CN113584313B - Method for producing coarse copper powder from high-arsenic copper bismuth slag - Google Patents

Method for producing coarse copper powder from high-arsenic copper bismuth slag Download PDF

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CN113584313B
CN113584313B CN202110858611.XA CN202110858611A CN113584313B CN 113584313 B CN113584313 B CN 113584313B CN 202110858611 A CN202110858611 A CN 202110858611A CN 113584313 B CN113584313 B CN 113584313B
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arsenic
bismuth
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bismuth slag
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CN113584313A (en
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邓远久
韩朝云
丁旭
田惟维
吴红林
胡如忠
任晓
王宝龙
郭德燕
侯刚
魏源
张小丽
沈林丽
李月梅
杨华
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Yunnan Chihong Resources Comprehensive Utilization Co ltd
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    • C22B7/007—Wet processes by acid leaching
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    • C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
    • C22B7/04—Working-up slag
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Abstract

The invention relates to a method for producing coarse copper powder from high-arsenic copper bismuth slag, which belongs to the technical field of metallurgy and specifically comprises the following steps: 1) Pretreatment: ball-milling the raw material high-arsenic copper bismuth slag for later use; 2) Alkaline leaching: obtaining sodium arsenate leachate and arsenic-removed copper-bismuth slag; 3) And (3) arsenic precipitation: obtaining alkali liquor and calcium arsenate slag; 4) Acid leaching: obtaining copper sulfate leaching liquid and copper removal slag; 5) And (3) replacement: adding zinc powder into the copper sulfate leaching solution obtained in the step 4) to react to obtain crude copper powder and a zinc sulfate solution. The invention firstly carries out dearsenification treatment on the high-arsenic copper bismuth slag to obtain the calcium arsenate slag which can be safely buried without causing pollution. And the copper-bismuth slag after dearsenification is subjected to acid leaching in sulfuric acid, and finally, zinc powder is added to generate coarse copper powder and a zinc sulfate solution through a displacement reaction, so that the coarse copper powder is directly obtained, the process is short in flow, the leaching rate of copper is high, flow materials can be effectively recycled, and valuable metals of the copper-bismuth slag can be rapidly recycled.

Description

Method for producing coarse copper powder from high-arsenic copper bismuth slag
Technical Field
The invention belongs to the technical field of nonferrous metallurgy, and particularly relates to a method for producing coarse copper powder from high-arsenic copper bismuth slag.
Background
The copper-bismuth slag is one of valuable slag produced in the precious metal metallurgy process, is rich in copper, bismuth, silver and lead, has high value, and is researched by production enterprises in a dispute on recycling of the copper-bismuth slag. In the process of treating the copper-bismuth slag, due to the existence of arsenic, regardless of a pyrogenic process or a wet process, arsenic can bring great pollution to the environment in the process of treating the anode slime, so that the flow becomes complicated, the quality of other comprehensive utilization products is influenced, and in addition, the dearsenification is more and more emphasized due to the continuous improvement of the current environmental protection requirement. The pyrogenic process for treating the lead anode slime is simple in process, but generates a large amount of arsenic-antimony smoke dust, causes great harm to the environment, and is very difficult to recycle.
The patent of application No. 201510138800.4 discloses a method for producing copper sulfate from copper-bismuth slag, which comprises the steps of crushing and grinding, oxygen pressure leaching, iron removal, calcium and magnesium removal and concentrated crystallization to produce a copper sulfate pentahydrate product. Although the technology can recover copper, dearsenification cannot be carried out, and the recovered product is copper sulfate pentahydrate, so that crude copper powder cannot be recovered.
The patent application No. 201610990078.1 discloses a process for selectively and efficiently extracting copper and bismuth from high-copper bismuth slag, which comprises crushing, grinding, high-pressure oxygen leaching, cyclone electrolysis of leachate to produce electrocopper, leaching with concentrated hydrochloric acid to separate bismuth, electrodepositing to obtain sponge bismuth, and refining to obtain refined bismuth. The technique also fails to remove arsenic and the product is electrolytic copper and refined bismuth, not coarse copper powder.
The process flow disclosed by the patent does not remove arsenic from the copper-bismuth slag, so that certain environmental protection risks exist, the process flow is long, the coarse copper powder cannot be directly obtained finally, the cost is high, and valuable metal copper in the copper-bismuth slag cannot be quickly recovered and reproduced.
