Phosphoric acid industrial production

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. 

Some of the H2SiFg so produced finds commercial outlets (p. 810), but it has been estimated that 500 000 tonnes of H2SiFe is discarded annually by the US phosphoric acid industry, equivalent to 1 million tonnes of fluorspar — enough to supply that nation s entire requirements for HF. Production figures and major uses are in the Panel. 

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. 

Israel Mining Industries developed a process in which hydrochloric acid, instead of sulfuric acid, was used as the acidulant (37). The acidulate contained dissolved calcium chloride which then was separated from the phosphoric acid by use of solvent extraction using a recyclable organic solvent. The process was operated commercially for a limited time, but the generation of HCl fumes was destmctive to production equipment. 

The catalyst used in the production of maleic anhydride from butane is vanadium—phosphoms—oxide (VPO). Several routes may be used to prepare the catalyst (123), but the route favored by industry involves the reaction of vanadium(V) oxide [1314-62-1] and phosphoric acid [7664-38-2] to form vanadyl hydrogen phosphate, VOHPO O.5H2O. This material is then heated to eliminate water from the stmcture and irreversibly form vanadyl pyrophosphate, (V(123,124). Vanadyl pyrophosphate is befleved to be the catalyticaHy active phase required for the conversion of butane to maleic anhydride (125,126). 

Acid Treatment. The treatment of petroleum products with acids has been in use for a considerable time in the petroleum industry. Various acids such as hydrofluoric acid, hydrochloric acid, nitric acid, and phosphoric acid have been used in addition to the most commonly used sulfuric acid, but in most instances there is Httie advantage in using any acid other than sulfuric. 

Elemental phosphoms from the electrothermal process is a distilled product of high purity and yields phosphoric acid pure enough for most industrial uses without any further treatment. The main impurity is ca 20—100 ppm arsenic present in the phosphoms as the element and in the phosphoric acid as arsenious acid. To remove the arsenic, the phosphoric acid destined for food, pharmaceutical, and some industrial-grade appHcations is treated with excess hydrogen sulfide, filtered, and blown with air to strip out excess H2S. This treatment generally reduces the arsenic content of the phosphoric acid to less than 0.5 ppm. The small amount of filter cake is disposed of in approved chemical landfills. 

Because monocalcium phosphate is incongmently soluble, it is typically contaminated with various amounts (6—10%) of dicalcium phosphate and free phosphoric acid resulting from in-process disproportionation of the monocalcium salt. Free phosphoric acid may render the product hygroscopic, and absorbed water plus acid catalyzes further decomposition to additional free acid and dicalcium phosphate. For this reason, industrial monocalcium phosphate may contain some dicalcium phosphate resulting from excess lime addition and then aged to ensure the removal of residual free phosphoric acid. 

Alkali Meta.IPhospha.tes, A significant proportion of the phosphoric acid consumed in the manufacture of industrial, food, and pharmaceutical phosphates in the United States is used for the production of sodium salts. Alkali metal orthophosphates generally exhibit congment solubility and are therefore usually manufactured by either crystallisation from solution or drying of the entire reaction mass. Alkaline-earth and other phosphate salts of polyvalent cations typically exhibit incongment solubility and are prepared either by precipitation from solution having a metal oxide/P20 ratio considerably lower than that of the product, or by drying a solution or slurry with the proper metal oxide/P20 ratio. 

The estimated world production of wet-process phosphoric acid was 24,001,000 metric tons of P20 in 1993. Capacity was 34,710,000 metric tons. Over 90% of phosphoric acid production is wet-process (agricultural-grade) acid the remainder is industrial-grades (technical, food, pharmaceutical, etc) made by the thermal route or by the purification of wet-process acid. Table 11 fists U.S. production of wet-process and industrial-grade acids. 

