Phosphor manufacture

Phosphor manufacture is still a dominant factor for suppliers of rare earth chemicals. According to industry sources (29), approximately 1/3 of the monetary volume of rare earth chemicals is used by the electronics industry. Included in this figure is Sm O for samarium-cobalt magnets. The remainder includes Gd O, La.,0 and Tb 0, for x-ray and lighting phosphors, and Y O ana... 

Overall, the total monetary volume of rare earths used for U.S. CRT phosphor manufacture is 20-25M. The volume by weight is only roughly 1% of total rare earth production, but the monetary volume is large because of the high value of Eu O.. and Y 0 compared to other rare earth oxides, and the high purity required of phosphor grade chemicals. 

Applications include pipe and tubing in phosphoric acid manufacture, sulfuric acid manufacture, and fertilizer and pesticide manufacture. The alloy is also used in the evaporators of commercial wet process phosphoric manufacturing systems. This process contains complex mixtures of phosphoric, sulfuric, and hydrofluoric acids and various oxides. Under these conditions, the corrosion rate for alloy G-30 was 6 mpy as compared to 16 mpy for alloy G-3 and alloy 625. 

Industrially. phosphoric(V) acid is manufactured by two processes. In one process phosphorus is burned in air and the phos-phorus(V) oxide produced is dissolved in water. It is also manufactured by the action of dilute sulphuric acid on bone-ash or phosphorite, i.e. calcium tetraoxophosphate(V). Ca3(P04)2 the insoluble calcium sulphate is filtered off and the remaining solution concentrated. In this reaction, the calcium phosphate may be treated to convert it to the more soluble dihydrogenphosphatc. CafHjPOjj. When mixed with the calcium sulphate this is used as a fertiliser under the name "superphosphate . 

Chemistry ndProperties. The chemistry of phosphoric acid manufacture and purification is highly complex, largely because of the presence of impurities in the rock. The main chemical reaction in the acidulation of phosphate rock using sulfuric acid to produce phosphoric acid is... 

Simplicity of production, high analysis, and excellent agronomic quaUty are reasons for the sustained high production and consumption of TSP. A contributing factor is that manufacture of the triple superphosphate has been an outlet for so-called sludge acid, the highly impure phosphoric acid obtained as a by-product of normal acid purification. 

Economics. In contrast to NSP, the high nutrient content of TSP makes shipment of the finished product preferable to shipping of the raw materials. Plants, therefore, are located at or near the rock source. The phosphoric acid used, and the sulfuric acid required for its manufacture, usually are produced at the site of the TSP plant. As in the case of NSP, the cost of raw materials accounts for more than 90% of the total cost. Most of this is the cost of acid. 

The large amount of fluorine values released from phosphate rock in the manufacture of fertilisers (qv) gives a strong impetus to develop fluorine chemicals production from this source (see Phosphoric acid and the phosphates). Additional incentive comes from the need to control the emission of fluorine-containing gases. Most of the fluorine values are scmbbed out as fluorosiUcic acid, H2SiPg, which has limited useflilness. A procedure to convert fluorosihcic acid to calcium fluoride is available (61). 

Propylation of benzene with propylene, catalyzed by supported phosphoric acid (or related catalysts such as AlCl ), gives cumene [98-82-8] in another important industrial process. Cumene (qv), through the intermediacy of cumene hydroperoxide, is used in the manufacture of phenol (qv). Resorcinol similarly can be made from y -diisopropylbenzene (6). 

Hydrogen Chloride as By-Product from Chemical Processes. Over 90% of the hydrogen chloride produced in the United States is a by-product from various chemical processes. The cmde HCl generated in these processes is generally contaminated with impurities such as unreacted chlorine, organics, chlorinated organics, and entrained catalyst particles. A wide variety of techniques are employed to treat these HCl streams to obtain either anhydrous HCl or hydrochloric acid. Some of the processes in which HCl is produced as a by-product are the manufacture of chlorofluorohydrocarbons, manufacture of aUphatic and aromatic hydrocarbons, production of high surface area siUca (qv), and the manufacture of phosphoric acid [7664-38-2] and esters of phosphoric acid (see Phosphoric acid and phosphates). 

Inorganic Methods. Before the development of electrolytic processes, hydrogen peroxide was manufactured solely from metal peroxides. Eady methods based on barium peroxide, obtained by air-roasting barium oxide, used dilute sulfuric or phosphoric acid to form hydrogen peroxide in 3—8% concentration and the corresponding insoluble barium salt. Mote recent patents propose acidification with carbon dioxide and calcination of the by-product barium carbonate to the oxide for recycle. 

