CN1156589C - Dearsenifying method for Cu-Zn-Co material - Google Patents
Dearsenifying method for Cu-Zn-Co material Download PDFInfo
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- CN1156589C CN1156589C CNB021105529A CN02110552A CN1156589C CN 1156589 C CN1156589 C CN 1156589C CN B021105529 A CNB021105529 A CN B021105529A CN 02110552 A CN02110552 A CN 02110552A CN 1156589 C CN1156589 C CN 1156589C
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- sodium hydroxide
- hydroxide solution
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Abstract
The present invention relates to a dearsenifying method for Cu-Zn-Co materials, which is used for the preprocessing of a new smelting method for the Cu-Zn-Co materials. The present invention is characterized in that Cu-Zn-Co material particles are soaked in a sodium hydroxide solution, the concentration of the sodium hydroxide solution is 80 to 160 g/L, the weight compounding ratio of the sodium hydroxide solution and the solid materials is 3 to 7: 1, leaching time is 0.5 to 2 hours, and leaching temperature is 80 to 95 DEG C. The present invention has high arsenic and sulfur elimination rate, obtained leached mud products has few harmful impurities, Cu-Zn-Co grades can be greatly and correspondingly increased, and the present invention provides raw materials which completely accord with requirements for a new Cu-Zn-Co separation smelting method.
Description
Technical Field
The invention relates to the technical field of mineral pretreatment in non-ferrous metal smelting, in particular to the technical field of material arsenic removal by a copper ore smelting method.
Background
The traditional method for recovering cobalt from copper-cobalt ore or cobalt-nickel ore is to adopt cobalt in converter slag to perform sulfuration reduction smelting. Because the cobalt is distributed and dispersed in the process, part of the cobalt is lost in the smelting slag, and meanwhile, a large amount of quartz flux is added in the converter blowing, the cobalt enrichment multiple in the converter slag is low, namely, the traditional method has the problems of low cobalt recovery rate, low cobalt grade in the cobalt-rich slag, high further treatment cost and the like. The invention provides a novel pyrometallurgical smelting method, which utilizes different reduction sequences of oxides such as copper, zinc, cobalt, iron and the like in materials, uses metallurgical coke or other reducing agents to carry out smelting in a special blast furnace or an electric arc furnace, correspondingly adjusts the slag type of furnace slag, controls the reduction degree in the smelting process and achieves the purpose of separating copper, zinc and cobalt at one time. The copper is recovered in the form of crude copper, zinc in the form of zinc oxide and cobalt-rich slag. The process method has the characteristics of simple process, thorough separation, good comprehensive recovery of valuable metals of materials, high metal recovery rate, low recovery cost, good economic benefit and the like, opens up a new way for effectively treating the complex copper-zinc-cobalt materials, but the process has strict requirements on impurities such as arsenic, antimony, lead, tin, bismuth and the like inthe materials, especially has strict requirements on arsenic content, most of the materials can meet the requirements on the impurity content at present, and can be directly added into a furnace for smelting, but a large number of materials contain more impurities and can be put into the furnace for smelting only after being pretreated.
Disclosure of Invention
The invention aims to solve the technical problem of providing a method for removing arsenic from copper-zinc-cobalt materials in the prior art, which removes impurities such as arsenic from the arsenic-containing copper-zinc-cobalt materials to produce materials with low arsenic content for a new smelting method for separating copper, cobalt and zinc to obtain high-quality crude copper, zinc oxide and cobalt-rich slag.
The technical scheme adopted by the invention for solving the technical problems is as follows: the method for removing arsenic from copper-zinc-cobalt material is characterized in that sodium hydroxide solution is adopted to impregnate copper-zinc-cobalt material particles, the concentration of the sodium hydroxide solution is 80-160 g/L, the mass ratio of the sodium hydroxide solution to solid material is 3-7: 1, the leaching time is 0.5-2 hours, and the leaching temperature is 80-95 ℃.
