Phosphoric acid solvent extraction

McAlister, D.R., Horwitz, E.P. 2007. Characterization of extraction of chromatographic materials containing bis(2-ethyl-l-hexyl)phosphoric acid, 2-ethyl-1-hexyl (2-ethyl-1-hexyl) phosphonic acid, and bis(2,4,4-trimethyl-l-pentyl)phosphinic acid. Solvent Extraction and Ion Exchange 25(6) 757-769. 

Crude phosphoric acid is often black and contains dissolved metals and fluorine, and dissolved and colloidal organic compounds. Suspended solid impurities are usually removed by settling and solvent extraction (using a partially miscible solvent, such as n-butanol, /.so-butanol, or n-heptanol), or solvent precipitation is used to remove the dissolved impurities. The phosphoric acid is extracted, and the impurities are left behind. Back-extraction with water recovers the purified phosphoric acid. Solvent precipitation uses a completely miscible solvent plus alkalis or ammonia to precipitate the impurities as phosphate salts. After filtration, the solvent is separated by distillation and recycled. 

The extractant agent is di-2-ethylhexyl phosphoric acid. The extraction grade depends on the pH of the operation, in a range between 1.5 and 5. In the lower range, the solvent extraction capacity is relatively low, compared to that obtained at pH = 5. However, it is not possible to operate at high pH s because of the presence of iron and other cations in the zinc-rich solution which precipitate as hydroxides, causing troubles in the phase distribution. 

Wet acid is made by allowing phosphate rock to react with sulfuric acid to form calcium sulfate, gypsum, and crude phosphoric acid. Phosphoric acid is extracted selectively into an organic solvent, from which it is stripped to yield a good quality of phosphoric acid. Furnace acid or purified wet acid can be purchased for similar prices. For many uses they are of approximately equal value. I remain biased toward furnace acid when purity is an issue. 

FIGURE 15.5 HPLC chromatograms of 70% methanolic extract of rapeseed meal indicating benzoic acid derivatives (a) at 275 nm and sinapic acid derivatives (b) at 330 nm. Chromatographic conditions elution using water/methanol (90 10) with 1.25% O-phosphoric acid as solvent A and methanol (100%) with 0.1% ( -phosphoric acid solvent B in a C-8 Chrospher column (Knauer). Sinapoyl glucose (GP), sinapine (SP), sinapic acid (SA), others non-identified phenolic constituents. 

Selectivity-structure trends in the extraction of cobalt(II) and nickel(II) by dialkyl phosphoric, alkyl alkylphosphonic, and dialkylphosphinic acids. Solvent Extraction and Ion Exchange, 3,4,135-452, ISSN 0736-6399... 

A process developed in Israel (263) uses solvent extraction using a higher alcohol or other solvating solvent. This removes phosphoric acid and some hydrochloric acid from the system driving the equiHbrium of equation 42 to the right. The same principle can be appHed in other salt—acid reactions of the form... 

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. 

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. 

Solvent Extraction. Liquid—hquid extractioa, well known ia the chemical iadustry, was first used ia extractive metallurgy for the processiag of uranium. When a dilute solution of uranium is contacted with an extractant such as di(2-ethylhexyl) phosphoric acid (D2EHPA) or R2HPO4, dissolved ia... 

F. J. Hurst, D. J. Crouse, and K. B. Brown, Solvent Extraction of Craniumfrom Wet Process Phosphoric Acid, ORNL-TM-2522, U.S. Atomic Energy Commission, Washington, D.C., 1969. 

Solvent extraction—purification of wet-process phosphoric acid is based on preferential extraction of H PO by an organic solvent vs the cationic impurities present in the acid. Because selectivity of acid over anionic impurities is usually not sufficient, precipitation or evaporation steps are included in the purification process for removal. Cmde wet-process acid is typically concentrated and clarified prior to extraction to remove post-precipitated sludge and improve partition of the acid into the solvent. Concentration also partially eliminates fluoride by evaporation of HF and/or SiF. Chemical precipitation of sulfate (as Ba or Ca salts), fluorosiUcates (as Na salt), and arsenic (as sulfides) may also be used as a prepurification step preceding solvent extraction. 

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. 

Fig. 4. Schematic diagram of the solvent extraction purification of wet-process phosphoric acid.

For solvent extraction of a tetravalent vanadium oxyvanadium cation, the leach solution is acidified to ca pH 1.6—2.0 by addition of sulfuric acid, and the redox potential is adjusted to —250 mV by heating and reaction with iron powder. Vanadium is extracted from the blue solution in ca six countercurrent mixer—settler stages by a kerosene solution of 5—6 wt % di-2-ethyIhexyl phosphoric acid (EHPA) and 3 wt % tributyl phosphate (TBP). The organic solvent is stripped by a 15 wt % sulfuric acid solution. The rich strip Hquor containing ca 50—65 g V20 /L is oxidized batchwise initially at pH 0.3 by addition of sodium chlorate then it is heated to 70°C and agitated during the addition of NH to raise the pH to 0.6. Vanadium pentoxide of 98—99% grade precipitates, is removed by filtration, and then is fused and flaked. 

