Compositions and processes for removing heavy metals from phosphoric acid solutions
US-2019106324-A1 · Apr 11, 2019 · US
US12508636B2 · US · B2
| Field | Value |
|---|---|
| Publication number | US-12508636-B2 |
| Application number | US-202118008849-A |
| Country | US |
| Kind code | B2 |
| Filing date | Jun 16, 2021 |
| Priority date | Jun 16, 2020 |
| Publication date | Dec 30, 2025 |
| Grant date | Dec 30, 2025 |
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A method comprising a) mixing and dissolving the solid hazardous heavy metal-containing composition with an acid solution; b) precipitating the heavy metal from the hazardous heavy metal acid compositions by; c) precipitating the heavy metal from the hazardous heavy metal acid composition with a heavy metal-precipitation agent; and d) separating out the heavy metal precipitate from the aqueous supernatant, whereby the heavy metal-precipitation agent comprises a diorgano-dithiophosphinic acid or the alkali metal or ammonia salts thereof.
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The invention claimed is: 1 . A method for converting a solid hazardous heavy metal-containing composition into a solid non-hazardous heavy metal-containing composition and an aqueous composition essentially free of heavy metals, comprising the steps of a) mixing and dissolving the solid hazardous heavy metal-containing composition with an acid solution, thereby obtaining an hazardous heavy metal acid composition, wherein the solid hazardous heavy-metal containing composition is the end product of a precipitation process of heavy metals, containing heavy metals, and leaches more than 2 ppm of cadmium, or more than 5 ppm of arsenic, or more than 50 ppm of copper, or more than 0.5 ppm of mercury, or more than 10 ppm of nickel, or more than 10 ppm of lead, or more than 50 ppm of zinc, according to a Modified EU Standard NS-EN 12457-2 using 10 l of water per kg of the solid hazardous heavy metal-containing composition; b) precipitating the heavy metals from the hazardous heavy metal acid composition by reacting the hazardous heavy metal acid composition with a heavy metal-precipitation agent at a pH of at least 0.9, wherein the pH of the acid composition is measured after a 13-fold dilution by volume in water, and adjusting the pH of the hazardous heavy metal acid composition to at least 0.9 if the measured pH is below 0.9; and reacting the hazardous heavy metal acid composition with a heavy metal-precipitation agent, thereby forming a heavy metal precipitate and an aqueous supernatant; and c) separating out the heavy metal precipitate from the aqueous supernatant, whereby the heavy metal precipitate is the solid non-hazardous heavy metal-containing composition, wherein the solid non-hazardous heavy metal-containing composition leaches 2 ppm or less of cadmium into an aqueous solution, upon treatment of the solid non-hazardous heavy metal-containing composition according to the Modified EU Standard, and the aqueous supernatant is the aqueous-composition essentially free of heavy metal and comprising less than 12 ppm cadmium; wherein the heavy metal-precipitation agent comprises a diorgano-dithiophosphinic acid or the alkali metals or ammonia salts thereof, represented by Formula 1: and wherein R is a linear or branched hydrocarbon group selected from alkyl, aryl, alkylaryl, or aralkyl, and wherein the hydrocarbon group contains 3 to 20 carbon atoms, and M is H, alkali metal or ammonia. 2 . The method according to claim 1 , wherein the solid hazardous heavy metal-containing composition is a solid cadmium-containing composition, and wherein the solid non-hazardous heavy metal-containing composition is a solid cadmium-containing composition, and wherein the aqueous composition is essentially free of cadmium. 3 . The method according to claim 1 , wherein the acid solution used in step a) has a pK a of less than 2.3. 4 . The method according to claim 1 , wherein the solid hazardous heavy metal-containing composition further comprises from 1 to 10 weight % phosphorous and from 1 to 18 weight % calcium. 5 . The method according to claim 1 , wherein the pH in step b) is adjusted if necessary to values ranging from 0.9 to 1.6, measured after a 13-fold dilution by volume using water. 6 . The method according to claim 1 , wherein the pH value of the aqueous composition in step c) is adjusted using gaseous ammonia. 7 . The method according to claim 1 , wherein R in Formula 1 is selected from the group consisting of cyclohexyl, isopropyl, isobutyl, n-propyl, octyl, hexyl, phenylethyl and 2,4,4-trimethylpentyl. 8 . The method according to claim 1 , wherein the heavy metal-precipitation agent is sodium diisobutyldithiophosphinate. 9 . The method according to claim 1 , wherein the hazardous heavy metal acid composition comprises a solid sludge, and wherein the method comprises, before the precipitating step b), the step of: d) removing at least part of the solid sludge in the hazardous heavy metal acid composition. 10 . The method according to claim 1 , wherein the method further comprises the step of: e) adding a flocculating agent, thereby forming flocculants, wherein the flocculating agent is added after the mixing and dissolving step a). 11 . The method according to claim 10 , wherein the flocculating agent is added before the precipitating step b), and/or during the precipitating step b) and/or after the precipitating step b). 12 . The method according to claim 11 , wherein the flocculating agent is added after the precipitating step b). 13 . The method according to claim 10 , wherein the flocculating agent is a cationic polymer. 14 . The method of claim 1 wherein the precipitation process in step a) is the Odda process.
Multistage treatment of water, waste water or sewage · CPC title
pH · CPC title
Cationic impurities {, e.g. arsenic compounds} · CPC title
by liquid-liquid extraction using organic compounds · CPC title
by extraction · CPC title
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