IP Library Granted Patent US 9,580,831
Granted Patent B2
US 9,580,831 · App. 13/627,022 · Granted Feb 28, 2017

Stainless steel pickling in an oxidizing, electrolytic acid bath

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Quick Facts
Patent No.
US 9,580,831
App. No.
13/627,022
Granted
Feb 28, 2017
Kind
B2
Abstract

A pickling process designed for pickling a metal strip such as a stainless steel strip reduces the amount of HF and/or HNO 3 . The strip is immersed in at least one first pickling tub that contains a mixture of an acid such as H 2 SO 4 , an excess of at least one oxidizing agent, and includes electrodes that may apply a current to the strip that runs through the mixture.

Claims (31)

1. A process for pickling a strip of ferritic stainless steel consisting of:

treating the steel with a first mixture disposed in a first tub, the first mixture consisting of H 2 SO 4 , and an oxidizing agent selected from a group consisting of H 2 O 2 and HNO 3 , wherein the step of treating the steel with the first mixture consists of reacting the first mixture with the steel, wherein reaction of the first mixture with the steel produces a concentration of ferrous sulfate, wherein said oxidizing agent is in excess relative to the ferrous sulfate so as to convert the ferrous sulfate to ferric sulfate (Fe 2 (SO 4 ) 3 ) resulting in a concentration of Fe 2 (SO 4 ) 3 , and

applying a current to the steel while the steel is in the first tub, wherein the first mixture does not include HF.

2. The process of claim 1 , wherein the concentration of Fe 2 (SO 4 ) 3 is from about 5 g/L to about 100 g/L.

3. The process of claim 1 , wherein the oxidizing agent is H 2 O 2 .

4. The process of claim 1 , wherein the concentration of H 2 SO 4 is from about 10 g/L to about 200 g/L.

5. The process of claim 1 , wherein the first tub is a sole tub used in the pickling process.

6. The process of claim 1 , wherein the steel is pickled in a continuous fashion.

7. The process of claim 1 , wherein the step of applying a current to the steel consists of applying a current via at least one of a cathode or anode.

8. The process of claim 1 , wherein the oxidizing agent is HNO 3 .

9. The process of claim 7 , wherein the steel consists of one of the cathode or anode.

10. A process for pickling a continuous strip of stainless steel consisting of:

treating the steel with a first mixture disposed in a first tub, the first mixture consisting of a concentration of H 2 SO 4 , an oxidizing agent selected from a group consisting of H 2 O 2 and HNO 3 , and optionally a concentration of HF, wherein the step of treating the steel with the first mixture consists of reacting the first mixture with the steel, wherein reaction of the first mixture with the steel produces a concentration of ferrous sulfate, wherein said oxidizing agent consists of an excessive concentration relative to the ferrous sulfate so as to convert a total amount of the ferrous sulfate to ferric sulfate (Fe 2 (SO 4 ) 3 ) resulting in a concentration of Fe 2 (SO 4 ) 3 , and

applying a current to the steel, wherein a concentration of H 2 SO 4 is from about 10 g/L to about 200 g/L; and

optionally, treating the steel with a second composition disposed in a second tub, wherein second composition consists of about 10 g/L to about 130 g/L HNO 3 or about 10 g/L to about 130 g/L HNO 3 and HF; and

optionally, treating the steel with a third mixture disposed in a third tub, wherein the third mixture consists of HNO 3 , and wherein a concentration of HNO 3 is from about 10 g/L to about 130 g/L.

11. The process of claim 10 , wherein the concentration of Fe 2 (SO 4 ) 3 is from about 5 g/L to about 100 g/L.

12. The process of claim 10 , wherein the oxidizing agent is H 2 O 2 .

13. The process of claim 10 , wherein the first mixture further consists of a concentration of HF.

14. The process of claim 10 , wherein the step of applying a current to the steel consists of applying a current via at least one of a cathode or anode.

15. The process of claim 10 , further consisting of treating the steel with the second composition disposed in the second tub, wherein the second composition consists of about 10 g/L to about 130 g/L HNO 3 or about 10 g/L to about 130 g/L HNO 3 and HF.

16. The process of claim 10 , wherein the steel is pickled in a continuous fashion.

17. The process of claim 10 , where a temperature of the first mixture is in the range of from about 70° F. to 180° F. or in the range of from about 80° F. to 130° F.

18. The process of claim 10 , wherein an amount of total dissolved metals in the first mixture after the first mixture treats the strip is equal to or less than about 80 g/L.

19. The process of claim 10 , wherein step of applying a current to the steel consists of applying a current via electrodes that consists of a cathode-anode-cathode arrangement, wherein the electrodes are operable to apply a current in the range of from about 10 Coulombs/dm 2 to about 200 Coulombs/dm 2 with a current density in the range of from about 1 Amps/dm 2 to about 100 Amps/dm 2 .

20. The process of claim 13 , wherein the concentration of H 2 SO 4 is from about 25 g/L to about 35 g/L, and wherein the concentration of HF in the first mixture is from about greater than 0 g/L to about 100 g/L.

