CN1156588C - Sulfurizing reduction and roasting and voltizing dearsenication method for copper-zine-cobalt material - Google Patents
Sulfurizing reduction and roasting and voltizing dearsenication method for copper-zine-cobalt material Download PDFInfo
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- CN1156588C CN1156588C CNB021105715A CN02110571A CN1156588C CN 1156588 C CN1156588 C CN 1156588C CN B021105715 A CNB021105715 A CN B021105715A CN 02110571 A CN02110571 A CN 02110571A CN 1156588 C CN1156588 C CN 1156588C
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Abstract
The present invention relates to a dearsenization processing technique for Cu-Zn-Co containing minerals in non-ferrous metal metallurgy, which can effectively remove arsenic. The present invention is characterized in that 36 to 58% of Cu-Zn-Co materials, 36 to 58% of low-sulfur vulcanizer copper glance and 4 to 8% of reducing agent carbonaceous mass are ground and uniformly mixed for granulating, and the mixture is reduced and calcined at 700 to 900 DEG C. The present invention has the advantages of reasonable and scientific process, little pollution and high arsenic elimination rate and is suitable for being popularized for non-ferrous metal metallurgy.
Description
Technical Field
The invention relates to the technical field of mineralpretreatment 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-containing nickel ore is to adopt cobalt in converter slag to carry out sulfuration reduction smelting, part of cobalt is lost in the smelting slag due to the dispersion and dispersion of the cobalt in the process, and meanwhile, a large amount of quartz flux is added in the converter blowing, so that the cobalt concentration 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 processing 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 in the materials, especially has strict requirements on arsenic content, most of the materials can meet the requirementson 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.
The traditional sulfurizing roasting method is to add a large amount of pyrite or arsenious sulfide ore into the material to roast together to volatilize arsenic in the form of arsenious sulfide, but because a large amount of sulphide ore is added as a vulcanizing agent, and a large amount of sulfur dioxide smoke is generated at the same time, which is not suitable for increasingly strict environmental protection requirements.
Disclosure of Invention
The invention aims to solve the technical problem of providing a method for removing arsenic by sulfurizing, reducing, roasting and volatilizing of a copper-zinc-cobalt material, which can well remove arsenic from the material, and roasted product roasted sand of the material is used for a new copper-zinc-cobalt separation smelting method to produce a crude copper product, 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 by sulfurizing, reducing, roasting and volatilizing of the copper-zinc-cobalt material is characterized by comprising the following steps: 36 to 58 percent of copper-zinc-cobalt material, 36 to 58 percent of low-sulfur vulcanizing agent chalcocite and 2 to 10 percent of carbonaceous material by mass percent, uniformly mixing and granulating after crushing, and then carrying out vulcanization reduction roasting at the temperature of 700 ℃ and 900 ℃, wherein the time for the vulcanization reduction roasting is controlled to be 1.5 to 2.5 hours.
The optimizedproportion of the copper-zinc-cobalt material, the low-sulfur vulcanizing agent chalcocite and the carbonaceous material is 46-48%, 46-48% and 4-8%.
The granulation is preferably carried out by humidifying with water and granulating, and the diameter of the granules is controlled to be 3-6 mm.
The above-mentioned sulfidation reduction roasting is carried out in a rotary kiln for a period of time controlled within a range of 1.5 to 2.5 hours, preferably within a range of 2 hours.
The above temperature is preferably 800 degrees.
The carbonaceous material is coal powder or coke powder.
Compared with the prior art, the invention has the advantages that: the sulfurizing agent provided by the invention is also a copper raw material of a new smelting method, so that only a small amount of reducing agent and adhesive are actually used, particularly after the adhesive adopts water, the reducing agent is evaporated and decomposed in the roasting process and most of the reducing agent carbon materials are reacted, and the problem of post-treatment process is avoided, so that the process design is reasonable and scientific, and the cost is low. The process of the invention has great adaptability to raw materials, can not only treat intermediate materials containing arsenic, lead, antimony and bismuth, but also can treat copper concentrate containing low-sulfur and high arsenic, high lead and high antimony, and has satisfactory removal capability to V group element impurities harmful to crude copper smelting, and has considerable removal effect to lead, antimony, bismuth and even tin except arsenic. The sulfidation reduction roasting process is an ideal method for the material pretreatment process of the blister copper direct smelting method.
Detailed Description
The present invention will be described in further detail with reference to examples.
Example 1
47 percent of copper-zinc-cobalt material
Low sulfur vulcanizing agent chalcocite 47%
6 percent of coke powder of carbonaceous material
The above-mentioned percentages are mass percentages,
the mass ratio of copper to sulfur of the low-sulfur vulcanizing agent chalcocite is preferably more than 2. Then, the material is ball-milled and crushed by a ball mill, and the particles are as fine as possible in principle, and the ball milling is generally performed at about 100 meshes. And then selecting a binding agent, wherein water is preferably used, humidifying and granulating, the particle size can be adapted to a roasting furnace in principle, and no special requirement is needed, but the particle diameter is controlled within the range of 3-6mm in order to take reaction effect and granulation cost into consideration. At 800 deg.c, sulfurizing, reducing and roasting in a rotary kiln with non-oxidizing atmosphere for 1.5-2.5 hr, preferably 2 hr. The roasted calcine is used for new smelting method.