The concentration of the sodium hydroxide solution is better controlled to be 110-130 g/L, the mass ratio of the sodium hydroxide solution to the solid material is 5: 1, the leaching time is 1 hour, the leaching temperature is 90 ℃, the dipping adopts multi-section countercurrent dipping, and the number of the sections is controlled to be 2-4 sections.
In order to achieve the purposes of completely recycling the solution and no sewage discharge, the sodium hydroxide solution is used as a leaching solution after being soaked in copper-zinc-cobalt material particles, the leaching solution is recycled by mother liquor after concentration and crystallization, the crystallization mixture is replaced by calcium hydroxide after being dissolved in water, calcium arsenate is recovered, the mother liquor is concentrated and crystallized to generate mirabilite, and then the residual solution is used for washing leaching residues and is recycled to be used for soaking the copper-zinc-cobalt material.
In order to be more beneficial to impurity leaching, the particle size of the copper-zinc-cobalt material is preferably less than 100 meshes, and accounts for more than 80% of the total mass.
Compared with the prior art, the invention has the advantages that: the arsenic and sulfur removal rate is extremely high, the obtained leaching residue product contains few harmful impurities, the grade of copper, zinc and cobalt is correspondingly improved greatly, and raw materials which completely meet the requirements are provided for a new copper, zinc and cobalt separation smelting method. Taking the consumption of one ton of material as an example, 150 kg of sodium hydroxide, 40 kg of calcium hydroxide, 500 kg of coal and a proper amount of sodium sulfide are mainly used, and the method has the advantages of simplicity and low cost. Particularly, the invention also recovers the arsenic, lead, zinc and mirabilite from the impregnation liquid, avoids producing highly toxic substances arsenic oxide in the process of treatment and recovery, concentrates, cools and crystallizes the mirabilite and sodium arsenate, separates and produces calcium arsenate as an insecticide product, and the solution can be completely recycled without discharging sewage, thereby achieving the air and environmental protection.
Detailed Description
The present invention will be described in further detail with reference to examples.
Example 1
Soaking copper-zinc-cobalt material particles in a sodium hydroxide solution, wherein the concentration of the sodium hydroxide solution is 120 g/L, the mass ratio of the sodium hydroxide solution to solid materials is 5: 1, the leaching time is 1 hour, the leaching temperature is 90 ℃, and three-section countercurrent soaking is adopted.
The copper-zinc-cobalt material before impregnation comprises the following chemical component components: 23.33 percent of Cu, 25.91 percent of Zn, 0.87 percent of Co, 1.63 percent of Fe, 3.81 percent of As, 6.88 percent of S, 1.69 percent of Pb, 3.15 percent of Cd, 0.15 percent of Ni, 0.47 percent of Mn, 0.012 percent of Bi, 0.0066 percent of Sn, 0.86 percent of CaO, 1.09 percent of MgO, Al2O30.16％、SiO23.96% and other trace components.
After the treatment of strong alkaline solution, the obtained slag contains Cu 35.48%, Zn 32.26%, Co 1.21%, Fe 1.74%, CaO 0.98%, MgO 1.05%, and SiO26.40 percent, 0.17 percent of As, 0.48 percent of S, 4.26 percent of Cd, 97.7 percent of leaching rate of As, 96 percent of S, 53.8 percent of Pb and 16.6 percent of Zn, and the material can completely meet the new smelting requirement of copper-zinc-cobalt separation. And the arsenic content is low, the sulfur content is low, so that the arsenic content of the crude copper produced in the later smelting is lower than 0.4 percent, and a foundation is laid for reducing sulfur dioxide in the sintering flue gas.
