Process for the removal of heavy metals from a phosphoric acid containing composition using an ionic polymeric surfactant and use of said surfactant in the precipitation of heavy metals in a phosphoric acid containing composition

Patent metadata

Field	Value
Publication number	US-12545584-B2
Application number	US-202118008880-A
Country	US
Kind code	B2
Filing date	Jun 16, 2021
Priority date	Jun 16, 2020
Publication date	Feb 10, 2026
Grant date	Feb 10, 2026

Abstract

Improved methods for the removal of heavy metals, in particular cadmium, from an aqueous phosphoric acid containing composition, wherein an organothiophosphorous heavy metal precipitating agent and an ionic polymeric surfactant, particularly a cationic polyacrylamide copolymer surfactant, are both added to a phosphoric acid containing composition, particularly under vigorous mixing conditions, such as between 500 and 700 rpm. The ionic polymeric surfactant promotes the precipitation of the heavy metals. More in particular, the phosphoric acid containing composition is obtained by the acid digestion of phosphate rock, preferably by nitric acid, sulfuric acid, or a combination thereof.

First claim

We claim:

1 . A process for the removal of heavy metals from a phosphoric acid containing composition, comprising the steps of:
(a) providing a phosphoric acid containing composition comprising dissolved heavy metals; (b) precipitating the dissolved heavy metals by adding a heavy metal precipitating agent and a surfactant having a molecular weight of 4×10 6 Dalton to 8×10 6 Dalton, to the composition of step (a), at a pH of 1.6 to 2.2, thereby obtaining a heavy metal precipitate in a phosphoric acid containing composition, wherein the heavy metal precipitating agent comprises a diorgano-dithiophosphinic acid or an alkali metal or ammonia salt thereof, represented by Formula 1:

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; and
(c) separating the heavy metal precipitate from the phosphoric acid containing composition of step (b),
wherein the surfactant is a cationic polymeric surfactant wherein from 20% to 80% of the moieties making up the cationic polymeric surfactant are cationic charged moieties, an anionic polymeric surfactant wherein from 1% to 10% of the moieties making up the anionic polymeric surfactant are anionic charged moieties, or a mixture thereof, and
the phosphoric acid containing composition is an acidic aqueous composition comprising from 6-21 wt % nitric acid, from 25 to 33 wt % phosphoric acid, from 3.5 to 5 wt % calcium and dissolved heavy metals, with wt % based on the total weight of the composition.

2 . The process according to claim 1 , wherein the surfactant is a (meth) acrylamide based anionic polymer, a (meth) acrylamide based cationic polymer, or a mixture thereof.

3 . The process according to claim 2 , wherein the surfactant is a copolymer of (meth) acrylamide and a chloro-methylated monomer.

4 . The process of claim 3 wherein the surfactant is dimethylaminoethyl (meth)acrylate.

5 . The process according to claim 1 , wherein the surfactant is added in a dose of 3 to 30 g/m 3 acid composition.

6 . The process of claim 5 wherein the dose is 3 to 20 g/m 3 acid composition.

7 . The process according to claim 1 , wherein the weight ratio of precipitating agent to surfactant ranges from 1:1 to 10:1.

8 . The process of claim 7 wherein the weight ratio of precipitating agent to surfactant ranges from 3:1 to 6:1.

9 . The process according to claim 1 , wherein step (a) further comprises the steps of
(i) adjusting the pH of a phosphoric acid containing composition comprising dissolved heavy metals to a pH of 1.6 to 2.2; thereby obtaining a phosphoric acid containing composition comprising a sludge fraction; (ii) optionally adding a first flocculating agent to the composition of step (i); and (iii) separating the sludge fraction from the composition of step (i) or (ii).

10 . The process of claim 9 wherein the pH of the phosphoric acid containing composition is adjusted by the addition of ammonia.

11 . The process according to claim 1 , wherein step (c) comprises the steps of:
(c1) adding a second flocculating agent to the composition obtained in step (b), thereby obtaining agglomerates comprising the heavy metal precipitate in a phosphoric acid composition; and (c2) separating the agglomerates comprising the heavy metal precipitate from the phosphoric acid containing composition.

12 . The process according to claim 1 wherein the phosphoric acid containing composition is an acid digest of phosphate rock.

13 . The process of claim 12 wherein the phosphate rock is digested by nitric acid, or a mixture of sulfuric acid and nitric acid.

14 . The process 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.

15 . The process of claim 14 wherein the heavy metal-precipitation agent is sodium diisobutyldithiophosphinate.

16 . The process according to claim 1 , wherein the heavy metals are selected from cadmium, copper, nickel, lead, zinc and/or mercury.

17 . The process of claim 16 wherein the heavy metals are selected from cadmium, copper, and/or zinc.

18 . The process of claim 17 wherein the heavy metal is cadmium.

19 . The process of claim 1 wherein from 20% to 60% of the moieties making up the cationic polymeric surfactant are cationic charged moieties.

20 . The process of claim 1 wherein the dissolved heavy metal is cadmium.

Assignees

• Yara Int Asa

Inventors

• Kita Patrycja
• Vojnovic Tanja
• Bøyesen Katrine Lie

Classifications

• B03D3/06

  Flocculation · CPC title

• C22B3/26

  by liquid-liquid extraction using organic compounds · CPC title

• C22B3/382

  Phosphine chalcogenides, e.g. compounds of the formula R3P=X with X = O, S, Se or Te · CPC title

• C02F9/00

  Multistage treatment of water, waste water or sewage · CPC title

• C02F2209/06

  pH · CPC title