Lecture 40. Environmental impact of Solid Fertilizer Industry

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1 Lecture 40 Environmental impact of Solid Fertilizer Industry Solid fertilizers are produced in two stages. 1. Synthesis is performed by the following: Reaction of ammonia and CO 2 (ammonium carbonate and urea). Reaction between sulfuric and/or phosphoric acid with phosphate rock (SSP and TSP). Reaction between acids (sulfuric, phosphoric, and metric) and ammonia. 2. Providing the physical form of the product by crystallization, granulation, or prilling. It is economically feasible to eliminate all effluents and emissions during production of fertilizers. Raw Materials The principal raw materials for finished solid fertilizers are ammonia; nitric, sulfuric, and phosphoric acids; phosphate rock; and potassium chloride. Utilities The production of fertilizers requires steam, fuel for drying, and water for scrubbing of gases, mist, and dust from granulation or prilling units. Waste characteristics and Impacts Atmospheric Emissions 1. Single Superphosphate/triple Superphosphate- Phosphate rock usually contains between 3% and 4.5% of fluoride by weight. Released during the acidulation of phosphate rock, hydrogen fluoride is usually converted into fluosilicic acid by silica in the rock, most of which is retained in the TSP process, but about25% is released in SSP production. Wet scrubbers are required for production of SSP. In addition, fluoride emission continues during the curing process. Feed stocks- handling bins for phosphate rock must be equipped with individual bag filters from which recovered dust is recycled.

2 Efficient scrubber designs allow recovery of the H 2 SiF 6 as a concentrated solution, which could be processed to synthetic cryolite, aluminum fluoride, and various fluorosilicates. If no market is available for the acid or fluoride derivatives, the fluorosilicic acid can be neutralized by liming. The neutralized slurry may require further treatment before discharge. 2. Ammonium Phosphates (DAP/MAP) - The ammonia-acid reaction produces steam containing ammonia and fluorine; these are scrubbed by water and/ or acids. In granulation and prilling equipment the gases from dryers contain dust; they must be filtered by cyclone and bag filter systems when dry. To prevent condensation of water from drying gases, dust recovery equipment is insulated and heated externally. Most of the recovered materials is recycles to the process. 3. Nitro phosphates- The production of nitro phosphate in all stages of production emits the following gases: a. Acidulation of the phosphate rock with nitric acid produces NO x and fluorine compounds. An example of NO x treatment for a nitro phosphate plant is shown. Off gases from the nitric acid attack section and from calcium nitrate filtration are scrubbed; the remaining nitrate are decomposed in the reactor. Ammonium nitrate solution is recycled to the process. b. Evaporation (condensation) produces emission of fluorine compounds and ammonia. c. Prilling and granulation processes produce dust and ammonia emissions. 4. Ammonium Nitrate, Calcium Ammonium Nitrate, Ammonium Sulfate (AN/CAN/AS)- The main emissions to the atmosphere include the following: From the reaction and evaporation system: steam containing ammonia and ammonium nitrate; these are in small quantities and treated in the scrubbing system. Scrubbing waters are recycled to the reaction/evaporation system. Ammonium nitrate mist is released from the prilling tower. The dust in the cooling air disperses into the atmosphere and reaches soil many kilometers in radius from the prilling tower. Ammonium nitrate dust can be extremely harmful to pine trees.