And materials containing 1-7% of arsenic and 0-9% of sulfur can be treated, and arsenic, lead, zinc and mirabilite are recovered from the impregnation liquid. The method comprises the steps of dipping copper-zinc-cobalt material particles into a sodium hydroxide solution to obtain a leaching solution, concentrating and crystallizing, recycling mother liquor to dip the copper-zinc-cobalt material, dissolving a crystallization mixture in water, and replacing the crystallization mixture with calcium hydroxide, wherein the amount of lime with low price is more than three times of that of theoretical calculation amount, sodium arsenate generates precipitated calcium arsenate and regenerated alkali sodium hydroxide, and a part of mirabilite is also converted into regenerated alkali sodium hydroxide, so that a large amount of regenerated alkali is increased, the mother liquor is concentrated and crystallized to generate mirabilite after the calcium arsenate is recovered, and then washing leaching residues with residual liquor and recycling the leached copper-zinc-cobalt material.
As the calcium arsenate is used as the pesticide product, the solution can be completely recycled, no sewage is discharged, and air and environmental protection is achieved.
In order to facilitate the removal of arsenic from copper-zinc-cobalt material particles, the particles are in principle smaller and better, but this increases the production cost, generally, as long as the particles with the size of less than 100 meshes account for 80% by mass.
The main chemical reaction process is as follows:
when the sodium hydroxide solution is used for soaking the copper-zinc-cobalt material particles, arsenic in the material mainly exists in the form of copper arsenate and chemically reacts with sodium hydroxide.
The following chemical reactions occur when lime is added to the impregnation liquor.
Thereby generating a large amount of regenerated alkali, recycling residual liquid, and simultaneously recovering calcium arsenate to be used as the pesticide.
For 1 ton of material pretreatment, main medicament consumption:
NaOH 150 kg Ca (OH)280 kg coal 500 kg
Therefore, the cost is low, the process is scientific and reasonable, and the implementation is easy.
Example 2
Soaking copper-zinc-cobalt material particles in a sodium hydroxide solution, wherein the concentration of the sodium hydroxide solution is 160 g/L, the mass ratio of the sodium hydroxide solution to solid materials is 3: 1, the leaching time is 0.5 hour, the leaching temperature is 95 ℃, and two-stage countercurrent soaking is adopted.
The sodium hydroxide solution is used for dipping copper-zinc-cobalt material particles to form a leaching solution, the leaching solution is concentrated and crystallized, mother liquor is recycled to remove the dipping materials, a crystallization mixture is dissolved in water and is replaced by calcium hydroxide, calcium arsenate is recovered, the mother liquor is concentrated and crystallized to generate mirabilite, and then residual liquor is used for washing leaching residues and is recycled to remove the dipping copper-zinc-cobalt material.
Example 3
Soaking copper-zinc-cobalt material particles in a sodium hydroxide solution, wherein the concentration of the sodium hydroxide solution is 80 g/L, the mass ratio of the sodium hydroxide solution to solid materials is 7: 1, the leaching time is 2 hours, the leaching temperature is 85 ℃, and four-stage countercurrent soaking is adopted.
The sodium hydroxide solution is used for dipping copper-zinc-cobalt material particles to form a leachingsolution, the leaching solution is concentrated and crystallized, mother liquor is recycled to remove the dipping materials, a crystallization mixture is dissolved in water and is replaced by calcium hydroxide, calcium arsenate is recovered, the mother liquor is concentrated and crystallized to generate mirabilite, and then residual liquor is used for washing leaching residues and is recycled to remove the dipping copper-zinc-cobalt material.
Example 4
Soaking copper-zinc-cobalt material particles in a sodium hydroxide solution, wherein the concentration of the sodium hydroxide solution is 100 g/L, the mass ratio of the sodium hydroxide solution to solid materials is 4: 1, the leaching time is 0.75 hour, the leaching temperature is 90 ℃, and three-section countercurrent soaking is adopted.
The sodium hydroxide solution is used for dipping copper-zinc-cobalt material particles to form a leaching solution, the leaching solution is concentrated and crystallized, mother liquor is recycled to remove the dipping materials, a crystallization mixture is dissolved in water and is replaced by calcium hydroxide, calcium arsenate is recovered, the mother liquor is concentrated and crystallized to generate mirabilite, and then residual liquor is used for washing leaching residues and is recycled to remove the dipping copper-zinc-cobalt material.