Manufacture. Malononitiile can be produced batchwise by elimination of water from cyano acetamide [107-91-5] with phosphorous... 

Isopropylnaphthalenes can be prepared readily by the catalytic alkylation of naphthalene with propjiene. 2-lsopropylnaphthalene [2027-17-0] is an important intermediate used in the manufacture of 2-naphthol (see Naphthalenederivatives). The alkylation of naphthalene with propjiene, preferably in an inert solvent at 40—100°C with an aluminum chloride, hydrogen fluoride, or boron trifluoride—phosphoric acid catalyst, gives 90—95% wt % 2-isopropylnaphthalene however, a considerable amount of polyalkylate also is produced. Preferably, the propylation of naphthalene is carried out in the vapor phase in a continuous manner, over a phosphoric acid on kieselguhr catalyst under pressure at ca 220—250°C. The alkylate, which is low in di- and polyisopropylnaphthalenes, then is isomerized by recycling over the same catalyst at 240°C or by using aluminum chloride catalyst at 80°C. After distillation, a product containing >90 wt % 2-isopropylnaphthalene is obtained (47). 

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). 

Manufacture. Phosphoric acid, H PO, is the second largest volume mineral acid produced sulfuric acid is the first. The greatest consumption of phosphoric acid is in the manufacture of phosphate salts, as opposed to direct use as acid. Markets are differentiated according to the purity of the acid. Phosphoric acid is produced commercially by either the wet process or the thermal (furnace) process. Thermal acid, manufactured from elemental... 

Thermal Process. In the manufacture of phosphoric acid from elemental phosphoms, white (yellow) phosphoms is burned in excess air, the resulting phosphoms pentoxide is hydrated, heats of combustion and hydration are removed, and the phosphoric acid mist collected. Within limits, the concentration of the product acid is controlled by the quantity of water added and the cooling capabiUties. Various process schemes deal with the problems of high combustion-zone temperatures, the reactivity of hot phosphoms pentoxide, the corrosive nature of hot phosphoric acid, and the difficulty of collecting fine phosphoric acid mist. The principal process types (Fig. 3) include the wetted-waH, water-cooled, or air-cooled combustion chamber, depending on the method used to protect the combustion chamber wall. 

Wet-process acid is manufactured by the digestion of phosphate rock (calcium phosphate) with sulfuric acid. Depending on availabiHty, other acids such as hydrochloric may be used, but the sulfuric-based processes are by far the most prevalent. Phosphoric acid is separated from the resultant calcium sulfate slurry by filtration. To generate a filterable slurry and to enhance the P2O5 content of the acid, much of the acid filtrate is recycled to the reactor. 

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. 

Uses. The principal use of monosodium phosphate is as a water-soluble soHd acid and pH buffer, primarily in acid-type cleaners. The double salt, NaH2P04 H PO, referred to as hemisodium orthophosphate or sodium hemiphosphate, is often generated in situ from monosodium phosphate and phosphoric acid in these types of formulations. Mixtures of mono- and disodium phosphates are used in textile processing, food manufacture, and other industries to control pH at 4—9. Monosodium phosphate is also used in boiler-water treatment, as a precipitant for polyvalent metal ions, and as an animal-feed supplement. 

The general manufacturing scheme for phosphate salts is shown in Figure 11. Condensed phosphates are prepared from the appropriate orthophosphate or mixture of orthophosphates, so the preparation of orthophosphates must be considered first for the manufacture of any phosphate salt. Phosphoric acid is neutralized to form a solution or slurry with a carefully adjusted acid/base ratio according to the desired orthophosphate product. The orthophosphate may be recovered either by crystallization from solution, or the entire solution or slurry may be evaporated to dryness. The dewatering (qv) method is determined by the solubihty properties of the product and by its desired physical properties such as crystal size and shape, bulk density, and surface area. Acid orthophosphate salts may be converted to condensed phosphates by thermal dehydration (calcination). 

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. 

Ammonium Phosphates. In the manufacture of ammonium phosphates, an atmosphere of ammonia may need to be maintained because the partial pressure of ammonia rises rapidly as either the temperature or the NH2/P20 mole ratio of the reaction mass increases. Phosphoric acid reacts quickly with ammonia vapor and is used in multistage reactor systems as a scmbber fluid to prevent NH emissions and recover ammonia values. For example, H PO scmbbing of coke-oven off-gases produces ammonium phosphates of relatively good purity. 

---