Preparation method of phosphotungstic acid

Patent metadata

Field	Value
Publication number	US-11214495-B2
Application number	US-201716327334-A
Country	US
Kind code	B2
Filing date	Aug 3, 2017
Priority date	Aug 26, 2016
Publication date	Jan 4, 2022
Grant date	Jan 4, 2022

Abstract

A preparation method of phosphotungstic acid includes mixing a mixed solution containing tungsten, phosphorus and an inorganic acid with an organic-alcohol-containing oil phase for extraction, stripping the obtained supported organic phase and distilled water according to an oil phase:aqueous phase volume ratio of 3:1 to 10:1 to obtain a stripping solution; and carrying out thermal evaporation crystallization or spray drying on the stripping solution to obtain a phosphotungstic acid crystal, wherein the organic alcohol is a C7-C20 alcohol. The inventors have found out that the addition of an inorganic acid to a solution of phosphorus or tungsten and the use of an organic alcohol as an extractant can achieve simultaneous and efficient extraction of phosphotungstic acid. It has also been found that the organic-alcohol-containing oil phase has excellent selectivity for phosphotungstic acid molecules in the mixed solution.

First claim

What is claimed is:

1. A preparation method of phosphotungstic acid, comprising:
mixing a mixed solution containing tungsten, phosphorus and an inorganic acid with an organic-alcohol-containing oil phase for extraction, the organic-alcohol-containing oil phase includes an extractant, wherein the extractant is consisting of an organic alcohol, combining an obtained supported organic phase with a stripping agent according to an oil phase:aqueous phase volume ratio of 3:1 to 10:1 to obtain a stripping solution, wherein the stripping agent is consisting of distilled water, and carrying out thermal evaporation crystallization or spray drying on the stripping solution to obtain a phosphotungstic acid crystal;
comprising Scheme A, Scheme B, Scheme C or Scheme D:
Scheme A: the mixed solution is obtained by reacting a tungsten source of white tungstic acid or artificial scheelite with an aqueous solution of a phosphorus compound and the inorganic acid;
Scheme B: the mixed solution is obtained by dissolving an industrial sodium tungstate crystal in water, then adding the phosphorus compound and the inorganic acid and mixing;
in the extraction process in Scheme A and Scheme B, the oil phase:aqueous phase volume ratio is 2:1 to 1:5;
Scheme C: the mixed solution is a phosphotungstic acid solution containing the inorganic acid, which is obtained by dissolving an industrial phosphotungstic acid crystal in water, adding the inorganic acid and mixing, wherein the concentration of tungsten trioxide is 50 to 150 g/L, and the volumetric molar concentration of the inorganic acid is 0.5 to 6 mol/L; in the extraction process, the volume concentration of the organic alcohol in the organic-alcohol-containing oil phase is 5 to 50%; the oil phase:aqueous phase volume ratio is 1:1 to 10:1; and
Scheme D: the mixed solution is a tungsten-containing sulfuric acid-phosphoric acid mixture solution; wherein the concentration of tungsten trioxide is 25 to 150 g/L, the concentration of phosphoric acid is 10 to 200 g/L, and the concentration of sulfuric acid is adjusted to 1.5 to 2.5 mol/L; and the oil phase:aqueous phase volume ratio in the extraction process is 3:1 to 1:3.

2. The preparation method of phosphotungstic acid according to claim 1 , wherein in Scheme A or Scheme B, the phosphorus compound is one or more of phosphoric acid, sodium phosphate and phosphorus pentoxide.

3. The preparation method of phosphotungstic acid according to claim 1 , wherein the inorganic acid is one or more of sulfuric acid, hydrochloric acid and nitric acid.

4. The preparation method of phosphotungstic acid according to claim 1 , wherein in Scheme A, the volumetric molar concentration of the inorganic acid is 1 to 4 mol/L.

5. The preparation method of phosphotungstic acid according to claim 4 , wherein in Scheme A, the mixed solution contains 10 to 150 g/L of tungsten trioxide and 5 to 100 g/L of phosphorus.

6. The preparation method of phosphotungstic acid according to claim 1 , wherein in Scheme B, the mixed solution contains 10 to 150 g/L of tungsten trioxide and 10 to 100 g/L of phosphorus; and the volumetric molar concentration of the inorganic acid is 1 to 4 mol/L.

7. The preparation method of phosphotungstic acid according to claim 1 , wherein in Scheme C, in the mixed solution, the volumetric molar concentration of the inorganic acid is 1 to 4 mol/L.