Disclosure of Invention
In order to overcome the problems in the background art, the invention provides a method for producing crude copper powder from high-arsenic copper-bismuth slag, which can be used for dearsenifying the high-arsenic copper-bismuth slag and reducing arsenic pollution, can directly obtain the crude copper powder, has short process flow, high leaching rate of copper and can effectively recover process materials and quickly recover valuable metals from the copper-bismuth slag.
In order to realize the purpose, the invention is realized by the following technical scheme:
a method for producing coarse copper powder from high-arsenic copper bismuth slag specifically comprises the following steps:
1) Pretreatment: ball-milling the raw material high arsenic copper bismuth slag for later use;
2) Alkaline leaching: adding the copper-bismuth slag obtained in the step 1) into a leaching tank, adding a sodium hydroxide solution with the liquid-solid volume ratio of 4-8 times, introducing ozone for reaction for 5-10 h at the temperature of 60-90 ℃ under normal pressure, and performing filter pressing for liquid-solid separation to obtain a sodium arsenate leaching solution and arsenic-removed copper-bismuth slag;
3) Precipitating arsenic: adding calcium hydroxide into the sodium arsenate leaching solution obtained in the step 2) at the temperature of 60-80 ℃ under normal pressure for reaction for 2-4 h, and performing filter pressing for liquid-solid separation to obtain alkali liquor and calcium arsenate residues;
4) Acid leaching: adding the arsenic-removed copper-bismuth slag obtained in the step 2) into a sulfuric acid solution with the liquid-solid volume ratio of 4-6 times, introducing ozone for reaction for 8-24 h at the temperature of 50-60 ℃ under normal pressure, and performing filter pressing for liquid-solid separation to obtain a copper sulfate leaching solution and copper-removed slag;
5) Replacement: adding zinc powder into the copper sulfate leaching solution obtained in the step 4) at the temperature of 70-90 ℃ under normal pressure to react for 0.5-2 h, and after the pH value at the displacement end point is 4-5 and is stabilized for 0.5-1 h, carrying out centrifugal filtration to carry out liquid-solid separation to obtain crude copper powder and a zinc sulfate solution.
Further, in the step 1), the copper-bismuth slag contains 15-45% of copper, 15-20% of bismuth, 1-3% of arsenic, 4-7% of silver and 20-30% of lead.
Further, in the step 1), the ball milling particle size of the copper-bismuth slag is less than 100 meshes.
Further, in the step 2), the content of the sodium hydroxide is more than or equal to 98.5 percent, and the content of the sodium hydroxide in the sodium hydroxide solution is 100-150 g/L.
Further, in the step 3), the content of calcium hydroxide is more than or equal to 95 percent, and the dosage of the calcium hydroxide is 1.1 to 1.4 times of the theoretical value.
Further, in the step 2) and the step 4), ozone is supplied from an ozone generator at a supply amount of 30 to 60g/h and a concentration of 70 to 100mg/L.
Further, in the step 4), the sulfuric acid content is more than or equal to 98 percent, and the sulfuric acid content of the sulfuric acid solution is 100-150 g/L.
Further, in the step 5), the total zinc is more than or equal to 98 percent, the metal zinc is more than or equal to 96 percent, the granularity of the zinc powder is 50-80 meshes, and the dosage of the zinc powder is 1.1-1.3 times of the theoretical value.
The invention has the beneficial effects that:
according to the invention, the high-arsenic copper bismuth slag is subjected to dearsenization treatment to obtain calcium arsenate slag, the leaching concentration of any one harmful component in the calcium arsenate slag is lower than the regulation of GB 5085.3-2007 hazardous waste identification Standard-leaching toxicity identification, the slag can be safely buried, pollution is not caused, and no environmental protection risk exists. And the acid leaching is carried out on the arsenic-removed copper-bismuth slag in sulfuric acid, the disproportionation reaction of Cu2O is carried out during the sulfuric acid leaching, ozone is introduced, so that the copper generated by the disproportionation reaction can be continuously oxidized into copper oxide to be leached by the sulfuric acid, besides, cuprous oxide can be oxidized into copper oxide to be leached, finally, zinc powder is added to carry out displacement reaction with a copper sulfate solution to generate copper powder and a zinc sulfate solution, so that the crude copper powder is directly obtained, the process is short, the leaching rate of copper is high, the process materials can be effectively recycled, and valuable metals of the copper-bismuth slag can be rapidly recycled.
