CN111961852A - Method for deeply removing selenium in zinc sulfate solution - Google Patents
Method for deeply removing selenium in zinc sulfate solution Download PDFInfo
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- CN111961852A CN111961852A CN202011033373.0A CN202011033373A CN111961852A CN 111961852 A CN111961852 A CN 111961852A CN 202011033373 A CN202011033373 A CN 202011033373A CN 111961852 A CN111961852 A CN 111961852A
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- zinc sulfate
- sulfate solution
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/20—Treatment or purification of solutions, e.g. obtained by leaching
- C22B3/44—Treatment or purification of solutions, e.g. obtained by leaching by chemical processes
- C22B3/46—Treatment or purification of solutions, e.g. obtained by leaching by chemical processes by substitution, e.g. by cementation
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B19/00—Obtaining zinc or zinc oxide
- C22B19/32—Refining zinc
Abstract
The invention belongs to the field of zinc hydrometallurgy, and particularly discloses a method for deeply removing selenium in a zinc sulfate solution, which comprises the steps of (1) preparing alloy powder, (2) replacing, (3) heating under reduced pressure, and (4) filtering and removing slag; the metal powder comprises Mn, Ag, Pt, Re, Bi and Au; the selenium removing method disclosed by the invention has the advantages of short flow, no special requirements on equipment, mild reaction, low selenium removing cost and good selenium removing effect.
Description
Technical Field
The invention belongs to the field of zinc hydrometallurgy, and particularly discloses a method for deeply removing selenium in a zinc sulfate solution.
Background
The zinc hydrometallurgy of zinc refers to a process of dissolving zinc in zinc calcine or other zinc sulfide materials and zinc in zinc sulfide concentrate in water solution and extracting metallic zinc or zinc compounds from the zinc calcine or other zinc sulfide materials and zinc sulfide concentrate, and is a main method of modern zinc smelting. Consists of three large links of zinc leaching, purification from zinc solution and zinc electrolytic deposition. The zinc hydrometallurgy mainly comprises the working procedures of roasting, leaching, leachate purification, electrodeposition and the like. After roasting, the zinc concentrate is subjected to neutral leaching by using electrolytic waste liquid to dissolve most of zinc oxide, and supernatant and underflow ore pulp are separated from the obtained ore pulp. And (4) after the supernatant is purified, electrodepositing to produce metal zinc, and casting into ingots. The supernatant is zinc sulfate solution, which contains a certain amount of selenium, and the electrode potential of the zinc sulfate solution is more positive than that of zinc, so that the zinc sulfate solution is harmful to the long-period electrodeposition process of more than 48 hours. Because it is a valence-variable metal, it exists in the form of ion under the condition of acidity (pH1.5-2.5), and under the condition of pH2.6-5.4, it exists in the form of zinc sulfate solution with pH 3.8-5.4 opposite to acid radical ion, and the selenium and tellurium in the solution exist in the form of acid radical ion, and it can not be removed by using conventional existent zinc powder (metal zinc powder, zinc powder electric furnace and aluminium-free alloy zinc powder) substitution method, and its other purification cost is high, so that it is not economical in industrial production. Therefore, it is urgently needed to find an efficient metal powder for replacing selenium in the zinc sulfate removing solution.
Disclosure of Invention
Based on the method, the method for deeply removing the selenium in the zinc sulfate solution is mild in reaction, low in selenium removal cost and good in selenium removal effect.
The technical scheme of the invention is as follows:
a method for deeply removing selenium in a zinc sulfate solution comprises the following steps:
(1) preparing alloy powder: mixing metals containing Mn, Ag, Pt, Re, Bi, Au and the like, adding the mixture into melting equipment for melting, controlling the temperature of the melting equipment to be 800-plus-1200 ℃, stirring and alloying, cooling, grinding the alloy into powder, and collecting the alloy powder after passing through a 100-plus-150-mesh screen;
(2) and (3) replacement: adding the alloy powder into zinc sulfate solution according to the addition of 0.2-0.5g/L, and stirring the solution for 10-20min under the ultrasonic condition by controlling the rotation speed of a stirrer to be 200-250 rpm;
(3) and (3) reduced pressure heating: placing the solution in a reaction kettle, and adding organic acid to adjust the pH value to be 3-5; closing the kettle cover, decompressing and heating, controlling the pressure to be 0.05-0.1Mpa and the temperature to be 150-;
(4) filtering and deslagging: and (3) performing pressure filtration on the solution by using a filter press to obtain filtrate for deep selenium removal.
Further, according to the method for deeply removing selenium in the zinc sulfate solution, the metals comprise the following components in parts by weight:
mn 100 parts
10-20 parts of Ag
8-16 parts of Pt
Re 5-10 parts
4 to 8 portions of Bi
And 2-4 parts of Au.
Further, in the method for deeply removing selenium from zinc sulfate solution, in the step 2, the organic acid is one or more selected from oxalic acid, maleic acid, tartaric acid and sulfamic acid.
Further, according to the method for deeply removing selenium in the zinc sulfate solution, the organic acid is a mixture of oxalic acid and tartaric acid, and the molar ratio of the oxalic acid to the tartaric acid is 2: 1.
Further, the ultrasonic condition is intermittent ultrasonic, and the ultrasonic treatment is stopped for 5s after 10 s.