8. The preparation method of phosphotungstic acid according to claim 1 , wherein the organic-alcohol-containing oil phase contains the organic alcohol and a diluent sulfonated kerosene.

9. The preparation method of phosphotungstic acid according to claim 8 , wherein the organic alcohol is a C7-C20 alcohol.

10. The preparation method of phosphotungstic acid according to claim 9 , wherein the organic alcohol is octanol to dodecanol.

11. The preparation method of phosphotungstic acid according to claim 9 , wherein in the organic-alcohol-containing oil phase, the concentration of the organic alcohol is 10 to 50%.

12. The preparation method of phosphotungstic acid according to claim 11 , wherein in the organic-alcohol-containing oil phase, the volumetric concentration of the organic alcohol is 10 to 30%.

13. The preparation method of phosphotungstic acid according to claim 1 , wherein in Scheme C, if the industrial phosphotungstic acid crystal raw material contains molybdenum, hydrogen peroxide is firstly added in an amount of 2 to 2.5 times the total molar amount of tungsten and molybdenum into the stripping solution obtained in step III, and the molybdenum is removed by extraction with tributyl phosphate.

14. The preparation method of phosphotungstic acid according to claim 1 , further comprising Scheme E: ammonia water is added or ammonia gas is introduced into the stripping solution in Scheme D, and the free ammonia in the solution is controlled at 1 to 2 mol/L to obtain an ammonium tungstate solution; and phosphorus is removed from the ammonium tungstate solution, and evaporation crystallization is carried out to obtain ammonium paratungstate.

15. The preparation method of phosphotungstic acid according to claim 3 , wherein in Scheme A, the volumetric molar concentration of the inorganic acid is 1 to 4 mol/L.

16. The preparation method of phosphotungstic acid according to claim 8 , further comprising Scheme E: ammonia water is added or ammonia gas is introduced into the stripping solution in Scheme D, and the free ammonia in the solution is controlled at 1 to 2 mol/L to obtain an ammonium tungstate solution; and phosphorus is removed from the ammonium tungstate solution, and evaporation crystallization is carried out to obtain ammonium paratungstate.

17. The preparation method of phosphotungstic acid according to claim 9 , further comprising Scheme E: ammonia water is added or ammonia gas is introduced into the stripping solution in Scheme D, and the free ammonia in the solution is controlled at 1 to 2 mol/L to obtain an ammonium tungstate solution; and phosphorus is removed from the ammonium tungstate solution, and evaporation crystallization is carried out to obtain ammonium paratungstate.

18. The preparation method of phosphotungstic acid according to claim 10 , further comprising Scheme E: ammonia water is added or ammonia gas is introduced into the stripping solution in Scheme D, and the free ammonia in the solution is controlled at 1 to 2 mol/L to obtain an ammonium tungstate solution; and phosphorus is removed from the ammonium tungstate solution, and evaporation crystallization is carried out to obtain ammonium paratungstate.

19. The preparation method of phosphotungstic acid according to claim 11 , further comprising Scheme E: ammonia water is added or ammonia gas is introduced into the stripping solution in Scheme D, and the free ammonia in the solution is controlled at 1 to 2 mol/L to obtain an ammonium tungstate solution; and phosphorus is removed from the ammonium tungstate solution, and evaporation crystallization is carried out to obtain ammonium paratungstate.

20. The preparation method of phosphotungstic acid according to claim 12 , further comprising Scheme E: ammonia water is added or ammonia gas is introduced into the stripping solution in Scheme D, and the free ammonia in the solution is controlled at 1 to 2 mol/L to obtain an ammonium tungstate solution; and phosphorus is removed from the ammonium tungstate solution, and evaporation crystallization is carried out to obtain ammonium paratungstate.

Assignees

• Univ Central South

Inventors

• Zhao Zhongwei
• Li Yongli

Classifications

• C01B25/16

  Oxyacids of phosphorus; Salts thereof (peroxyacids or salts thereof C01B15/00) · CPC title

• B01J27/199 Primary

  with chromium, molybdenum, tungsten or polonium · CPC title

• C01G41/003

  Preparation involving a liquid-liquid extraction, an adsorption or an ion-exchange · CPC title

• B01J27/188 Primary

  with chromium, molybdenum, tungsten or polonium · CPC title

• C30B7/02

  by evaporation of the solvent · CPC title