Example 4
Soaking copper-zinc-cobalt material particles in a sodium hydroxide solution, wherein the concentration of the sodium hydroxide solution is 140 g/L, the mass ratio of the sodium hydroxide solution to solid materials is 6: 1, the leaching time is 0.5 hour, the leaching temperature is 90 ℃, and three-section countercurrent soaking is adopted.
The sodium hydroxide solution is used for dipping copper-zinc-cobalt material particles to form aleaching solution, the leaching solution is concentrated and crystallized, mother liquor is recycled to remove the dipping materials, a crystallization mixture is dissolved in water and is replaced by calcium hydroxide, calcium arsenate is recovered, the mother liquor is concentrated and crystallized to generate mirabilite, and then residual liquor is used for washing leaching residues and is recycled to remove the dipping copper-zinc-cobalt material.
Claims (8)
1. A method for removing arsenic from a copper-zinc-cobalt material is characterized by comprising the following steps: soaking copper-zinc-cobalt material particles by using a sodium hydroxide solution, wherein the concentration of the sodium hydroxide solution is 80-160 g/L, and the mass ratio of the sodium hydroxide solution to solid materials is 3-7: 1, the leaching time is 0.5-2 hours, and the leaching temperature is 80-95 ℃.
2. The method as set forth in claim 1, wherein the concentration of the sodium hydroxide solution is 110 g/L and 130 g/L.
3. The method according to claim 1, wherein the mass ratio of the sodium hydroxide solution to the solid material is 5: 1.
4. A method according to claim 1, characterized in that the leaching time is 1 hour.
5. A method according to claim 1, characterized in that the leaching temperature is at 90 ℃.
6. The method of claim 1, wherein the impregnation is performed by a multi-stage countercurrent impregnation, and the number of stages is controlled to be 2-4 stages.
7. The method according to claim 1, wherein the sodium hydroxide solution is used as a leaching solution after the copper-zinc-cobalt material particles are soaked, the leaching solution is concentrated and crystallized, mother liquor is recycled to remove the soaking material, the crystallized mixture is dissolved in water and is replaced by calcium hydroxide to recover calcium arsenate, the mother liquor is concentrated and crystallized to generate mirabilite, and then the residual solution is used for washing leaching residues and is recycled to remove the copper-zinc-cobalt material.
8. The method according to claim 1, wherein the Cu-Zn-Co material has a particle size of less than 100 mesh accounting for more than 80% of the total mass.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB021105529A CN1156589C (en) | 2002-01-14 | 2002-01-14 | Dearsenifying method for Cu-Zn-Co material |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB021105529A CN1156589C (en) | 2002-01-14 | 2002-01-14 | Dearsenifying method for Cu-Zn-Co material |
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| CN1375565A CN1375565A (en) | 2002-10-23 |
| CN1156589C true CN1156589C (en) | 2004-07-07 |
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| CNB021105529A Expired - Fee Related CN1156589C (en) | 2002-01-14 | 2002-01-14 | Dearsenifying method for Cu-Zn-Co material |
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Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103290221A (en) * | 2012-02-28 | 2013-09-11 | 兰州理工大学 | Method for recovering copper, arsenium and antimony from black copper sludge |
| CN105349771A (en) * | 2015-10-13 | 2016-02-24 | 盐城同济新材料科技有限公司 | Method for recycling copper from arsenic-containing copper slag |
| CN109650412B (en) * | 2018-12-28 | 2021-09-21 | 焱鑫环保科技有限公司 | Method for producing sodium sulfite by removing sulfur in sulfur-containing flue gas by arsenic-containing industrial alkaline residue |
| CN113584313B (en) * | 2021-07-28 | 2023-03-17 | 云南驰宏资源综合利用有限公司 | Method for producing coarse copper powder from high-arsenic copper bismuth slag |
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