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FIG. 1 is a process flow diagram of the present invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, preferred embodiments of the present invention will be described in detail below to facilitate understanding of the skilled person.
A method for producing coarse copper powder from high-arsenic copper-bismuth slag specifically comprises the following steps:
1) Pretreatment: ball-milling the raw material high-arsenic copper bismuth slag for standby, wherein the high-arsenic copper bismuth slag contains 15-45% of copper, 15-25% of bismuth, 10-30% of arsenic, 4-8% of silver and 15-30% of lead, and the ball-milling particle size of the copper bismuth slag is smaller than 100 meshes.
2) Alkaline leaching: adding the copper-bismuth slag obtained in the step 1) into a leaching tank, adding a sodium hydroxide solution with the liquid-solid volume ratio of 4-8 times, introducing ozone at the temperature of 60-90 ℃ under normal pressure for reaction for 5-10 h, and performing filter pressing for liquid-solid separation to obtain a sodium arsenate leaching solution and arsenic-removed copper-bismuth slag, wherein the ozone is supplied by an ozone generator, the supply amount is 30-60 g/h, and the concentration is 70-100 mg/L; the content of the sodium hydroxide is more than or equal to 98.5 percent, and the content of the sodium hydroxide in the sodium hydroxide solution is 100-150 g/L.
3) And (3) arsenic precipitation: adding calcium hydroxide into the sodium arsenate leachate obtained in the step 2) at the temperature of 60-80 ℃ under normal pressure for reaction for 2-4 h, and performing filter pressing for liquid-solid separation to obtain an alkali liquor and calcium arsenate slag, wherein the content of the calcium hydroxide is more than or equal to 95%, and the dosage of the calcium hydroxide is 1.1-1.4 times of the theoretical value.
4) Acid leaching: adding the arsenic-removed copper-bismuth slag obtained in the step 2) into a sulfuric acid solution with the liquid-solid volume ratio of 4-6 times, wherein the sulfuric acid content is not less than 98%, and the sulfuric acid content of the sulfuric acid solution is 100-150 g/L. Under the normal pressure and the temperature of 50-60 ℃, ozone is introduced to react for 8-24 h, the ozone is supplied by an ozone generator, the supply amount is 30-60 g/h, the concentration is 70-100 mg/L, copper in the copper bismuth slag mainly exists in a cuprous oxide form, the ozone with the parameter amount is introduced, the relative density of the ozone is 1.5 times that of oxygen, the solubility in water is 10 times that of oxygen, the reaction activity is strong, the property is more active than oxygen, the reaction time is 50% of oxygen, the reaction time can be saved, the efficiency is greatly improved, the production cost is reduced, meanwhile, a large amount of heat is emitted during the ozone reaction, the heating energy consumption can be reduced, in addition, the ozone preparation process is simple, the ozone is generally produced and used on site, the storage is not needed, the ozone preparation process is more convenient, and the leaching rate of the copper can be maximized. And finally, carrying out filter pressing and liquid-solid separation to obtain a copper sulfate leaching solution and decoppered slag.
5) Replacement: adding zinc powder into the copper sulfate leaching solution obtained in the step 4) at the temperature of 70-80 ℃ under normal pressure to react for 0.5-2 h, wherein the specification of the zinc powder is as follows: more than or equal to 98 percent of total zinc, more than or equal to 96 percent of metal zinc, 50 to 80 meshes of zinc powder granularity, 1.1 to 1.3 times of the theoretical value of the zinc powder, 4 to 5 of the pH value of the replacement end point, and after 0.5 to 1 hour of stabilization, the solution is centrifugally filtered to carry out liquid-solid separation to obtain crude copper powder and zinc sulfate solution.
As a result:
the obtained calcium arsenate slag comprises the following components: 40 to 50 percent of calcium oxide, 28 to 32 percent of arsenic, 6 to 8g/t of copper, 5 to 7g/t of bismuth, 0.4 to 0.8g/t of silver and 3 to 5g/t of lead. The leaching concentration of any hazardous component is lower than the regulation of GB 5085.3-2007 identification Standard for hazardous waste-identification of leaching toxicity, and the hazardous component can be safely buried.
