Process for recovering titanium dioxide

Patent metadata

Field	Value
Publication number	US-12331380-B2
Application number	US-202117927232-A
Country	US
Kind code	B2
Filing date	May 18, 2021
Priority date	May 26, 2020
Publication date	Jun 17, 2025
Grant date	Jun 17, 2025

Abstract

A process for recovering titanium dioxide from a titanium-bearing material, the process including the steps of: leaching the titanium-bearing material in a first leaching step at atmospheric pressure and at a temperature of 70 to 97° C. with a first lixiviant to produce a first leach solution comprising undissolved first leach solids that include a titanium content and a first leach liquor, the first lixiviant comprising hydrochloric acid at a concentration of less than 23% w/w; separating the first leach liquor and the undissolved first leach solids; leaching the first leach solids in a second leaching step at atmospheric pressure and at a temperature of 60 to 80° C. with a second lixiviant in the presence of a Fe powder reductant to produce a second leach solution comprising undissolved second each solids and a second leach liquor that includes a leached titanium content and iron content, the second lixiviant comprising a mixed chloride solution comprising less than 23% w/w hydrochloric acid and an additional chloride selected from alkali metal chlorides, magnesium chloride and calcium chloride, or mixtures thereof; separating the second leach liquor and the undissolved second leach solids; and thereafter separating the titanium dioxide and the iron content from the second leach liquor by precipitation, and regenerating the second lixiviant for recycle to the second leaching step.

First claim

The invention claimed is:

1. A process for recovering titanium dioxide from a titanium-bearing material, the process including the steps of:
leaching the titanium-bearing material in a first leaching step at atmospheric pressure and at a temperature of 70 to 97° C. with a first lixiviant to produce a first leach solution comprising undissolved first leach solids that include a titanium content and a first leach liquor, the first lixiviant comprising hydrochloric acid at a concentration of less than 23% w/w;
separating the first leach liquor and the undissolved first leach solids;
leaching the first leach solids in a second leaching step at atmospheric pressure and at a temperature of 60 to 80° C. with a second lixiviant in the presence of a Fe powder reductant to produce a second leach solution comprising undissolved second leach solids and a second leach liquor that includes a leached titanium content and iron content, the second lixiviant comprising a mixed chloride solution comprising less than 23% w/w hydrochloric acid and an additional chloride selected from alkali metal chlorides, magnesium chloride and calcium chloride, or mixtures thereof;
separating the second leach liquor and the undissolved second leach solids;
precipitating titanium dioxide from the second leach liquor by addition of heated or boiling water under an inert gas or nitrogen atmosphere to raise the temperature of the second leach liquor to 85 to 100° C. to produce a treated second leach liquor and a titanium dioxide containing solid;
separating the titanium dioxide containing solid from the treated second leach liquor;
precipitating the iron content from the treated second leach liquor by adding a neutralising agent and an oxidant to the treated second leach liquor at a temperature of 70 to 90° C. to raise the pH of the second leach liquor to 4 to 8 to produce an iron removed slurry comprising an iron removed second leach liquor and an iron precipitated solid;
separating the iron removed second leach liquor from the iron precipitated solid; and
regenerating the second lixiviant for recycle to the second leaching step,
thereby recovering the titanium from the second leach solution as titanium dioxide.

2. The process according to claim 1 , wherein the first leaching step is conducted with the first lixiviant comprising 20 to 22% w/w HCl solution, preferably at 85 to 97° C.

3. The process according to claim 1 , wherein the titanium-bearing material includes at least one value metal selected from iron, vanadium, manganese, magnesium or aluminium and the first leach liquor is subjected to steps to recover the at least one value metal therefrom.

4. The process according to claim 3 , wherein the at least one value metal includes vanadium and/or aluminium, and the process further comprises a vanadium and/or aluminium removal step comprising:
adding a neutralising agent, preferably at least one of limestone, lime or MgO, to the first leach liquor at a temperature of 50 to 80° C. under an inert gas or nitrogen atmosphere, to raise the pH of the liquor to 3 to 6 thereby precipitating vanadium and aluminium to produce a V/Al removed slurry; and
separating the V/Al removed slurry into a liquid fraction comprising a V/Al removed liquor and a solid fraction comprising the V/Al precipitated solid.

