Sohd phosphoric acid

SPA Catalyst. The sohd phosphoric acid (SPA) catalyst process has been the domiaant source of cumene siace the 1930s. This process accounts for more than 90% of cumene operating capacity (59). A simplified process flow diagram is given ia Figure 5. 

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). 

Cumene as a pure chemical intermediate is produced in modified Friedel-Crafts reaction processes that use acidic catalysts to alkylate benzene with propylene (see Alkylation Friedel-CRAFTSreactions). The majority of cumene is manufactured with a soHd phosphoric acid catalyst (7). The remainder is made with aluminum chloride catalyst (8). 

Alkymax A process for removing benzene from petroleum fractions. They are mixed with light olefin fractions (containing mainly propylene) and passed over a fixed-bed catalyst, which promotes benzene alkylation. The catalyst is sohd phosphoric acid (SPA), made by mixing a phosphoric acid with a sihceous solid carrier, and calcining. Invented in 1980 by UOP... 

InAlk [Indirect Alkylation] A process for converting C3 and C4 streams in oil refinery to Cg to Q streams for use in gasoline. The catalyst is either a sulfonic acid resin or sohd phosphoric acid. Developed by UOP from 2000. 

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. 

Production Technology. Processes for extraction of P2O3 from phosphate rock by sulfuric acid vary widely, but all produce a phosphoric acid—calcium sulfate slurry that requires soHds-Hquid separation (usually by filtration (qv)), countercurrent washing of the soHds to improve P2O3 recovery, and concentration of the acid. Volatilized fluorine compounds are scmbbed and calcium sulfate is disposed of in a variety of ways. 

A newer self-intumescent phosphoric acid salt has been introduced by Albright WHson as Amgard EDAP, mainly as an additive for polyolefins. It is a finely divided soHd, mp 250°C, having a reported phosphoms content of 63 wt % as H PO. It appears to be the ethylenediamine salt of phosphoric acid (1 1). Unlike ammonium polyphosphate, it does not require a char-forming synergist (62). 

Fig. 5. Vapoi—liquid phase diagram of the H2O—P20 system at 101 kPa (1 atm), where 3 is ortho, 2 pyro, and 1 meta phosphoric acid. The soHd line...

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. 

Properties and Reactions. Phosphoms sulfochloride [3982-91-0] (thiophosphoryl chloride), PSCI3, is a colorless fuming Hquid andis made by the reaction of phosphoms trichloride with sulfur and by the reaction of PCI3 with P2S3. Phosphoms sulfochloride is dimorphic in the soHd state. It reacts with water, forming either phosphoric acid or dichlorothiophosphoric acid [14500-94-8] depending on the reaction conditions. 

Properties and Structure. Phosphoms(V) oxide, the extremely hygroscopic acid anhydride of the phosphoric acids, exists in several forms but is often referred to by its empirical formula, P2O3. Three crystalline polymorphs, two distinct Hquids, and several amorphous or glassy soHds are recogni2ed. Some properties of the various forms of phosphoric oxide are Hsted in Table 10. 

The vapor-phase conversion of aniline to DPA over a soHd catalyst has been extensively studied (18,22). In general, the catalyst used is pure aluminum oxide or titanium oxide, prepared under special conditions (18). Promoters, such as copper chromite, nickel chloride, phosphoric acid, and ammonium fluoride, have also been recommended. Reaction temperatures are usually from 400 to 500°C. Coke formed on the catalyst is removed occasionally by burning. In this way, conversions of about 35% and yields of 95% have been reported. Carba2ole is frequently a by-product. 

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. 

Acid-Gatalyzed Synthesis. The acid-catalysed reaction of alkenes with hydrogen sulfide to prepare thiols can be accompHshed using a strong acid (sulfuric or phosphoric acid) catalyst. Thiols can also be prepared continuously over a variety of soHd acid catalysts, such as seoHtes, sulfonic acid-containing resin catalysts, or aluminas (22). The continuous process is utilised commercially to manufacture the more important thiols (23,24). The acid-catalysed reaction is commonly classed as a Markownikoff addition. Examples of two important industrial processes are 2-methyl-2-propanethiol and 2-propanethiol, given in equations 1 and 2, respectively. 

Boron phosphate, BPO, is a white, infusible soHd that vapori2es slowly above 1450°C, without apparent decomposition. It is normally prepared by dehydrating mixtures of boric acid and phosphoric acid at temperatures up to 1200°C. 

Under certain conditions hydrogen cyanide can polymerize to black soHd compounds, eg, hydrogen cyanide homopolymer [26746-21-4] (1) and hydrogen cyanide tetramer [27027-02-2], C H N (2). There is usually an incubation period before rapid onset of polymer formation. Temperature has an inverse logarithmic effect on the incubation time. Acid stabilizers such as sulfuric and phosphoric acids prevent polymerization. The presence of water reduces the incubation period. 

Catalytic Condensation Also known colloquially as CATCON. A process for oligomerizing olefins, or alkylating aromatic hydrocarbons with olefins. The catalyst is a sohd containing free or combined phosphoric acid. Developed by UOP. 

When heated with sohd sodium bromide, phosphoric acid yields sodium dihydrogen phosphate, hberating hydrogen bromide ... 

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