The chemical process mainly comprises the following steps:
the arsenic in the Cu-Zn-Co material exists mostly in the form of copper arsenate, which is chemically decomposed during roasting
Reduction of copper oxide to copper by carbon or carbon monoxide in the presence of a reducing agent such as coke powder
Meanwhile, the chalcocite decomposes sulfur vapor under the reducing atmosphere and combines with copper to generate stable Cu2S, preventing the subsequent arsenic from combining with metallic copper, and arsenic is selected from arsenic trioxide or arsenic vaporThe morphology is volatilized and removed.
The method consumes reducing agent coke powder, the added vulcanizing agent chalcocite is a copper raw material of the company, the main consumption is heavy oil consumption of the rotary kiln, and therefore the smelting cost is low.
Example 2
48 percent of copper-zinc-cobalt material
Low sulfur vulcanizing agent chalcocite 48%
4 percent of carbonaceous material coal powder
The above-mentioned percentages are mass percentages,
the roasting temperature is controlled to be 800 ℃,
otherwise as in example 1
Example 3
46 percent of copper, zinc and cobalt material
46 percent of low-sulfur vulcanizing agent chalcocite
8 percent of carbonaceous material coal powder
The above-mentioned percentages are mass percentages,
the roasting temperature is controlled to be 800 ℃,
otherwise as in example 1
Example 4
58 percent of copper-zinc-cobalt material
36 percent of low-sulfur vulcanizing agent chalcocite
6 percent of carbonaceous material coal powder
The above-mentioned percentages are mass percentages,
the roasting temperature is controlled to be 700 ℃,
otherwise as in example 1
Example 5
36 percent of copper, zinc and cobalt materials
58 percent of low-sulfur vulcanizing agent chalcocite
6 percent of carbonaceous material coal powder
The above-mentioned percentages are mass percentages,
the roasting temperature is controlled at 900 ℃,
otherwise as in example 1
Example 6
52 percent of copper-zinc-cobalt material
Low-sulfur vulcanizing agent chalcocite 42%
6 percent of coke powder of carbonaceous material
The above-mentioned percentages are mass percentages,
the roasting temperature is controlled to be 800 ℃,
otherwise as in example 1
Example 7
42 percent of copper-zinc-cobalt material
Low-sulfur vulcanizing agent chalcocite 52%
6 percent of carbonaceous material coal powder
The above-mentioned percentages are masspercentages,
the roasting temperature is controlled to be 800 ℃,
otherwise as in example 1
Claims (8)
1. A method for removing arsenic by sulfurization reduction roasting volatilization of copper-zinc-cobalt material is characterized in that:
36 to 58 percent of copper-zinc-cobalt material
36 to 58 percent of low-sulfur vulcanizing agent chalcocite
2 to 10 percent of carbonaceous material
The components are mixed according to the mass percentage,
after being crushed, the materials are mixed evenly for granulation, and then the vulcanization reduction roasting is carried out at the temperature of 700-900 ℃, and the time of the vulcanization reduction roasting is controlled to be 1.5-2.5 hours.
2. The method of claim 1, wherein the mixture ratio of the copper-zinc-cobalt material, the low-sulfur vulcanizing agent chalcocite and the carbonaceous material is 46-48%, 46-48% and 4-8%.
3. The method of claim 1, wherein said granulating is carried out by moistening with water and granulating.
4. A method according to claim 3, characterized in that the particles have a diameter of 3-6 mm.
5. The method of claim 1, wherein the sulfido-reduction roasting is performed in a rotary kiln.
6. The method of claim 1, wherein the sulfido-reductive roasting time iscontrolled to be 2 hours.
7. The method of claim 1 wherein the carbonaceous material is coal fines or coke fines.
8. The method of claim 1, wherein the temperature is 800 degrees.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB021105715A CN1156588C (en) | 2002-01-16 | 2002-01-16 | Sulfurizing reduction and roasting and voltizing dearsenication method for copper-zine-cobalt material |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB021105715A CN1156588C (en) | 2002-01-16 | 2002-01-16 | Sulfurizing reduction and roasting and voltizing dearsenication method for copper-zine-cobalt material |
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| Publication Number | Publication Date |
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| CN1377979A CN1377979A (en) | 2002-11-06 |
| CN1156588C true CN1156588C (en) | 2004-07-07 |
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| CNB021105715A Expired - Fee Related CN1156588C (en) | 2002-01-16 | 2002-01-16 | Sulfurizing reduction and roasting and voltizing dearsenication method for copper-zine-cobalt material |
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Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103468932A (en) * | 2013-08-25 | 2013-12-25 | 云南锡业集团有限责任公司研究设计院 | Method for removing antimony from high-antimony copper concentrate |
| CN103952563A (en) * | 2014-04-25 | 2014-07-30 | 云南锡业集团有限责任公司研究设计院 | Method for removing arsenic from white smoke |
| CN106367602B (en) * | 2016-09-13 | 2018-07-24 | 昆明理工大学 | A kind of method that high-arsenic antimony flue dust vulcanization detaches arsenic and recycles antimony |
| CN106756113B (en) * | 2016-12-29 | 2018-09-07 | 湖南工业大学 | A kind of method that arsenic sulfide slag reduction sulphur fixing roast directly produces metallic arsenic |
| CN106756112B (en) * | 2016-12-29 | 2018-09-07 | 湖南工业大学 | A kind of method that heavy arsenic slag reduction sulphur fixing roast directly produces metallic arsenic |
| CN110819810B (en) * | 2019-11-21 | 2021-07-06 | 株洲冶炼集团股份有限公司 | Comprehensive recovery method for purifying cobalt-nickel slag by zinc hydrometallurgy arsenic salt |
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