5. The process according to claim 3 , wherein the at least one value metal includes iron, and the process further comprises an iron removal step comprising:
adding a neutralising agent, preferably at least one of limestone, lime or MgO, and an oxidant to the first leach liquor at a temperature of 70 to 90° C. to raise the pH of the liquor to 4 to 7 thereby precipitating iron to produce an iron removed slurry; and
separating the iron removed slurry into a liquid fraction comprising an iron removed liquor and a solid fraction comprising the iron precipitated solid.

6. The process according to claim 5 , wherein the oxidant comprises at least one of alkali metal peroxide, alkali metal perchlorate, ammonium perchlorate, magnesium perchlorate, magnesium chlorate, alkali metal chlorate, chlorine, alkali metal hypochlorite, hydrogen peroxide, perchloric acid, or an oxygen containing gas, preferably at least one of hydrogen peroxide or an oxygen containing gas, more preferably oxygen or air.

7. The process according to claim 5 , wherein the iron removal step is conducted after the vanadium and/or aluminium removal step.

8. The process according to claim 3 , wherein the at least one value metal includes manganese and/or magnesium, and the process further comprises a manganese and/or magnesium removal step comprising:
adding a neutralising agent, preferably lime, and an oxidant, preferably H 2 O 2 or an oxygen containing gas, more preferably air, to the iron removed liquor at a temperature of 60 to 90° C. to raise the pH of the liquor to 9 to 10 thereby precipitating Mg and/or Mn to produce a Mg/Mn removed slurry; and
separating the removed Mg/Mn slurry into a liquid fraction comprising a Mg/Mn removed liquor and a solid fraction comprising the precipitated Mg and/or Mn solid, wherein the manganese and/or magnesium removal step is conducted after the iron removal step.

9. The process according to claim 1 , further comprising:
regenerating the first lixiviant and recycling the first lixiviant to the first leaching step and wherein the first lixiviant is regenerated by:
concentrating the chloride content of the Mg/Mn removed liquor through water removal, preferably boiling and/or evaporation, to produce an evaporated liquor;
reacting the evaporated liquor with at least 98% w/w sulphuric acid at a temperature of 30 to 90° C., preferably at 80 to 85° C. under atmospheric conditions to produce 20 to 22% w/w hydrochloric acid and a solid precipitate,
separating the precipitated solid and hydrochloric acid liquor; and
recycling the hydrochloric acid liquor to the first leaching step.

10. The process according to claim 4 , further comprising the following steps prior to precipitating vanadium and aluminium from the first leach liquor:
neutralising at least part of the free acid (HCl) in the first leach liquor by adding to the first leach liquor at least one of: the feed titanium-bearing material, limestone, lime or MgO, to produce a first liquor neutralised slurry including a neutralised leach solid; and
separating the first liquor neutralised slurry into a solid fraction comprising the neutralised leach solid and a liquid fraction comprising the neutralised first leach liquor.

11. The process according to claim 10 , further comprising the following steps following the neutralising steps:
reduction of the neutralised first leach liquor at 45 to 75° C. by the addition of metallic iron, preferably iron powder, to convert ferric chloride in the first leach liquor to ferrous chloride; and
separating the reduced first leach liquor into a liquid fraction comprising a reduced liquor and a solid fraction comprising any unreacted solid iron powder.

12. The process according to claim 1 , wherein the iron is substantially precipitated as magnetite, preferably precipitated as magnetite only.

13. The process according to claim 1 , wherein the second leaching step is conducted with a second lixiviant comprising a mixed chloride solution of 20 to 22% w/w HCl and the additional chloride having a total chloride concentration of 400 to 550 g/L, preferably at 70 to 80° C.

14. The process according to claim 1 , wherein the second leaching step includes two leach regimes, comprising:
a first leach regime performed in the mixed chloride solution (without any iron powder addition); and
a second l

Assignees

• Commw Scient Ind Res Org

Inventors

• Das Goutam Kumar

Classifications

• C22B47/00

  Obtaining manganese · CPC title

• C22B34/22

  Obtaining vanadium · CPC title

• C22B26/22

  Obtaining magnesium · CPC title

• C22B21/0015

  by wet processes (C22B21/02, C22B21/04 and C22B21/06 take precedence) · CPC title

• C22B3/44

  by chemical processes (treatment or purification of solutions by liquid-liquid extraction C22B3/26, by ion-exchange extraction C22B3/42) · CPC title