Coke making process and its environmental impacts:
Coke is a solid carbon fuel and carbon source used to melt and reduce iron ore. Coke and coke by-products, including coke oven gas, are produced by the pyrolysis (heating in the absence of air) of suitable grades of coal. The process also includes the processing of coke oven gas to remove tar, ammonia (usually recovered as ammonium sulfate), phenol, naphthalene, light oil, and sulfur before the gas is used as fuel for heating the ovens.
A. Coke making process: In the coke-making process, bituminous coal is fed (usually after processing operations to control the size and quality of the feed) into a series of ovens, which are sealed and heated at high temperatures in the absence of oxygen, typically in cycles lasting 14 to 36 hours. Volatile compounds that are driven off the coal are collected and processed to recover combustible gases and other by-products. The solid carbon remaining in the oven is coke. It is taken to the quench tower, where it is cooled with a water spray or by circulating an inert gas (nitrogen), a process known as dry quenching. The coke is screened and sent to a blast furnace or to storage. 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. 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 the separator on the final cooler. Light oil is then removed from the coke oven gas and is fractionated to recover benzene, toluene, and xylene. During the coke quenching, handling, and screening operation, coke breeze is produced. It is either reused on site (e.g., in the sinter plant) or sold off site as a by-product.
B. Pollution during coke making process:
The coke oven is a major source of fugitive air emissions. The coking process emits particulate matter (PM); volatile organic compounds (VOCs); polynuclear aromatic hydrocarbons (PAHs); methane, at approximately 100 grams per metric ton (g/t) of coke; ammonia; carbon monoxide; hydrogen sulfide (50–80 g/t of coke from pushing operations); hydrogen cyanide; and sulfur oxides, SOx (releasing 30% of sulfur in the feed). Significant amount of VOCs may also be released in by- product recovery operations. For every ton of coke produced, approximately 0.7 to 7.4 kilograms (kg) of PM, 2.9 kg of SOx (ranging from 0.2 to 6.5 kg), 1.4 kg of nitrogen oxides (NOx), 0.1 kg of ammonia, and 3 kg of VOCs (including 2 kg of benzene) may be released into the atmosphere if there is no vapor recovery system. Coal-handling operations may account for about 10% of the particulate load. Coal charging, coke pushing, and quenching are major sources of dust emissions.
Wastewater is generated at an average rate ranging from 0.3 to 4 cubic meters (m3) per ton of coke processed. Major wastewater streams are generated from the cooling of the coke oven gas and the processing of ammonia, tar, naphthalene, phenol, and light oil. Process wastewater may contain 10 milligrams per liter (mg/l) of benzene, 1,000 mg/l of biochemical oxygen demand (BOD) (4 kg/t of coke), 1,500–6,000 mg/l of chemical oxygen demand (COD), 200 mg/l of total suspended solids, and 150–2,000 mg/l of phenols (0.3–12 kg/t of coke). Wastewaters also contain PAHs at significant concentrations (up to 30 mg/ l), ammonia (0.1–2 kg nitrogen/t of coke), and cyanides (0.1–0.6 kg/t of coke). Coke production facilities generate process solid wastes other than coke breeze (which averages 1 kg/t of product). Most of the solid wastes contain hazardous components such as benzene and PAHs. Waste streams of concern include residues from coal tar recovery (typically 0.1 kg/t of coke), the tar decanter (0.2 kg/t of coke), tar storage (0.4 kg/t of coke), light oil processing (0.2 kg/t of coke), wastewater treatment (0.1 kg/t of coke), naphthalene collection and recovery (0.02 kg/t of coke), tar distillation (0.01 kg/t of coke), and sludges from biological treatment of wastewaters.
C. Pollution Prevention and Control: Pollution prevention in coke making is focused on reducing coke oven emissions and developing coke-less iron & steel-making techniques. The following pollution prevention and control measures should be considered.
1. General -
(a) Use cokeless iron- and steel-making processes, (b) such as the direct reduction process, to eliminate the need to manufacture coke. (c) Use beneficiation (preferably at the coal mine) and blending processes that improve the quality of coal feed to produce coke of desired quality and reduce emissions of sulfur oxides and other pollutants. (d) Use enclosed conveyors and sieves for coal and coke handling. Use sprinklers and plastic emulsions to suppress dust formation. Provide windbreaks where feasible. Store materials in bunkers or warehouses. Reduce drop distances. (e) Use and preheat high-grade coal to reduce coking time, increase throughput, reduce fuel consumption, and minimize thermal shock to refractory bricks.
2. Coke Oven Emissions –
(a) Charging: dust particles from coal charging should be evacuated by the use of jumper-pipe systems and steam injection into the ascension pipe or controlled by fabric filters.
(b) Coking: use large ovens to increase batch size and reduce the number of chargings and pushings, thereby reducing the associated emissions. Reduce fluctuations in coking conditions, including temperature. Clean and seal coke oven openings to minimize emissions. Use mechanical cleaning devices (preferably automatic) for cleaning doors, door frames, and hole lids. Seal lids, using a slurry. Use low-leakage door construction, preferably with gas sealing.
(c) Pushing: emissions from coke pushing can be reduced by maintaining a sufficient coking time, thus avoiding “green push.” Use sheds and enclosed cars, or consider use of traveling hoods. The gases released should be removed and passed through fabric filters.
(d) Quenching: where feasible, use dry instead of wet quenching. Filter all gases extracted from the dry quenching unit. If wet quenching, is used, provide interceptors (baffles) to remove coarse dust. When wastewater is used for quenching, the process transfers pollutants from the wastewater to the air, requiring subsequent removal. Reuse quench water.
(e) Conveying and sieving: enclose potential dust sources, and filter evacuated gases.
3. By-Product Recovery –
(a) Use vapor recovery systems to prevent air emissions from light oil processing, tar processing naphthalene processing, and phenol and ammonia recovery processes.
(b) Segregate process water from cooling water.
(c) Reduce fixed ammonia content in ammonia liquor by using caustic soda and steam stripping.
(d) Recycle all process solid wastes, including tar decanter sludge, to the coke oven.
(e) Recover sulfur from coke oven gas. Recycle Claus tail gas into the coke oven gas system.
