available in sufficient quantities, can be sold into local grids. 

An electrostatic precipitator is used to remove more tar from coke oven gas. The tar is then sent to storage. Ammonia liquor is also separated from the tar decanter and sent to wastewater treatment after ammonia recovery. Coke oven gas is further cooled in a final cooler. Naphthalene is removed in a separator on the final cooler. Light oil is then removed from the coke oven gas and is fractionated to recover benzene, toluene, and xylene. Some facilities may include an onsite tar distillation unit. The Claus process is normally used to recover sulfur from coke oven gas. During the coke quenching, handling, and screening operation, coke breeze is produced. The breeze is either reused on site (e.g., in the sinter plant) or sold offsite as a by-product. 

Baghouses are preferred over venturi scrubbers for controlling particulate matter emissions from loading and pushing operations because of the higher removal efficiencies. ESPs are effective for final tar removal from coke oven gas. Stack air emissions should be monitored continuously for particulate matter. Alternatively, opacity measurements of stack gases can suffice. Fugitive emissions should be monitored annually for VOCs. 

Recover sulfur from coke oven gas. Recycle Claus tail gas into coke oven gas system. 

A coking operation has about 1 million cubic meters per year of excess coke oven gas that it generally sends to flares. (A) Instead of burning this offgas in flares, what else could be done with it (B) What is the value of this gas (assume it to be essentially natural gas or methane) ... 

J Consider the coke-oven gas COG sweetening process shown in Fig. 3.22. The basic objective of COG sweetening is the removal of acidic impurities, primarily hydrogen sulfide, from COG (a mixture of H2, CH4, CO, N2, NH3, CO2, and H2S). Hydrogen sulfide m undesirable impurity, because it is corrosive and contributes to SO2 emission when the G... 

Entgasungs-gaa, n. coke-oven gas. -mittel, n. degassing agent, -warme, /. Coke) heat of carbonization. 

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