Preparation of rare earth metals and other chemicals from industrial waste coal ash

Patent metadata

Field	Value
Publication number	US-2024271247-A1
Application number	US-202418407664-A
Country	US
Kind code	A1
Filing date	Jan 9, 2024
Priority date	Nov 20, 2017
Publication date	Aug 15, 2024
Grant date	—

Abstract

A process disclosed herein is related to the isolation and purification of substantially pure chemicals, including silica gel, sodium silicate, aluminum silicate, iron oxide, and rare earth elements (or rare earth metals, REEs), from massive industrial waste coal ash. In one embodiment, the process includes a plurality of caustic extractions of coal ash at an elevated temperature, followed by an acidic treatment to dissolve aluminum silicate and REEs. The dissolved aluminum silicate is precipitated out by pH adjustment as a solid product while REEs remain in the solution. REEs are captured and enriched using an ion exchange column. Alternatively, the solution containing aluminum silicate and REEs is heated to produce silica gel, which is easily separated from the enriched REEs solution. REEs are then isolated and purified from the enriched solution to afford substantially pure individual REE by a ligand-assisted chromatography. Additionally, a simplified process using one caustic extraction and one acidic extraction with an ion exchange process was also investigated and optimized to afford a comparable efficiency.

First claim

What is claimed is:

1 . A process for preparing substantially pure chemicals from coal ash, the process comprising:
a. extracting coal ash with a first caustic solution at an elevated temperature; b. separating undissolved solid residue from said first caustic extracting solution, wherein said first caustic solution is stored for later processing and said solid residue is washed briefly with water, c. treating the water washed solid residue with a first acid, wherein pH of the resulting acidic solution is maintained at about 3 and then the leftover solid is separated and washed with water; d. extracting the water washed solid with a second caustic solution at an elevated temperature; e. separating undissolved solid residue from the second caustic extracting solution and washing briefly with water; f. treating the undissolved solid with a second acid to bring the pH of the resulting acidic solution to about 3, and isolating the leftover solid as a substantially pure iron oxide with some aluminum silicate; g. combining the acidic extraction solutions from steps c and f, and adjusting the pH to about 5 with a base whereby substantially pure aluminum silicate precipitates out from the solution as a product and the leftover solution containing enriched rare earth elements (REEs); and h. combining the first and the second caustic extracting solutions to recover substantially pure sodium silicate by pH adjustment with an acid.

2 . The process of claim 1 further comprising steps of isolation and purification of each individual REE from said leftover acid extraction solution by a ligand-assisted chromatography comprising
a. enriching by capturing said REEs on an ion exchange column;
b. eluting REEs from said ion exchange column with a chelating ligand;
c. binding said chelating ligand solution of REEs to an absorbent column;
d. eluting individual REE with an isocratic or gradient of a ligand;
e. combining fractions of pure individual REE separately; and
f. recovering individual REE from the combined fractions.

3 . The process of claim 2 further comprising a step of precipitating and recycling EDTA salt.

4 . The process of claim 1 , wherein the coal ash is fly ash.

5 . The process of claim 1 , wherein the second caustic extracting solution is the solution from the first caustic extraction.

6 . The process of claim 1 , wherein said caustic extracting solution is made of sodium hydroxide or potassium hydroxide.

7 . The process of claim 1 , wherein the concentration of the caustic extracting solution is from about 1 M to about 15 M, preferably from about 5 M to 12 M.

8 . The process of claim 1 , wherein said acid is hydrochloric acid, sulfuric acid, or nitric acid.

9 . The process of claim 1 , wherein the concentration of said acid is from about 0.01 M to about 12 M, preferably from about 0.1 to 5 M.

10 . The process of claim 1 , wherein the elevated temperature is from about 50° C. to about 250° C., preferably from about 80° C. to about 150° C.

11 . The process of claim 1 , wherein the mass ratio of coal ash to base of said caustic solution is from about 1:1 to about 1:10

12 . The process of claim 1 , wherein said sodium silicate from caustic extraction is acidified to afford silica gel.

13 . A product of the process of claim 1 .

14 . The product of claim 13 , wherein said product comprises substantially pure silica gel, sodium silicate, aluminum silicate, iron oxide, and rare earth elements.

15 . A process for preparing substantially pure chemicals from coal ash, the process comprising:
a. extracting coal ash with a caustic solution at an elevated temperature; b. separating undissolved solid residue from said caustic extraction solution and washing it briefly with water; c. treating the water washed solid residue with an acid at a ratio of solid to acid about 1:10 and then separating the leftover solid to afford an acidic extraction solution; d. loading the acidic extraction solution to a cation exchange column and collecting the pass-through eluent; e. treating the pass-through eluent with a base to pH about 3, at which point iron hydroxide precipitates out and is isolated; then bringing the pH of the solution up to about 8 whereby aluminum hydroxide precipitates out and is isolated; and f. eluting the loaded cation exchange column first with a solution of sodium choride to afford fractions containing aluminum and iron, and then with a solution of a chelating ligand to afford fractions of enriched REEs;

16 . The process of claim 15 further comprising steps of isolation and purification each individual REE from said fractions of enriched REEs, the steps comprising
a. capturing said REEs on an ion exchange column,
b. eluting REEs from said ion exchange column with a chelating ligand,
c. binding said chelating ligand solution of REEs to an absorbent column,
d. eluting individual REE with an isocratic or gradient of a ligand,
e. combining fractions of pure individual REE separately, and
f. recovering individual REE from the combined fractions.

17 . The process of claim 16 further comprising a step of precipitating and recycling EDTA salt.

18 . The process of claim 15 further comprising a step washing coal ash with a strong, dilute acid to remove calcium oxide and other salts of alkali earth metals before extracting with a caustic solution at an elevated temperature.

19 . The process of claim 15 further comprising a step of exposing the leftover solid from acid extraction to a magnetic field and collecting those materials attracted to said magnetic field as an iron-enriched product.

20 . The process of claim 15 further comprising a step acidifying said caustic extraction solution to afford substantially silica gel.

21 . The process of claim 15 , wherein the caustic extracting solution is made of sodium hydroxide or potassium hydroxide.

22 . The process of claim 15 , wherein the caustic extracting solution has a concentration from about 1 M to about 15 M, preferably from about 5 M to 12 M.

23 . The process of claim 15 , wherein the acidic extraction solution is made of an acid selected from the group consisting of hydrochloric acid, sulfuric acid, and nitric acid.

24 . The process of claim 15 , wherein the acidic extraction solution has a concentration from about 0.1 M to about 12 M, preferably from about 1 M to about 5 M.

25 . The process of claim 15 , wherein said elevated temperature is from about 50° C. to about 250° C., preferably from about 80° C. to about 150° C.

26 . A product of the process of claim 15 .

27 . The product of claim 25 , wherein said product comprises substantially pure silica gel, sodium silicate, aluminum silicate, iron oxide, and rare earth elements.

Assignees

• Purdue Research Foundation

Inventors

• Wang Nien-Hwa Linda
• Choi Hoon
• Harvey David

Classifications

• C22B3/08

  Sulfuric acid {, other sulfurated acids or salts thereof} · CPC title

• C22B3/065

  Nitric acids or salts thereof · CPC title

• C01F17/271

  Chlorides · CPC title

• C01G49/10

  Halides {(C01G49/0018 takes precedence)} · CPC title

• C01B33/32

  Alkali metal silicates ({C01B33/24} , C01B33/26 take precedence) · CPC title