Phosphoric acid fertilizers

Becker, P. Phosphates and Phosphoric acid. Fertilizer Science and Technology Series, Vol. 6,... 

Duchon (135) concluded that the favorable action of colloidal silica on crop yields in sand cultures with insufficient phosphoric acid fertilization is due mainly to... 

Uses Antifoam for yeast fermentation, wet process of phosphoric acid fertilizers, water-color stuff m. ... 

White phosphorus may be made by several methods. By one process, tri-calcium phosphate, the essential ingredient of phosphate rock, is heated in the presence of carbon and silica in an electric furnace or fuel-fired furnace. Elementary phosphorus is liberated as vapor and may be collected under phosphoric acid, an important compound in making super-phosphate fertilizers. 

In recent years, concentrated phosphoric acids, which may contain as much as 70% to 75% P2O5 content, have become of great importance to agriculture and farm production. World-wide demand for fertilizers has caused record phosphate production. Phosphates are used in the production of special glasses, such as those used for sodium lamps. 

Mixed with additives, urea is used in soHd fertilizers of various formulations, eg, urea—ammonium phosphate (UAP), urea—ammonium sulfate (UAS), and urea—phosphate (urea + phosphoric acid). Concentrated solutions of urea and ammonium nitrate (UAN) solutions (80—85 wt%) have a high nitrogen content but low crystallization point, suitable for easy transportation, pipeline distribution, and direct spray appHcation. 

Uranium is present in small (50—200 ppm) amounts in phosphate rock and it can be economically feasible to separate the uranium as a by-product from the cmde black acid (30% phosphoric acid) obtained from the leaching of phosphate for fertilizers (qv). The development and design of processes to produce 500 t U Og per year at Ereeport, Louisiana have been detailed (272). 

Wet-Process Phosphoric Acid. As indicated in Figure 7, over 95% of the phosphate fertilizer used in the United States is made by processes that require an initial conversion of all or part of the phosphate ore to phosphoric acid. On a worldwide basis also, the proportion of phosphate fertilizer made with phosphoric acid is very high. Thus processes for production of phosphoric acid are of great importance to the fertilizer industry (see PHOSPHORIC ACID AND THE PHOSPHATES). 

There are numerous variations of the wet process, but all involve an initial step in which the ore is solubilized in sulfuric acid, or, in a few special instances, in some other acid. Because of this requirement for sulfuric acid, it is obvious that sulfur is a raw material of considerable importance to the fertilizer industry. The acid—rock reaction results in formation of phosphoric acid and the precipitation of calcium sulfate. The second principal step in the wet processes is filtration to separate the phosphoric acid from the precipitated calcium sulfate. Wet-process phosphoric acid (WPA) is much less pure than electric furnace acid, but for most fertilizer production the impurities, such as iron, aluminum, and magnesium, are not objectionable and actually contribute to improved physical condition of the finished fertilizer (35). Impurities also furnish some micronutrient fertilizer elements. 

Nitric acid acidulation of phosphate rock produces phosphoric acid, together with dissolved calcium nitrate. Separation of the phosphoric acid for use as an intermediate in other fertilizer processes has not been developed commercially. Solvent extraction is less effective in the phosphoric—nitric system than in the phosphoric—hydrochloric system. Instead, the nitric acid acidulate is processed to produce nitrophosphate fertilizers. 

Triple (Concentrated) Superphosphate. The first important use of phosphoric acid in fertilizer processing was in the production of triple superphosphate (TSP), sometimes called concentrated superphosphate. Basically, the production process for this material is the same as that for normal superphosphate, except that the reactants are phosphate rock and phosphoric acid instead of phosphate rock and sulfuric acid. The phosphoric acid, like sulfuric acid, solubilizes the rock and, in addition, contributes its own content of soluble phosphoms. The result is triple superphosphate of 45—47% P2 s content as compared to 16—20% P2 5 normal superphosphate. Although triple superphosphate has been known almost as long as normal superphosphate, it did not reach commercial importance until the late 1940s, when commercial supply of acid became available. 

Since about 1968, triple superphosphate has been far outdistanced by diammonium phosphate as the principal phosphate fertilizer, both in the United States and worldwide. However, production of triple superphosphate is expected to persist at a moderate level for two reasons (/) at the location of a phosphoric acid—diammonium phosphate complex, production of triple superphosphate is a convenient way of using sludge acid that is too impure for diammonium phosphate production and (2) the absence of nitrogen in triple superphosphate makes it the preferred source of phosphoms for the no-nitrogen bulk-blend fertilizers that frequendy are prescribed for leguminous crops such as soy beans, alfalfa, and clover. 

Nitric Phosphate. About 15% of worldwide phosphate fertilizer production is by processes that are based on solubilization of phosphate rock with nitric acid iastead of sulfuric or phosphoric acids (64). These processes, known collectively as nitric phosphate or nitrophosphate processes are important, mainly because of the iadependence from sulfur as a raw material and because of the freedom from the environmental problem of gypsum disposal that accompanies phosphoric acid-based processes. These two characteristics are expected to promote eventual iacrease ia the use of nitric phosphate processes, as sulfur resources diminish and/or environmental restrictions are tightened. 

