CN102242267A

CN102242267A - Method for recycling valuable metal in manganese-rich slag

Info

Publication number: CN102242267A
Application number: CN2011101599825A
Authority: CN
Inventors: 邓洪民
Original assignee: Jinchuan Group Co Ltd
Current assignee: Jinchuan Group Co Ltd
Priority date: 2011-06-15
Filing date: 2011-06-15
Publication date: 2011-11-16

Abstract

The invention discloses a method for recycling a valuable metal in manganese-rich slag. The method comprises the following process steps of: a, leaching out the manganese-rich slag by using a sulfuric acid solution with a concentration of 50-250g/L according to a ratio of solid to liquid of 1:1-1:5, and converting into a sulfate solution; b, carrying out constant-temperature crystallization on the leached sulfate solution at 180-250 DEG C for 10-30min; c, filtering at 180-250 DEG C to obtain a crystallization master liquid and manganese sulfate crystals; d, cooling down the manganese sulfate crystals to 20-50 DEG C for dissolving, and filtering to obtain a pure manganese sulfate solution; e, carrying out constant-temperature recrystallization on the pure manganese sulfate solution at 180-200 DEG C for 10-30min, filtering at 180-200 DEG C and drying the crystals to obtain manganese sulfate monohydrate crystals; and f, settling the filtered crystallization master liquid in the step c by using sodium sulfide with 2-5 times of theoretical amount to obtain a sulfate sediment. According to the method disclosed by the invention, the valuable metal in the manganese-rich slag is recycled by using a high-temperature recrystallization method, the recycling rate of the valuable metal is high, and the recycled valuable metal can be recycling with a responsive crude ore, thus the recycling process flow of is shortened, and the production cost is reduced.

Description

Recycle the method for valuable metal in the rich manganese slag

Technical field

The present invention relates to chemical industry, hydrometallurgy field, particularly a kind of method of recycling valuable metal in the rich manganese slag.

Background technology

At present when handling the ore of valuable metals such as nickeliferous, cobalt, copper, zinc, manganese, usually adopt extraction process that valuable metals such as the nickel in the ore, cobalt, copper are extracted, produce relevant nickel, cobalt, copper valuable metal product, in leaching process, isolated zinc, manganese solution (carrying valuable metals such as part of nickel, cobalt, copper secretly) are rich manganese slag with carbonate deposition, reclaim cobalt, copper through pyrogenic attack then, zinc wherein vapors away in the pyrogenic process removal process, and manganese is abandoned or adopted by slag making.This method exists recovery rate of valuable metals low, problem such as energy consumption height, environmental pollution are serious; Also having with isolated zinc, the manganese solution that contains the valency metal is raw material, adopts the technology of multistep extraction, reclaims organo-metallic wherein.There are problems such as technical process is long, production cost is high, production environment difference in this method.

Summary of the invention

Technical problem to be solved by this invention is the problem that exists at existing treatment process, a kind of method that adopts the high temperature recrystallization method to recycle valuable metal in the rich manganese slag is provided, reclaim technical process to shorten, reduce production costs, improve recovery rate of valuable metals.

The present invention adopts following technical scheme for solving the problems of the technologies described above:

A kind of method of recycling valuable metal in the rich manganese slag, its processing step is as follows:

A is the sulphuric acid soln of rich manganese slag with 50～250g/L, is that the ratio of 1:1～1:5 leaches in solid-to-liquid ratio, is converted into sulfate liquor;

B with the sulfate liquor that leaches at 180 ℃～250 ℃ following thermostatical crystallization 10min～30min;

C filters down at 180 ℃～250 ℃, gets crystalline mother solution and manganous sulfate crystal;

D is cooled to 20 ~ 50 ℃ with the manganous sulfate crystal and makes its dissolving, filter purified manganese sulfate solution;

E under 180 ℃～200 ℃, behind constant temperature recrystallization 10min～30min, filters purified manganese sulfate solution down at 180 ℃～200 ℃, with the crystal drying, gets the manganese sulfate monohydrate crystal;

The crystalline mother solution that f the filters out c sodium sulphite precipitation of 2 ~ 5 times of theoretical amount gets sulfide precipitation.

The present invention adopts the high temperature recrystallization method to recycle valuable metal in the rich manganese slag, and recovery rate of valuable metals height, the valuable metal that is recovered to can be incorporated in the raw ore of response and reclaim, and have shortened the recovery technical process, reduce production costs.