21. The process of claim 14 , wherein the steel consists of one of the cathode or anode.

22. The process of claim 15 , wherein the first mixture further consists of HF.

23. The process of claim 15 , wherein the stainless steel consists of a ferritic stainless steel and the second composition consists of HNO 3 .

24. The process of claim 15 , wherein the stainless steel consists of an austenitic stainless steel and the second composition consists of HNO 3 and HF, and wherein the second composition consists of about 5 g/L to about 25 g/L HF.

25. The process of claim 15 , further consisting of treating the steel with a third mixture disposed in a third tub, wherein the third mixture consists of HNO 3 , and wherein a concentration of HNO 3 is from about 10 g/L to about 130 g/L.

Assignments (11)
RELEASE OF SECURITY INTEREST Recorded Apr 5, 2024
From: U.S. BANK NATIONAL ASSOCIATION
To: CLEVELAND-CLIFFS INC.; CLEVELAND-CLIFFS STEEL CORPORATION (F/K/A AK STEEL CORPORATION); CLEVELAND-CLIFFS STEEL PROPERTIES INC. (F/K/A AK STEEL PROPERTIES, INC.)
Reel/Frame 067025/0974 →
RELEASE OF SECURITY INTEREST Recorded May 11, 2022
From: U.S. BANK TRUST COMPANY, NATIONAL ASSOCIATION, SUCCESSOR IN INTEREST TO U.S. BANK NATIONAL ASSOCIATION
To: CLEVELAND-CLIFFS INC.; CLEVELAND-CLIFFS STEEL CORPORATION (F/K/A AK STEEL CORPORATION),; CLEVELAND-CLIFFS STEEL PROPERTIES, INC. (F/K/A AK STEEL PROPERTIES, INC.); IRONUNITS LLC
Reel/Frame 063272/0001 →
CORRECTIVE ASSIGNMENT TO CORRECT THE RECEIVING PARTY DATA FROM CLEVELAND-CLIFFS STEEL PROPERTIES TO CLEVELAND-CLIFFS STEEL PROPERTIES INC. PREVIOUSLY RECORDED AT REEL: 056313 FRAME: 0443. ASSIGNOR(S) HEREBY CONFIRMS THE CHANGE OF NAME. Recorded Jul 2, 2021
From: AK STEEL PROPERTIES, INC.
To: CLEVELAND-CLIFFS STEEL PROPERTIES INC.
Reel/Frame 057941/0376 →
CORRECTIVE ASSIGNMENT TO CORRECT THE RECEIVING PARTY DATA PREVIOUSLY RECORDED AT REEL: 056228 FRAME: 0566. ASSIGNOR(S) HEREBY CONFIRMS THE ASSIGNMENT. Recorded May 20, 2021
From: AK STEEL PROPERTIES, INC.
To: CLEVELAND-CLIFFS STEEL PROPERTIES
Reel/Frame 056313/0443 →
CHANGE OF NAME Recorded May 13, 2021
From: AK STEEL PROPERTIES, INC.
To: CLEVELAND-CLIFFS STEEL PROPERTIES INC.
Reel/Frame 056228/0566 →
RELEASE OF SECURITY INTEREST Recorded Mar 15, 2021
From: U.S. BANK NATIONAL ASSOCIATION
To: AK STEEL CORPORATION; AK STEEL PROPERTIES, INC.
Reel/Frame 055587/0118 →
PATENT SECURITY AGREEMENT Recorded Apr 17, 2020
From: CLEVELAND-CLIFFS INC.; AK STEEL CORPORATION; AK STEEL PROPERTIES, INC.
To: U.S. BANK NATIONAL ASSOCIATION, AS NOTES COLLATERAL AGENT
Reel/Frame 052432/0166 →
PATENT SECURITY AGREEMENT Recorded Mar 13, 2020
From: CLEVELAND-CLIFFS INC.; AK STEEL CORPORATION; AK STEEL PROPERTIES, INC.
To: U.S. BANK NATIONAL ASSOCIATION, AS NOTES COLLATERAL AGENT
Reel/Frame 052162/0865 →
PATENT SECURITY AGREEMENT Recorded Mar 13, 2020
From: CLEVELAND-CLIFFS INC.; AK STEEL CORPORATION; AK STEEL PROPERTIES, INC.
To: BANK OF AMERICA, N.A., AS AGENT
Reel/Frame 052162/0782 →
PATENT SECURITY AGREEMENT Recorded Mar 13, 2020
From: AK STEEL CORPORATION; AK STEEL PROPERTIES, INC.
To: U.S. BANK NATIONAL ASSOCIATION, AS NOTES COLLATERAL AGENT
Reel/Frame 052162/0691 →
ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded Sep 26, 2012
From: GLASS, AMANDA R.; RODABAUGH, RONALD D.; PRICE, DAVID M.
To: AK STEEL PROPERTIES, INC.
Reel/Frame 029027/0712 →