U.S. consumption of industrial-grade phosphoric acid and phosphates in 1993 according to product categories (34) was phosphoric acid, at 29% sodium phosphate, 52% calcium phosphate, 7% potassium phosphate, 3% ammonium phosphate, 5% and others, 4%. Consumption according to market is given in Table 12. 

Trace contaminants in the phosphoms may be deterrnined by oxidation of the phosphoms by various techniques. The metals are then deterrnined by an inductively coupled plasma spectrophotometer or by atomic absorption. The most important trace metal is arsenic, which must be reduced in concentration for food-grade products. Numerous other trace metals have become important in recent years owing to the specifications for electronic-grade phosphoric acid requited by the semiconductor industry (see Electronic materials Semiconductors). Some trace elements must be reduced to the low ppb range in phosphoric acid to comply. 

Catalysts. Nearly aU. of the industrially significant aromatic alkylation processes of the past have been carried out in the Hquid phase with unsupported acid catalysts. For example, AlCl HF have been used commercially for at least one of the benzene alkylation processes to produce ethylbenzene (104), cumene (105), and detergent alkylates (80). Exceptions to this historical trend have been the use of a supported boron trifluoride for the production of ethylbenzene and of a soHd phosphoric acid (SPA) catalyst for the production of cumene (59,106). 

Ammonia is consumed in the manufacture of ammonium phosphates and ammonium sulfate by reaction with phosphoric acid and sulfuric acid, respectively. The phosphates may contain ortho- and polyphosphate values. Ammonium sulfate is also a by-product from other ammonia-using industries such as caprolactam (qv) and hydrogen cyanide (see Cyanides). 

Activated alumina and phosphoric acid on a suitable support have become the choices for an iadustrial process. Ziac oxide with alumina has also been claimed to be a good catalyst. The actual mechanism of dehydration is not known. In iadustrial production, the ethylene yield is 94 to 99% of the theoretical value depending on the processiag scheme. Traces of aldehyde, acids, higher hydrocarbons, and carbon oxides, as well as water, have to be removed. Fixed-bed processes developed at the beginning of this century have been commercialized in many countries, and small-scale industries are still in operation in Brazil and India. New fluid-bed processes have been developed to reduce the plant investment and operating costs (102,103). Commercially available processes include the Lummus processes (fixed and fluidized-bed processes), Halcon/Scientific Design process, NIKK/JGC process, and the Petrobras process. In all these processes, typical ethylene yield is between 94 and 99%. 

On an industrial scale PCI3 is sprayed into steam at 190 and the product sparged of residual water and HCl using nitrogen at 165. Phosphorous acid forms colourless, deliquescent crystals, mp 70. T, in which the structural units shown form four essentially linear H bonds (O - H 155-I60pm) which. stabilize a complex 3D network. The molecular dimensions were determined by low-temperature single-crystal neutron diffraction at 15K.f - ... 

Polyphosphoric acid supported on diatomaceous earth (p. 342) is a petrochemicals catalyst for the polymerization, alkylation, dehydrogenation, and low-temperature isomerization of hydrocarbons. Phosphoric acid is also used in the production of activated carbon (p. 274). In addition to its massive use in the fertilizer industry (p. 524) free phosphoric acid can be used as a stabilizer for clay soils small additions of H3PO4 under moist conditions gradually leach out A1 and Fe from the clay and these form polymeric phosphates which bind the clay particles together. An allied though more refined use is in the setting of dental cements. 

In 1950 the Fischer-Tropsch synthesis was banned in Germany by the allied forces. Sinarol, a high paraffinic kerosene fraction sold by Shell, was used as a substitute. This ban coincided with the rapid development of the European petrochemical industry, and in due time Fischer-Tropsch synthesis applied to the production of paraffins became uneconomic anyway. After the war there was a steady worldwide increase in the demand for surfactants. In order to continually meet the demand for synthetic detergents, the industry was compelled to find a substitute for /z-paraffin. This was achieved by the oligomerization of the propene part of raffinate gases with phosphoric acid catalyst at 200°C and about 20 bars pressure to produce tetrapropene. Tetrapropene was inexpensive, comprising a defined C cut and an olefinic double bond. Instead of the Lewis acid, aluminum chloride, hydrofluoric acid could now be used as a considerably milder, more economical, and easier-to-handle alkylation catalyst [4],... 