The obtained crude copper powder comprises the following components: 85 to 90 percent of copper, 200 to 400g/t of bismuth, 0.1 to 1.0 percent of arsenic, 500 to 1000g/t of silver and 1 to 2 percent of lead.
The obtained zinc sulfate solution comprises the following components: zinc 70-100 g/L, copper 0.2-0.4 mg/L, bismuth 0.01-0.03 mg/L, arsenic 20-50 mg/L, silver 0.01-0.03 mg/L, lead 50-55 mg/L.
The leaching rate of copper is as follows: 78 to 88 percent
The working mechanism of the invention is as follows:
the arsenic content in the high-arsenic copper bismuth slag is large, the high-arsenic copper bismuth slag is harmful, and the environment is easy to pollute, so that before copper is leached, the high-arsenic copper bismuth slag is subjected to dearsenification treatment, the high-arsenic copper bismuth slag is added into a sodium hydroxide solution, and ozone is introduced. As arsenic is oxidized to arsenic trioxide and arsenic pentoxide at high temperature. When ozone is introduced, arsenic and ozone generate oxidation reaction to generate arsenic trioxide, as shown in formula (1), and the added sodium hydroxide respectively reacts with the arsenic trioxide and the arsenic pentoxide to generate sodium arsenate, as shown in formulas (2) and (3); adding calcium hydroxide, sodium arsenate and calcium hydroxide to perform a displacement reaction to generate calcium arsenate as shown in a formula (4);
after dearsenification is finished, dearsenified copper bismuth slag is obtained, because copper can be oxidized into Cu during high-temperature blowing 2 O, therefore, cu 2 Leaching of O in sulphuric acidDisproportionation reaction occurs, as shown in formula (5), the generated metal copper does not react with dilute sulfuric acid under the condition that no oxidant exists, and the copper generated by the reaction is wrapped on the surface of the mineral to further hinder the leaching of copper-bismuth slag. Under the condition of ozone introduction, the copper generated by the disproportionation reaction can be continuously oxidized into copper oxide, so that the copper oxide is leached by sulfuric acid, as shown in formulas (6) and (7); in addition, cuprous oxide is also oxidized to cupric oxide and leached as shown in (8) and (9), and finally, zinc powder is charged to cause a substitution reaction with a copper sulfate solution to produce copper powder and a zinc sulfate solution as shown in (10).
2As+O 3 = As 2 O 3 （1）
As 2 O 3 ﹢6NaOH﹢O 2 =2 Na 3 AsO 4 ﹢3H 2 O （2）
As 2 O 5 ﹢6NaOH=2 Na 3 AsO 4 ﹢3H 2 O （3）
3Na 3 AsO 4 +3Ca（OH） 2 =2Ca 3 （AsO 4 ） 2 +6NaOH （4）
Cu 2 O+H 2 SO 4 =CuSO 4 +Cu+H 2 O （5）
3Cu+O 3 =3CuO （6）
Cu+H 2 SO 4 =CuSO 4 +H 2 O （7）
2Cu 2 O+O 3 =4CuO （8）
CuO+H 2 SO 4 =CuSO 4 +H 2 O （9）
Zn+CuSO 4 =ZnSO 4 +Cu （10）
Example 1
1) Pretreatment: ball-milling the raw material high-arsenic copper bismuth slag for later use, wherein the high-arsenic copper bismuth slag contains 15% of copper, 25% of bismuth, 10% of arsenic, 8% of silver and 15% of lead, and the ball-milling particle size of the copper bismuth slag is smaller than 100 meshes.
2) Alkaline leaching: adding the copper-bismuth slag obtained in the step 1) into a leaching tank, adding a sodium hydroxide solution with the liquid-solid volume ratio of 8 times, introducing ozone for reaction for 5 hours at the temperature of 90 ℃ under normal pressure, and performing filter pressing for liquid-solid separation to obtain a sodium arsenate leaching solution and arsenic-removed copper-bismuth slag, wherein the ozone is supplied by an ozone generator, the supply amount is 60g/h, and the concentration is 100mg/L; the content of the sodium hydroxide is more than or equal to 98.5 percent, and the content of the sodium hydroxide in the sodium hydroxide solution is 100g/L.
3) Precipitating arsenic: and 3) adding calcium hydroxide into the sodium arsenate leachate obtained in the step 2) at the temperature of 80 ℃ under normal pressure for reaction for 4 hours, and performing pressure filtration and liquid-solid separation to obtain an alkali liquor and calcium arsenate residues, wherein the content of calcium hydroxide is more than or equal to 95%, and the dosage of calcium hydroxide is 1.1 times of the theoretical value.