3 The amount emitted from specially equipped prilling towers (dust collection and Brinks filter system) may be between 0.25 and 0.5kg of AN / tonne of fertilizer. 5. Urea The main air pollution in area plants originates from the prilling tower. The vented hot air amounts to 10,000-15,000 mg of Nm 3 / tonne of urea containing an average of 500-1,000 mg of urea /Nm 3 of air before treatment. Dust removal systems such as the impinger type baffle-plant system may decrease concentrations of dust to mg of urea/nm 3 of air. The remaining dust is very fine (less than 10 micro meters); therefore, dry cyclones are not effective in further reducing emissions. Improved dust removal system developed recently may reduce the emissions down 30 gm of urea/ Nm3 of air and bring the losses to 0.3kg/tonne of urea. Waste water Direct process liquid effluents originating from fertilizer processes are rare. In most cases in urea and ammonium nitrate production, wet scrubbers are operated at low concentrations to allow economic recovery. Solutions from scrubbers are concentrated by adding screened fines and dust to increase the concentration for recycling. Adequately sized holding tanks are required to prevent recyclable effluent from overflowing to the sewer during shutdown or abnormal conditions. Aqueous effluent from the fertilizer plant can originate from spills, leaking pumps, or flanges. The severity of leakage depends on operating and maintenance standards. Solid Waste- Solid wastes are not generally produced in finished fertilizer production processes because off size material is recycled to the process. Hazardous Waste-There are no hazardous wastes in fertilizer production other than the cadmium contained in certain fertilizers. Fugitive Emissions- Small amounts of fluorine derivatives are released into the atmosphere. Similarly there can be small amounts of fertilizers released during maintenance. Contaminants of Concerns- There are no contaminants of major concern in fertilizer production. The cadmium level in fertilizers produced using phosphoric acid is increasingly causing concern, and this may influence the choice of raw materials.

4 Environmental Impact- Fertilizer production processes that are suitability abating emissions do not release material in harmful quantities to the atmosphere. The following emissions that have negative impact on the environment could be expected. Ammonia and acidic fumes may create in the plant s vicinity and can cause damage to vegetation. Fluoride emissions cause damage to vegetation and harm to livestock that consume vegetation. If the dust released into the atmosphere is excessive, it may cau8se damage to vegetation, especially to the pine forests. If plant nutrients are released to the aquatic environment from the scrubber system or runoff water, it is possible that eutrophication of water resources may take place, especially in lakes and closed reservoirs. Pollution Prevention and Control a. Source Reduction-Most emissions of fluorides into the atmosphere can be reduced by selecting efficient absorption equipment. NO 2 Emissions from the nitro phosphate process can be controlled by adding urea to the digestion stage. Gases from the digestion stage are treated in wet scrubbers. Waste can be minimized by high level of operation and maintenance to avoid spillages. Any spillage, whether solid or liquid, should be returned to the process. b. Recycling and Byproduct Recovery- All materials resulting from fertilizer production can be recycled. Efficient equipment for scrubbing and dust recovery must be utilized. c. Hazardous Materials Handling, Management, and Disposal- If they are manufactured accounting to international standards, fertilizer products are generally of low hazard. Ammonium nitrate and high ammonium nitrate fertilizers are considerd to be oxidizing agents and require special transport and storage measures. They should not in any case be mixed with hydrocarbons or carbohydrates. It is necessary to avoid any contact of ammonium nitrate with open flame.

5 As much as possible, the fluorides should be transformed into useful industrial products. In critical cases when there is no market for such a product, wash waters must be returned to the process and discharged with phosphogypsum. d. Treatment Technologies-The precise combination of abatement installations and the required treatment will be dependent on the types of processes available and limits and targets of the pollution allowed. Dust generated in the process can be passed through cyclones to returns the larger particles to the process. For finer particle a bag filter or wet scrubber may be required. Other gases, mist, and fumes may be treated by water scrubbing or, in case of ammonia, water containing phosphoric acid. In this case installation requires an anticorrosive lining. The scrubber liquors may be concentrated and recycled to the process. When recycling Is not possible, wastewaters must be treated before they are returned to the aquatic environment. Removal of the radionuclide s from phosphoric acid is operations; industrially by the concentration of the phosphoric acid or extraction. There are at present no commercial processes for the removal of cadmium from phosphoric fertilizers; however, extensive research is being conducted in view of expected stricter regulations on cadmium emissions. Gaseous contaminants (fluorides) are removed by scrubbing the gases and transforming fluorides into useful products. The remaining fluorides from sewage waters are removed by a two-stage lime treatment.

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