Phosphoric acid esters of polyoxyalkylenes of a high degree of alkoxylation still show many properties of the base products [37,38], Thus these products derived from nonionics are only mildly anionic. They have a better performance in such applications as institutional and industrial cleansers with a high percentage of alkaline builders. 

The development of monoalkyl phosphate as a low skin irritating anionic surfactant is accented in a review with 30 references on monoalkyl phosphate salts, including surface-active properties, cutaneous effects, and applications to paste and liquid-type skin cleansers, and also phosphorylation reactions from the viewpoint of industrial production [26]. Amine salts of acrylate ester polymers, which are physiologically acceptable and useful as surfactants, are prepared by transesterification of alkyl acrylate polymers with 4-morpholinethanol or the alkanolamines and fatty alcohols or alkoxylated alkylphenols, and neutralizing with carboxylic or phosphoric acid. The polymer salt was used as an emulsifying agent for oils and waxes [70]. Preparation of pharmaceutical liposomes with surfactants derived from phosphoric acid is described in [279]. Lipid bilayer vesicles comprise an anionic or zwitterionic surfactant which when dispersed in H20 at a temperature above the phase transition temperature is in a micellar phase and a second lipid which is a single-chain fatty acid, fatty acid ester, or fatty alcohol which is in an emulsion phase, and cholesterol or a derivative. 

Soap is a salt made by reacting animal fats with lye, another name for a solution of sodium hydroxide in water. In the 1800s, the need for soap as the population expanded created a demand for sodium hydroxide. Thus, sodium hydroxide was another early product of the chemical industry. Other washing compounds can be made by treating phosphoric acid (or boric acid)... 

C03-0131. The seventh-ranked industrial chemical in U.S. production is phosphoric acid, whose chemical formula is H3 PO4. One method of manufacture starts with elemental phosphoms, which is burned in air the product of this reaction then reacts with water to give the final product. In 1995, the United States manufactured 2.619 X 10 pounds of phosphoric acid. How many moles is this If 15% of this material was made by burning elemental phosphoms, how many moles and how many kilograms of phosphoms were consumed ... 

The most important commercial product of phosphoms is phosphoric acid, H3 PO4. Phosphoric acid consistently ranks among the top ten industrial chemicals in the United States, with a yearly production of over 10,000 tons. 

P4 Oio(.y) -F 6H2 0(/) 4H3 POio(<2 ( ) More than 80% of the elemental phosphorus produced is converted to phosphoric acid. This pure product, which constitutes about 10% of the total industrial output of phosphoric acid, is the starting material for making food additives, pharmaceuticals, and detergents. 

No compound containing a halogen other than chlorine appears among the top 50 industrial chemicals, but fluorine nevertheless has considerable commercial value. Fluorine occurs as the mineral fluorite (CaF2) and is prevalent in phosphate-bearing rock. As already mentioned, HF produced from sulfiaric acid treatment of fluorite supplies some 70% of industrial HF the remainder comes as a by-product of phosphoric acid production. 

An acidic-cure catalyst is added to the urea-formaldehyde resin before it is used as an adhesive. Ammonium chloride and ammonium sulfate are the most widely used catalysts for resins in the forest products industry. A variety of other chemicals can be used as a catalyst, including formic acid, boric acid, phosphoric acid, oxalic acid, and acid salts of hexamethylenetetramine. 

Phosphoric acid is used in many ways that include foods and beverages. It is also used in cleaning metal surfaces, electroplating, fertilizer production, preparing flame-proofing compounds, and other processes in the chemical industry, making it one of the most important of the chemicals of commerce. 

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