Recovery of mixed acids from mixed salts

• US 4,999,095 A
• Filed: 05/16/1988
• Issued: 03/12/1991
• Est. Priority Date: 05/03/1985
• Status: Expired due to Fees

• Current Assignee: Graver Water Systems Incorporated
• Original Assignee: Alliedsignal Inc.
• Inventors: Mani, Krishnamurthy N., Chlanda, Frederick P.
• Primary Examiner(s): Niebling, John F.
• Assistant Examiner(s): Leader, William T.
• Application Number:
  US07/196,829
• Time in Patent Office: 1,030 Days
• Field of Search: 204/182.4, 204/182.5, 204/301
• US Class Current: 204/534
• CPC Class Codes: B01D 61/445 with bipolar membranes; Water splitting
• CPC Class Codes: C01B 21/42 Preparation from nitrates
• CPC Class Codes: C23G 1/36 Regeneration of waste pickling liquors

Abstract

A process for recovering concentrated mixed acids comprising HF from mixed salts at a high efficiency is disclosed. The process comprises the steps of providing an electrodialytic water splitter comprising at least one unit cell, each cell comprising a first compartment and a second compartment, feeding an aqueous solution comprising at least two salts formed from at least two different anions to the first compartment, one of said anions being fluoride, feeding a liquid comprising water to the second compartment, passing current through said electrodialytic water splitter to produce an aqueous product comprising mixed acids formed from the different anions in the second compartment, and an aqueous salt-containing product comprising a reduced concentration of said anions in the first compartment, and recovering aqueous products from the second compartment. The process is particularly useful in the production of concentrated HNO₃ at unexpectedly high current efficiencies, and has particular utility in the area of regenerating stainless steel pickling acid mixtures comprising HF and HNO₃.

Claims

1. A process for recovering a mixed acid solution comprising hydrofluoric acid from a solution comprising salts of the acids to be recovered comprising the steps of:

(a) providing an electrodialytic water splitter comprising at least two unit cells, each unit cell comprising a means for splitting water comprising a bipolar membrane or spaced apart anion and cation membranes, a first compartment and a second compartment, said electrodialytic water splitter additionally comprising a single pair of anode and cathode electrodes said at least two unit cells being between the anode electrode and the cathode electrode;

(b) feeding an aqueous solution comprising at least two salts formed from at least two different anions to the first compartment, one of said anions being fluoride anions;

(c) feeding a liquid comprising water to the second compartment;

(d) passing current through said electrodialytic water splitter to produce an aqueous product comprising mixed acids formed from the different anions in the second compartment, and an aqueous salt-containing product comprising a reduced concentration of said anions in the first compartment; and

(e) recovering aqueous product comprising hydrofluoric acid from the second compartment.

2. The process of claim 1 wherein the at least one unit cell further comprises a third compartment.

3. The process of claim 2 wherein a liquid comprising water is fed to the third compartment, and wherein a basified aqueous solution is produced in the third compartment upon passing the current therethrough.

4. The process of claim 3 further comprising the step of pretreating a spent process material comprising the at least two different anions, one of which is fluoride anion, with the basified aqueous solution to produce the aqueous solution.

5. The process of claim 4 wherein the spent process material is spent pickling liquor.

6. The process of claim 5 wherein the aqueous solution comprises alkali metal fluoride and alkali metal nitrate.

7. The process of claim 4 wherein the spent process liquor is spent stainless steel pickling liquor.

8. The process of claim 7 wherein the spent stainless steel pickling liquor further comprises nitrate ions.

9. The process of claim 8 wherein the basified aqueous solution comprises aqueous potassium hydroxide.

10. The process of claim 1 wherein another of said at least two different anions is selected from the group consisting of chloride, sulfate, nitrate, and phosphate.

11. The process of claim 1 further comprising the step of pretreating a spent process material comprising the at least two different anions, one of which is fluoride anion, to produce the aqueous solution.

12. The process of claim 11 wherein the step of pretreating the spent process material comprises contacting the spent process material with a basified aqueous solution.

13. The process of claim 1 wherein the means for water splitting is a bipolar membrane.

14. A process for recovering mixed acids from spent stainless steel pickling liquor comprising at least two different anions, one of which if fluoride anion, and heavy metal cations comprising the steps of:

(a) contacting the spent stainless steel pickling liquor with a basified aqueous solution to produce a solution a solution comprising salts of the acids to be recovered, one of which is a fluoride salt, and a precipitate comprising heavy metal ions;

(b) recovering said precipitate;

(c) subjecting the solution comprising salts to electrodialytic water splitting in an electrodialytic water splitter to produce a mixed acid product comprising hydrofluoric acid, the electrodialytic water splitter comprising at least two unit cells, each unit cell comprising a means for splitting water comprising a bipolar membrane or spaced apart anion and cation membranes, a first compartment and a second compartment, said electrodialytic water splitter additionally comprising a single pair of anode and cathode electrodes said at least two unit cells being between the anode electrode and the cathode electrode; and

(d) recovering the mixed acid product from one of the compartments.

15. The process of claim 14 wherein the means of water splitting is a bipolar membrane.