4) Acid leaching: adding the arsenic-removed copper-bismuth slag obtained in the step 2) into a sulfuric acid solution with the liquid-solid volume ratio of 6 times, wherein the sulfuric acid content is not less than 98%, and the sulfuric acid content of the sulfuric acid solution is 150g/L. Introducing ozone at 60 deg.C under normal pressure for reaction for 8 hr, supplying ozone with 60 g/hr and 100mg/L concentration by ozone generator, and press-filtering for liquid-solid separation to obtain copper sulfate leachate and copper-removed residue.
5) And (3) replacement: adding zinc powder into the copper sulfate leaching solution obtained in the step 4) at the temperature of 80 ℃ under normal pressure to react for 0.5, wherein the specification of the zinc powder is as follows: the total zinc is more than or equal to 98 percent, the metal zinc is more than or equal to 96 percent, the granularity of the zinc powder is 80 meshes, the using amount of the zinc powder is 1.3 times of the theoretical value, the pH value of the displacement end point is 4, and after the zinc powder is stabilized for 0.5h, the crude copper powder and the zinc sulfate solution are obtained by centrifugal filtration and liquid-solid separation.
As a result:
the obtained calcium arsenate slag comprises the following components: the alloy contains 40 percent of calcium oxide, 28 percent of arsenic, 6g/t of copper, 7g/t of bismuth, 0.8g/t of silver and 3g/t of lead.
The crude copper powder comprises the following components: 85% of copper, 400g/t of bismuth, 0.1% of arsenic, 1000g/t of silver and 2% of lead.
The zinc sulfate solution comprises the following components: 100g/L of zinc, 0.2mg/L of copper, 0.03mg/L of bismuth, 20mg/L of arsenic, 0.03mg/L of silver and 50mg/L of lead.
The leaching rate of copper is as follows: 78 percent of
Example 2
1) Pretreatment: the raw material high-arsenic copper bismuth slag is ball-milled for standby, the high-arsenic copper bismuth slag contains 30% of copper, 22.5% of bismuth, 20% of arsenic, 6% of silver and 22.5% of lead, and the ball-milling particle size of the copper bismuth slag is smaller than 100 meshes.
2) Alkaline leaching: adding the copper-bismuth slag obtained in the step 1) into a leaching tank, adding a sodium hydroxide solution with the liquid-solid volume ratio of 6 times, introducing ozone for reaction for 7.5 hours at the temperature of 75 ℃ under normal pressure, and performing pressure filtration for liquid-solid separation to obtain a sodium arsenate leaching solution and arsenic-removed copper-bismuth slag, wherein the ozone is supplied by an ozone generator, the supply amount is 45g/h, and the concentration is 85mg/L; the content of the sodium hydroxide is more than or equal to 98.5 percent, and the content of the sodium hydroxide in the sodium hydroxide solution is 125g/L.
3) And (3) arsenic precipitation: and 3) adding calcium hydroxide into the sodium arsenate leachate obtained in the step 2) at the temperature of 70 ℃ under normal pressure for reaction for 3 hours, and performing pressure filtration and liquid-solid separation to obtain an alkali liquor and calcium arsenate residues, wherein the content of calcium hydroxide is more than or equal to 95%, and the dosage of calcium hydroxide is 1.25 times of the theoretical value.
4) Acid leaching: adding the arsenic-removed copper-bismuth slag obtained in the step 2) into a sulfuric acid solution with the liquid-solid volume ratio of 5 times, wherein the sulfuric acid content is not less than 98%, and the sulfuric acid content of the sulfuric acid solution is 125g/L. Introducing ozone at 55 deg.C under normal pressure for reaction for 16h, supplying ozone from ozone generator at a supply amount of 45g/h and a concentration of 85mg/L, and press-filtering for liquid-solid separation to obtain copper sulfate leachate and copper-removed residue.
5) And (3) replacement: adding zinc powder into the copper sulfate leaching solution obtained in the step 4) to react for 1.25h at the temperature of 75 ℃ under normal pressure, wherein the specification of the zinc powder is as follows: the total zinc is more than or equal to 98 percent, the metal zinc is more than or equal to 96 percent, the granularity of the zinc powder is 65 meshes, the using amount of the zinc powder is 1.2 times of the theoretical value, the pH value of the displacement end point is 4.5, and after the zinc powder is stabilized for 0.75h, the solution is centrifugally filtered and subjected to liquid-solid separation to obtain crude copper powder and zinc sulfate solution.