Embodiment:

Embodiment 1:

The manganous carbonate slag 1kg that a will contain 5% nickel, cobalt, copper, zinc leaches with the sulfuric acid of 5kg 50g/L, the sulfate liquor of nickeliferous, cobalt, copper, zinc, manganese;

B with the sulfate liquor that leaches under 180 ℃, thermostatical crystallization 10min;

C filters down at 180 ℃, the crystalline mother solution and the manganese sulfate monohydrate crystal of nickeliferous, cobalt, copper, zinc;

D is cooled to 50 ℃ with manganese sulfate monohydrate crystal ordinary method and makes its dissolving, filter purified manganese sulfate solution;

E under 180 ℃, behind the constant temperature recrystallization 10min, filters purified manganese sulfate solution down at 180 ℃, and drying gets the manganese sulfate monohydrate crystal;

F precipitates the crystalline mother solution of nickeliferous, cobalt, copper, zinc with 120g sodium sulphite, get the mixed precipitation of cobaltous sulfide, cupric sulfide, nickelous sulfide, zinc sulphide, this precipitation is returned in cobaltous sulfide or cupric sulfide or the nickel sulfide ores reclaimed.

Embodiment 1 result is as shown in table 1:

Table 1 embodiment 1 result

Figure 2011101599825100002DEST_PATH_IMAGE001

Embodiment 2:

A will contain the sulfuric acid leaching of the rich manganese slag 5kg of 1% nickel, cobalt with 5kg250g/L, get the sulfate liquor of nickel and cobalt containing manganese;

B with the sulfate liquor that leaches under 250 ℃, thermostatical crystallization 30min;

C filters down at 250 ℃, gets crystalline mother solution and anhydrous manganous sulfate crystal nickeliferous, cobalt;

D is cooled to 20 ℃ with anhydrous manganous sulfate crystal ordinary method and makes its dissolving, filter purified manganese sulfate solution;

E under 200 ℃, behind the constant temperature recrystallization 30min, filters purified manganese sulfate solution down at 200 ℃, and drying gets the manganese sulfate monohydrate crystal;

F with the crystalline mother solution of nickel and cobalt containing with 330g sodium sulphite precipitation, the mixed sulphide precipitation of nickelous sulfide cobalt, the mixed sulphide precipitation of nickelous sulfide cobalt is returned in the ore of cobaltous sulfide or nickelous sulfide and is reclaimed.

Embodiment 2 results are as shown in table 2:

Table 2 embodiment 2 results

Embodiment 3:

A will contain the sulfuric acid leaching of the rich manganese slag 5kg of 2% cobalt with 10kg200g/L, must contain the sulfate liquor of cobalt manganese;

B with the sulfate liquor that leaches under 200 ℃, thermostatical crystallization 25min;

C filters down at 200 ℃, must contain the crystalline mother solution and the mixture crystal that contains manganese sulfate monohydrate and anhydrous manganous sulfate of cobalt;

D will mix the manganous sulfate crystal and be cooled to 40 ℃ and make its dissolving, filter purified manganese sulfate solution

E under 195 ℃, behind the constant temperature recrystallization 25min, filters purified manganese sulfate solution down at 195 ℃, and drying gets the manganese sulfate monohydrate crystal;

The crystalline mother solution that f will contain cobalt precipitates with 400g sodium sulphite, gets the precipitation of cobaltous sulfide, the cobaltous sulfide precipitation is returned in the cobaltous sulfide ore reclaimed.

Embodiment 3 results are as shown in table 3:

Table 3 embodiment 3 results

Figure 2011101599825100002DEST_PATH_IMAGE003

Claims

1. method of recycling valuable metal in the rich manganese slag, its processing step is as follows:

A, with the sulphuric acid soln of rich manganese slag with 50～250g/L, be that the ratio of 1:1～5 leaches in solid-to-liquid ratio, be converted into sulfate liquor;

B, with the sulfate liquor that leaches at 180 ℃～250 ℃ following thermostatical crystallization 10min～30min;

C, filtration under 180 ℃～250 ℃ get crystalline mother solution and manganous sulfate crystal;

D, the manganous sulfate crystal be cooled to 20 ~ 50 ℃ make its dissolving, filter purified manganese sulfate solution;

E, with purified manganese sulfate solution under 180 ℃～200 ℃, behind constant temperature recrystallization 10min～30min, filter down at 180 ℃～200 ℃, with the crystal drying, the manganese sulfate monohydrate crystal;

F, crystalline mother solution that c is filtered out be with the sodium sulphite precipitation of 2 ~ 5 times of theoretical amount, sulfide precipitation.