Chemical Recovery of Zinc Oxalate and Manganese Dioxide from Battery Black Paste

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Solution Overview

Problem

Current battery recycling processes face inefficiencies due to the mixing of unknown compositions after battery separation, leading to high energy and environmental costs in pyrometallurgical treatments.

Innovation Solution

A chemical treatment process involving selective dry extraction, water washing, sulfuric acid treatment, oxalic acid precipitation, and electrolysis to recover zinc oxalate and electrolytic manganese dioxide from alkaline and zinc-carbon battery black pastes, allowing for the separation and recycling of recyclable raw materials.

Engineering Contradictions & Design Principles

VSEngineering Contradiction Analysis

1Loss of substance

If pyrometallurgical treatment is used for battery recycling, then complete material recovery is achieved, but energy consumption and environmental costs increase significantly

Engineering Contradiction:
Improvematerial recovery completenessVSAvoidenergy consumption
Core Design Contradiction:
Loss of substanceVSUse of energy by moving object

Solution Approach 1:

The recycling process is divided into distinct stages: mechanical separation to isolate black paste, selective dissolution to separate zinc and manganese compounds, and targeted precipitation to recover pure materials. This segmentation allows each stage to be optimized independently, avoiding the high energy costs of complete pyrometallurgical processing while ensuring thorough material recovery.

Inventive Principle:
Principle #1Segmentation

Solution Approach 2:

The process utilizes controlled changes in chemical parameters (pH, concentration, temperature) to selectively dissolve and precipitate different battery components. By adjusting these parameters, zinc and manganese can be recovered in high purity through wet chemical methods, eliminating the need for energy-intensive melting and refining operations.

Inventive Principle:
Principle #35Parameter changes

2Ease of manufacture

If batteries are ground and washed with water to extract black paste components, then material separation is achieved, but the composition becomes unknown and variable

Engineering Contradiction:
Improveextraction simplicityVSAvoidcomposition control
Core Design Contradiction:
Ease of manufactureVSManufacturing precision

Solution Approach 1:

The process incorporates analytical monitoring to track the composition of the black paste and subsequent solution phases. This feedback enables real-time adjustment of dissolution and precipitation conditions, ensuring consistent recovery of zinc and manganese regardless of variations in incoming battery composition.

Inventive Principle:
Principle #23Feedback

Solution Approach 2:

By systematically controlling chemical parameters such as acid concentration, pH, and precipitation conditions, the process transforms variable black paste compositions into consistent, high-purity product streams. The controlled parameter changes ensure that zinc and manganese are reliably separated and recovered in predictable quantities and purities.

Inventive Principle:
Principle #35Parameter changes

3Manufacturing precision

If selective chemical treatment is applied to black paste, then high-purity zinc oxalate and manganese dioxide are recovered, but process complexity increases

Engineering Contradiction:
Improveproduct purityVSAvoidprocess complexity
Core Design Contradiction:
Manufacturing precisionVSDevice complexity

Solution Approach 1:

The process selectively extracts zinc and manganese from the black paste through controlled dissolution, then separates them via selective precipitation. Zinc is precipitated as oxalate while manganese remains in solution, and vice versa in subsequent steps. This targeted extraction approach achieves high purity products through straightforward chemical separations rather than complex multi-step procedures.

Inventive Principle:
Principle #2Taking out (Extraction)

Solution Approach 2:

Oxalic acid serves as an intermediary reagent that selectively precipitates zinc from the dissolved black paste, while manganese remains in solution. This intermediary substance enables clean separation of the two metals without requiring complex equipment or multiple processing stages, maintaining process simplicity while achieving high purity recovery.

Inventive Principle:
Principle #24Intermediary (Mediator)

Applied Scientific Principles

This section explains which scientific principles are used to turn an abstract innovation direction into a practical engineering solution.

Function Achieved in This Case

This process enables effective and environmentally friendly recovery of recyclable materials, reducing energy and environmental costs by achieving high-purity zinc oxalate and manganese dioxide recovery, with additional by-products for industrial and agricultural use.

Implementation Method 1

washing the black paste with water to separate the potassium hydroxide of the alkaline batteries and the ammonium chloride of zinc-carbon batteries in the form of a solution

Methodology Applied
Scientific EffectDissolution: Solvation

Implementation Method 2

treatment of the wet black paste resulting from step b) with an aqueous solution of sulfuric acid, achieving the solubilisation of metallic zinc and of its compounds and of manganese compounds

Methodology Applied
Scientific EffectAcid dissolution: Chemical Bonding

Implementation Method 3

treating the sulfuric solution obtained in step d) with oxalic acid in sub-stoichiometric amounts compared to zinc, obtaining the precipitation of zinc oxalate

Methodology Applied
Scientific EffectPrecipitation: Precipitation

Implementation Method 4

electrolysis of the acid solution with formation of MnO2 at the anode

Methodology Applied
Scientific EffectElectrolysis: Electrolysis

Implementation Method 5

electrolysis of the acid solution with formation of MnO2 at the anode

Methodology Applied
Scientific EffectElectrochemical oxidation: Oxidation

Data Source

PatentUS11578387B2Chemical process for the recovery of alkaline and zinc-carbon battery components
Publication Date: 2023.02.14 EVH SRL IN LIQUIDAZIONE

AI summary

A process is described for the recovery of the chemical components of the “black paste” resulting from the opening of dead alkaline and zinc-carbon batteries.