Fig. 24. Routes of wet-process phosphoric acid into solution-type and suspension-type mixed fertilizer.

Resources of Sulfur. In most of the technologies employed to convert phosphate rock to phosphate fertilizer, sulfur, in the form of sulfuric acid, is vital. Treatment of rock with sulfuric acid is the procedure for producing ordinary superphosphate fertilizer, and treatment of rock using a higher proportion of sulfuric acid is the first step in the production of phosphoric acid, a production intermediate for most other phosphate fertilizers. Over 1.8 tons of sulfur is consumed by the world fertilizer industry for each ton of fertilizer phosphoms produced, ie, 0.8 t of sulfur for each ton of total 13.7 X 10 t of sulfur consumed in the United States for all purposes in 1991, 60% was for the production of phosphate fertilizers (109). Worldwide the percentage was probably even higher. 

The third process involves careflil addition of aluminum hydroxide to fluorosiUcic acid (6) which is generated by fertilizer and phosphoric acid-producing plants. The addition of Al(OH)2 is critical. It must be added gradually and slowly so that the siUca produced as by-product remains filterable and the AIF. -3H20 formed is in the soluble a-form. If the addition of Al(OH)2 3H20 is too slow, the a-form after some time changes into the insoluble P-form. Then separation of siUca from insoluble P-AIF. -3H20 becomes difficult. 

Environmentally sound phosphate fertilizer plants recover as much of the fluoride value as H2SiFg as possible. Sales for production of AIF. -3H20 is one of the most important markets (see Fertilizers Phosphoric acid and the phosphates). 

The acid process has three advantages over the alkaline process, ie, (/) higher yield of phosphine (60 vs 25%) (2) more pure gas for use in subsequent reactions (95 vs 40%) and (J) by-product phosphoric acid is relatively valuable and can be sold into a number of markets, eg, in the manufacture of fertilizers and flame retardants. There is no ready outlet for the mixture of phosphites produced via the alkaline route and additional processing by oxidative spray drying is needed to produce phosphates for sale (3). 

Wet Process. Over 90% of the phosphoric acid produced, both in the United States and worldwide, is wet-process phosphoric acid used almost exclusively for agricultural appHcation as both fertilizers and animal feed supplements. Although constituting a small proportion of the total wet-acid production, a significant amount of phosphoric acid for food and technical appHcations is made by purification of wet-process acid. 

Modem commercial wet-acid purification processes (see Fig. 4) are based on solvents such as C to Cg alcohols, ethers, ketones, amines, and phosphate esters (10—12). Organic-phase extraction of phosphoric acid is accompHshed in one or more extraction columns or, less frequently, in a series of countercurrent mixer—settlers. Generally, 60—75% of the feed acid P2 s content is extracted into the organic phase as H PO. The residual phosphoric acid phase (raffinate), containing 25—40% of the original P2O5 value, is typically used for fertilizer manufacture such as triple superphosphate. For this reason, wet-acid purification units are almost always located within or next to fertilizer complexes. 

Condensed Phosphoric Acid. The largest use of polyphosphoric (superphosphoric) acid is as an intermediate in the production of high quahty Hquid fertilizers. The TVA pioneered the development of electric-furnace superphosphoric acid for this appHcation. However, wet-process superphosphoric acid prepared by evaporation of water from wet-process phosphoric acid has almost completely replaced furnace-grade acid in fertilizer manufacture. 

Monoammonium and diammonium phosphates are produced on a large scale as fertilizers. During the 1970s, these materials, produced from economical wet-process phosphoric acid, became the world s leading phosphate fertilizers. 

Devising an economical method of producing agricultural-grade potassium phosphates from potassium chloride and wet-process phosphoric acid has been the subject of intense agricultural—chemical research (37—39). Limited quantities have been produced industrially. The impact on the overall quantities of phosphoms and potassium compounds consumed by the fertilizer industry is small. Because potassium phosphates are an excellent source of two essential fertilizer elements, this research is expected to continue. 

As of 1993—1994, over 70% of sulfuric acid production was not sold as such, but used captively to make other materials. At almost all large fertilizer plants, sulfuric acid is made on site, and by-product steam from these sulfur-burning plants is generally used for concentrating phosphoric acid ia evaporators. Most of the fertilizer plants are located ia Florida, Georgia, Idaho, Louisiana, and North Carolina. In the production of phosphate fertilizers, the primary role of sulfuric acid is to convert phosphate rock to phosphoric acid and soHd calcium sulfates, which are removed by filtration. 

Phosphates. The primary constituent of phosphate rock is fluorapatite, Ca3FP2022- Industrial phosphates including phosphate fertilizers (qv), phosphoric acid, and calcium phosphates (11) (see Phosphoric acid and the phosphates) are obtained from the large deposits of fluorapatite found in Florida in the United States, and in Morocco. Because phosphate rock is too insoluble to be useful as a fertilizer, it is converted to superphosphate [12431 -88-8] Ca(H2P0 2 CaSO, by H2SO and to triple superphosphate [7758-23-8] by H PO (l )- Phosphoric acid may also be... 

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