Cyclohexanedione (5) 2,5-Dicarbethoxy-l,4-cyclohexanedione (10 g) is suspended in a solution of 34 g of 85 % phosphoric acid, 250 ml of water, and 5 ml of ethanol in a 500-ml round-bottom flask. The mixture is refluxed for 5 days (or until all the solid material has dissolved), cooled, and extracted six times with 100-ml portions of chloroform (or better, continuously extracted with chloroform). The combined chloroform extracts are dried (sodium sulfate) and the solvent is removed (rotary evaporator). The residue on distillation affords 1,4-cyclohexanedione, bp 130-133720 mm. The product solidifies and may be recrystallized from carbon tetrachloride, mp 11-19°. 

Preston, J. S. Solvent extraction of cobalt and nickel by organophosphorus acids. I. Comparison of phosphoric, phosphonic, and phosphinic acid systems. Hydrometallurgy 1982, 9, 115-133. 

Nucleic acids, DNA and RNA, are attractive biopolymers that can be used for biomedical applications [175,176], nanostructure fabrication [177,178], computing [179,180], and materials for electron-conduction [181,182]. Immobilization of DNA and RNA in well-defined nanostructures would be one of the most unique subjects in current nanotechnology. Unfortunately, a silica surface cannot usually adsorb duplex DNA in aqueous solution due to the electrostatic repulsion between the silica surface and polyanionic DNA. However, Fujiwara et al. recently found that duplex DNA in protonated phosphoric acid form can adsorb on mesoporous silicates, even in low-salt aqueous solution [183]. The DNA adsorption behavior depended much on the pore size of the mesoporous silica. Plausible models of DNA accommodation in mesopore silica channels are depicted in Figure 4.20. Inclusion of duplex DNA in mesoporous silicates with larger pores, around 3.8 nm diameter, would be accompanied by the formation of four water monolayers on the silica surface of the mesoporous inner channel (Figure 4.20A), where sufficient quantities of Si—OH groups remained after solvent extraction of the template (not by calcination). 

A mixture of 2.65 g. of freshly distilled 2,3-O-isopropylidene-D-glycerose, 1.5 ml. of ethyl acetoacetate, 0.7 g. of zinc chloride, 20 ml. of N sulfuric acid, and 20 ml. of 96% ethyl alcohol is kept at room temperature for twenty-four hours. After addition of 3 g. of crystalline sodium acetate and keeping for a further 48 hours at room temperature, the mixture is heated for 15 minutes at 90°. It is then repeatedly extracted with ether, and the united extracts are successively washed with water, an aqueous solution of sodium bisulfite, and a small quantity of aqueous sodium hydroxide solution. The ether layer is dried with anhydrous sodium sulfate and the solvent is evaporated, yielding an oil which is saponified with aqueous sodium hydroxide solution (4 ml. of 10%) by heating on a steam bath for one hour. The aqueous solution is extracted with ether, acidified (to Congo Red) with phosphoric acid, and then repeatedly extracted with ether the united extracts are dried with anhydrous sodium sulfate and the solvent is evaporated, giving a residue which crystallizes from water yield, 0.2 g. of the product (X) m. p., 153-155°. 

Dapex [Di-alkylphosphoric acid extraction] A process for the solvent extraction of uranium from sulfuric acid solutions using di-(2-ethylhexyl) phosphoric acid (HDEHP). The HDEHP is dissolved in kerosene containing 4 percent of tributyl phosphate. The uranium is stripped from the organic phase by aqueous sodium carbonate and precipitated as uranyl peroxide (yellow cake). The process was no longer in use in 1988. See also Amex. 

DEPA-TOPO [di (2-ethylhexyl) phosphoric acid and trioctylphosphine oxide] A process for recovering uranium from wet-process phosphoric acid, by solvent extraction with a mixture of the two named reagents. Developed at Oak Ridge National Laboratory and first commercialized in 1978 by Freeport Minerals Corporation and Wyoming Mineral Corporation. 

Haifa Also called IMI. One of the two Wet Processes for producing phosphoric acid by the acidulation of phosphate rock the other is the Dorr process. The Haifa process uses hydrochloric acid for the acidulation and solvent extraction for the purification. It is economic only where by-product hydrochloric acid is available. The overall reaction is ... 

Phorex [Phosphoric acid extraction] A process for purifying phosphoric acid by solvent extraction with -butyl or n-amyl alcohol. Developed by Azote et Produits Chimiques, France. 

Prayon One of the Wet processes for making phosphoric acid by reacting phosphate rock with sulfuric acid. The byproduct is gypsum, calcium sulfate dihydrate. It uses a compartmentalized, multi-section, lined, concrete reactor, with finishing tanks in which the gypsum crystals mature. In 1990 one third of the wet process phosphoric acid made in the Western World was made in this way. The process was developed in 1977 by the Societe de Prayon, Belgium. Variations are known as PH2, PHI 1, and PH12. One variation uses solvent extraction with isopropyl ether and tri-n-butyl phosphate. 

Zincex [Zinc extraction] A process for extracting zinc from pyrite cinder leachate, using organic solvents. The chloride leachate is first extracted with a secondary amine, and then with di(2-ethylhexyl)phosphoric acid to remove iron Developed by Tecnicas Reunidas, first commercialized in 1976, and now used in Spain and Portugal. 

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