As a result:
the obtained calcium arsenate slag comprises the following components: contains 45 percent of calcium oxide, 30 percent of arsenic, 7g/t of copper, 6g/t of bismuth, 0.6g/t of silver and 4g/t of lead.
The crude copper powder comprises the following components: 87.5 percent of copper, 300g/t of bismuth, 0.55 percent of arsenic, 750g/t of silver and 1.5 percent of lead.
The zinc sulfate solution comprises the following components: the zinc sulfate solution comprises the following components: 85g/L of zinc, 0.3mg/L of copper, 0.02mg/L of bismuth, 35mg/L of arsenic, 0.02mg/L of silver and 52.5mg/L of lead.
The leaching rate of copper is as follows: 83 percent
Example 3
1) Pretreatment: ball-milling the raw material high-arsenic copper bismuth slag for later use, wherein the high-arsenic copper bismuth slag contains 45% of copper, 15% of bismuth, 30% of arsenic, 4% of silver and 30% of lead, and the ball-milling particle size of the copper bismuth slag is smaller than 100 meshes.
2) Alkaline leaching: adding the copper-bismuth slag obtained in the step 1) into a leaching tank, adding a sodium hydroxide solution with the liquid-solid volume ratio of 4 times, introducing ozone for reaction for 10 hours at the temperature of 60 ℃ under normal pressure, and performing filter pressing for liquid-solid separation to obtain a sodium arsenate leaching solution and arsenic-removed copper-bismuth slag, wherein the ozone is supplied by an ozone generator, the supply amount is 30g/h, and the concentration is 70mg/L; the content of the sodium hydroxide is more than or equal to 98.5 percent, and the content of the sodium hydroxide in the sodium hydroxide solution is 150g/L.
3) And (3) arsenic precipitation: adding calcium hydroxide into the sodium arsenate leachate obtained in the step 2) at the temperature of 60 ℃ under normal pressure for reaction for 4 hours, and performing pressure filtration and liquid-solid separation to obtain an alkali liquor and calcium arsenate slag, wherein the content of the calcium hydroxide is more than or equal to 95%, and the dosage of the calcium hydroxide is 1.4 times of the theoretical value.
4) Acid leaching: adding the arsenic-removed copper-bismuth slag obtained in the step 2) into a sulfuric acid solution with the liquid-solid volume ratio of 4 times, wherein the sulfuric acid content is more than or equal to 98%, and the sulfuric acid content of the sulfuric acid solution is 100g/L. Introducing ozone at 50 deg.C under normal pressure for reaction for 24 hr, supplying ozone with 30 g/hr and 70mg/L concentration by ozone generator, and press-filtering for liquid-solid separation to obtain copper sulfate leachate and copper-removed residue.
5) And (3) replacement: adding zinc powder into the copper sulfate leaching solution obtained in the step 4) at the temperature of 70 ℃ under normal pressure for reacting for 2 hours, wherein the specification of the zinc powder is as follows: more than or equal to 98 percent of total zinc, more than or equal to 96 percent of metal zinc, 50-mesh granularity of zinc powder, 1.1 times of the theoretical value of the dosage of the zinc powder, 5 pH value of the displacement end point, and after 1 hour of stabilization, carrying out centrifugal filtration to carry out liquid-solid separation to obtain crude copper powder and zinc sulfate solution.
As a result:
the obtained calcium arsenate slag comprises the following components: 50% of calcium oxide, 32% of arsenic, 8g/t of copper, 5g/t of bismuth, 0.4g/t of silver and 5g/t of lead.
The crude copper powder comprises the following components: 90% of copper, 200g/t of bismuth, 1.0% of arsenic, 500g/t of silver and 1.0% of lead.
The zinc sulfate solution comprises the following components: 90 percent of copper, 200g/t of bismuth, 1.0 percent of arsenic, 500g/t of silver and 1.0 percent of lead.
The leaching rate of copper is as follows: 88 percent
Finally, it is noted that the above-mentioned preferred embodiments illustrate rather than limit the invention, and that, although the invention has been described in detail with reference to the above-mentioned preferred embodiments, it will be understood by those skilled in the art that various changes in form and detail may be made therein without departing from the scope of the invention as defined by the appended claims.

