Hydrometallurgical method for recycling lead from spent lead-acid battery paste

Patent metadata

Field	Value
Publication number	US-11502344-B2
Application number	US-201716499374-A
Country	US
Kind code	B2
Filing date	Oct 17, 2017
Priority date	Oct 11, 2017
Publication date	Nov 15, 2022
Grant date	Nov 15, 2022

Abstract

A method for recycling lead from spent lead-acid battery paste, relating to the technical field of hydrometallurgy. In the method, firstly a reducing agent, and a lead paste are added into a zinc chloride solution for leaching in a stirring mill to cause lead in the lead paste to enter the solution, a lead cementation is performed by using zinc in the leached solution, after the lead cementation, the electrolytic zinc is produced by controlling an electrodeposition on the zinc chloride solution for a short time, the reducing agent is zinc, lead or hydrogen peroxide, a part of the electrolytic zinc is returned as the reducing agent for leaching, the step of returning the electrolytic zinc as the reducing agent can be omitted when the lead or the hydrogen peroxide is used as the reducing agent.

First claim

What is claimed is:

1. A hydrometallurgical method for recycling lead from a spent lead-acid battery, comprising the following steps:
(1) leaching a lead paste from the spent lead-acid battery by using lead or hydrogen peroxide as a reducing agent, and a zinc chloride solution as a leaching agent; after the leaching is completed, obtaining a leaching residue and a leached solution by a liquid-solid separation;
(2) adding zinc to the leached solution obtained in the step (1) for a lead cementation to obtain the lead and a solution;
(3) performing an electrodeposition on the solution obtained in the step (2) to obtain an electrolytic zinc and an electrodeposited solution;
(4) using the electrolytic zinc obtained in the step (3) as a cementation reagent in the step (2) for the lead cementation;
(5) adding calcium chloride to the electrodeposited solution obtained in the step (3) to remove a sulfate ion in the solution and obtain calcium sulfate and a purified solution;
(6) using the purified solution obtained in the step (5) as the leaching agent in the step (1).

2. The method for recycling the lead from the spent lead-acid battery paste according to claim 1 , wherein the lead paste treated in the step (1) has a composition comprising 60% to 75% by weight of Pb.

3. The method for recycling the lead from the spent lead-acid battery paste according to claim 1 , wherein in the step (1), a leaching temperature is 20° C. to 95° C., a leaching time is 0.5 h to 4 h, and a concentration of the zinc chloride solution is 100 to 600 g/L, before leaching, a liquid-solid ratio in a mixed solution consisting of the lead paste, the zinc chloride solution and the reducing agent is 20-40:1, and an equipment used for the leaching is a stirring mill.

4. The method for recycling the lead from the spent lead-acid battery paste according to claim 1 , wherein in the step (1), hydrochloric acid is used to control a pH of the solution at 1.0 to 4.0 during the leaching process.

5. The method for recycling the lead from the spent lead-acid battery paste according to claim 1 , wherein in the step (2), the zinc used is electrolytic zinc, a cementation temperature is 20° C. to 90° C., an amount of the zinc used is 1 to 1.1 times of a theoretical amount of the zinc to corresponding to an amount of lead to complete lead cementation, and a cementation time is 0.5 h to 2 h.

6. The method for recycling the lead from the spent lead-acid battery paste according to claim 1 , wherein in a zinc electrodeposition in the step (3), a current density is 100 A/m 2 to 500 A/m 2 , a temperature is 10° C. to 60° C., an anode is graphite or a ruthenium-plated titanium plate, and a cathode is a titanium plate.

7. The method for recycling the lead from the spent lead-acid battery paste according to claim 1 , wherein in the step (5), a reaction temperature is 10° C. to 60° C., an amount of the calcium chloride used is 1 to 1.1 times of a theoretical amount of the calcium chloride corresponding to an amount of sulfate ion to complete a reaction for obtaining calcium sulfate, and a concentration of sulfate ions is controlled at 20 g/L.

8. A hydrometallurgical method for recycling lead from a spent lead-acid battery, comprising the following steps:
(1) leaching a lead paste from the spent lead-acid battery by using zinc as a reducing agent, and a zinc chloride solution as a leaching agent; after the leaching is completed, obtaining a leaching residue and a leached solution by a liquid-solid separation;
(2) adding zinc to the leached solution obtained in the step (1) for a lead cementation to obtain the lead and a solution;
(3) performing an electrodeposition on the solution obtained in the step (2) to obtain an electrolytic zinc and an electrodeposited solution;
(4) using a part of the electrolytic zinc obtained in the step (3) as the reducing agent in the step (1) for leaching, and using the remaining electrolytic zinc as a cementation reagent in the step (2) for the lead cementation;
(5) adding calcium chloride to the electrodeposited solution obtained in the step (3) to remove a sulfate ion in the solution and obtain calcium sulfate and a purified solution;
(6) using the purified solution obtained in the step (5) as the leaching agent in the step (1).

9. The method for recycling the lead from the spent lead-acid battery paste according to claim 8 , wherein the lead paste treated in the step (1) has a composition comprising 60% to 75% by weight of Pb.

10. The method for recycling the lead from the spent lead-acid battery paste according to claim 8 , wherein in the step (1), a leaching temperature is 20° C. to 95° C., a leaching time is 0.5 h to 4 h, and a concentration of the zinc chloride solution is 100 to 600 g/L, before leaching, a liquid-solid ratio in a mixed solution consisting of the lead paste, the zinc chloride solution and the reducing agent is 20-40:1, and an equipment used for the leaching is a stirring mill.

11. The method for recycling the lead from the spent lead-acid battery paste according to claim 8 , wherein in the step (1), hydrochloric acid is used to control a pH of the solution at 1.0 to 4.0 during the leaching process.

12. The method for recycling the lead from the spent lead-acid battery paste according to claim 8 , wherein in the step (2), the zinc used is electrolytic zinc, a cementation temperature is 20° C. to 90° C., an amount of the zinc used is 1 to 1.1 times of a theoretical amount of the zinc to corresponding to an amount of lead to complete lead cementation, and a cementation time is 0.5 h to 2 h.

13. The method for recycling the lead from the spent lead-acid battery paste according to claim 8 , wherein in a zinc electrodeposition in the step (3), a current density is 100 A/m 2 to 500 A/m 2 , a temperature is 10° C. to 60° C., an anode is graphite or a ruthenium-plated titanium plate, and a cathode is a titanium plate.

14. The method for recycling the lead from the spent lead-acid battery paste according to claim 8 , wherein in the step (5), a reaction temperature is 10° C. to 60° C., an amount of the calcium chloride used is 1 to 1.1 times of a theoretical amount of the calcium chloride corresponding to an amount of sulfate ion to complete a reaction for obtaining calcium sulfate, and a concentration of sulfate ions is controlled at 20 g/L.

Assignees

• Univ Beijing Science & Technology

Inventors

• Wang Chengyan
• Xing Peng
• Chen Yongqiang

Classifications

• Y02E60/10

  Energy storage using batteries · CPC title

• C22B13/045

  Recovery from waste materials · CPC title

• C22B3/44 Primary

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

• C01F11/46

  Sulfates (dehydration of gypsum {for the production of calcium sulfate cements} C04B11/02) · CPC title

• H01M4/14

  Electrodes for lead-acid accumulators · CPC title