Claims (7)

1. A method for producing coarse copper powder from high-arsenic copper bismuth slag is characterized by comprising the following steps: the method specifically comprises the following steps:
1) Pretreatment: ball-milling the raw material high arsenic copper bismuth slag for later use;
2) Alkaline leaching: adding the copper-bismuth slag obtained in the step 1) into a leaching tank, adding a sodium hydroxide solution with the liquid-solid volume ratio of 4-8 times, introducing ozone at the temperature of 60-90 ℃ under normal pressure for reaction for 5-10 h, and performing filter pressing for liquid-solid separation to obtain a sodium arsenate leaching solution and arsenic-removed copper-bismuth slag; wherein the ozone is supplied by an ozone generator, the supply amount is 30-60 g/h, and the concentration is 70-100 mg/L;
3) And (3) arsenic precipitation: adding calcium hydroxide into the sodium arsenate leaching solution obtained in the step 2) at the temperature of 60-80 ℃ under normal pressure for reaction for 2-4 h, and performing filter pressing for liquid-solid separation to obtain alkali liquor and calcium arsenate residues;
4) Acid leaching: adding the arsenic-removed copper-bismuth slag obtained in the step 2) into a sulfuric acid solution with the liquid-solid volume ratio of 4-6 times, introducing ozone at the temperature of 50-60 ℃ under normal pressure for reaction for 8-24 h, wherein the ozone is supplied by an ozone generator, the supply amount is 30-60 g/h, and the concentration is 70-100 mg/L; then carrying out filter pressing and liquid-solid separation to obtain a copper sulfate leaching solution and decoppered slag;
5) And (3) replacement: adding zinc powder into the copper sulfate leaching solution obtained in the step 4) at the temperature of 70-80 ℃ under normal pressure to react for 0.5-2 h, and after the pH value at the displacement end point is 4-5 and is stabilized for 0.5-1 h, carrying out centrifugal filtration to carry out liquid-solid separation to obtain crude copper powder and a zinc sulfate solution.
2. The method for producing the coarse copper powder from the high-arsenic copper-bismuth slag according to claim 1, which is characterized by comprising the following steps of: in the step 1), the copper-bismuth slag contains 15-45% of copper, 15-20% of bismuth, 1-3% of arsenic, 4-7% of silver and 20-30% of lead.
3. The method for producing the coarse copper powder from the high-arsenic copper bismuth slag according to claim 1 or 2, which is characterized in that: in the step 1), the ball milling particle size of the copper-bismuth slag is less than 100 meshes.
4. The method for producing the coarse copper powder from the high-arsenic copper bismuth slag according to claim 1, which is characterized by comprising the following steps of: in the step 2), the content of the sodium hydroxide is more than or equal to 98.5 percent, and the content of the sodium hydroxide in the sodium hydroxide solution is 100-150 g/L.
5. The method for producing the coarse copper powder from the high-arsenic copper bismuth slag according to claim 1, which is characterized by comprising the following steps of: in the step 3), the content of the calcium hydroxide is more than or equal to 95 percent, and the dosage of the calcium hydroxide is 1.1 to 1.4 times of the theoretical value.
6. The method for producing the coarse copper powder from the high-arsenic copper-bismuth slag according to claim 1, which is characterized by comprising the following steps of: in the step 4), the sulfuric acid content is more than or equal to 98 percent, and the sulfuric acid content of the sulfuric acid solution is 100-150 g/L.
7. The method for producing the coarse copper powder from the high-arsenic copper-bismuth slag according to claim 1, which is characterized by comprising the following steps of: in the step 5), the total zinc is more than or equal to 98 percent, the metal zinc is more than or equal to 96 percent, the granularity of the zinc powder is 50-80 meshes, and the dosage of the zinc powder is 1.1-1.3 times of the theoretical value.
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CA2002489C (en) * 1989-11-08 1999-01-12 Daniel A. D. Boateng Process for the manufacture of copper arsenate
CN1156589C (en) * 2002-01-14 2004-07-07 史汉祥 Dearsenifying method for Cu-Zn-Co material
CN104762483B (en) * 2015-03-27 2017-09-29 云南驰宏锌锗股份有限公司 A kind of method that copper bismuth slag produces copper sulphate
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