Further, in the method for deeply removing selenium in the zinc sulfate solution, the content of selenium in the zinc sulfate solution in the step 2 is 0.5-3 g/L.
Further, the method for deeply removing selenium in the zinc sulfate solution comprises the following steps:
(1) preparing alloy powder: mixing metals containing Mn, Ag, Pt, Re, Bi, Au and the like, adding the mixture into melting equipment for melting, controlling the temperature of the melting equipment to be 1000 ℃, stirring and alloying, cooling, grinding the alloy into powder, and collecting the alloy powder after passing through a 120-mesh screen;
(2) and (3) replacement: adding the alloy powder into a zinc sulfate solution according to the addition of 0.35g/L, and stirring the solution for 15min under the ultrasonic condition by controlling the rotating speed of a stirrer to be 220 rpm;
(3) and (3) reduced pressure heating: placing the solution in a reaction kettle, and adding organic acid to adjust the pH value to 4; closing the kettle cover, decompressing and heating, controlling the pressure to be 0.075Mpa and the temperature to be 200 ℃, and reacting for 2 hours;
(4) filtering and deslagging: and (3) performing pressure filtration on the solution by using a filter press to obtain filtrate for deep selenium removal.
Compared with the prior art, the invention has the beneficial effects that:
the invention discloses a method for deeply removing selenium in a zinc sulfate solution, which efficiently removes the selenium in the zinc sulfate solution in a zinc hydrometallurgy process by four steps of (1) preparing alloy powder, (2) replacing, (3) heating under reduced pressure and (4) filtering and deslagging, thereby preventing the selenium from generating harm in an electrodeposition process.
Detailed Description
A method for deeply removing selenium in a zinc sulfate solution comprises the following steps:
(1) preparing alloy powder: mixing metals containing Mn, Ag, Pt, Re, Bi, Au and the like, adding the mixture into melting equipment for melting, controlling the temperature of the melting equipment to be 800-plus-1200 ℃, stirring and alloying, cooling, grinding the alloy into powder, and collecting the alloy powder after passing through a 100-plus-150-mesh screen; preferably, the metals are as follows in parts by weight:
mn 100 parts
10-20 parts of Ag
8-16 parts of Pt
Re 5-10 parts
4 to 8 portions of Bi
And 2-4 parts of Au.
(2) And (3) replacement: adding the alloy powder into zinc sulfate solution according to the addition of 0.2-0.5g/L, and stirring the solution for 10-20min under the ultrasonic condition by controlling the rotation speed of a stirrer to be 200-250 rpm; preferably, the ultrasonic condition is intermittent ultrasonic, and ultrasonic treatment is stopped for 5s after 10 s; preferably, the content of selenium in the zinc sulfate solution is 0.5-3 g/L.
(3) And (3) reduced pressure heating: placing the solution in a reaction kettle, and adding organic acid to adjust the pH value to be 3-5; closing the kettle cover, decompressing and heating, controlling the pressure to be 0.05-0.1Mpa and the temperature to be 150-; preferably, the organic acid is selected from one or more of oxalic acid, maleic acid, tartaric acid and sulfamic acid; more preferably, the organic acid is a mixture of oxalic acid and tartaric acid, and the molar ratio of the oxalic acid to the tartaric acid is 2: 1;
(4) filtering and deslagging: and (3) performing pressure filtration on the solution by using a filter press to obtain filtrate for deep selenium removal.
The technical solution of the present invention will be further described in detail with reference to specific embodiments. The following examples are merely illustrative and explanatory of the present invention and should not be construed as limiting the scope of the invention. All the technologies realized based on the above-mentioned contents of the present invention are covered in the protection scope of the present invention.
Unless otherwise indicated, the raw materials and reagents used in the following examples are all commercially available products or can be prepared by known methods.
Example 1
A method for deeply removing selenium in a zinc sulfate solution comprises the following steps:
(1) preparing alloy powder: mixing metals containing Mn, Ag, Pt, Re, Bi, Au and the like, adding the mixed metals into melting equipment for melting, controlling the temperature of the melting equipment to be 800 ℃, stirring and alloying, cooling, grinding the alloy into powder, and collecting the alloy powder after passing through a 100-mesh screen; the metal comprises the following components in parts by weight:
mn 100 parts
10 portions of Ag
Pt 8 parts
Re 5 parts
Bi 4 parts
2 parts of Au;
(2) and (3) replacement: adding the alloy powder into a zinc sulfate solution according to the addition of 0.2g/L, and stirring the solution for 10min under the ultrasonic condition by controlling the rotating speed of a stirrer to be 200 rpm; preferably, the ultrasonic condition is intermittent ultrasonic, and ultrasonic treatment is stopped for 5s after 10 s; in the zinc sulfate solution, the selenium content is 0.5 g/L;
(3) and (3) reduced pressure heating: placing the solution in a reaction kettle, and adding organic acid to adjust the pH value to 3; closing the kettle cover, heating under reduced pressure at 0.051Mpa at 150 deg.C, and reacting for 1 h; the organic acid is maleic acid;
(4) filtering and deslagging: and (3) performing pressure filtration on the solution by using a filter press to obtain filtrate for deep selenium removal.
Detection shows that the selenium content in the final filtrate is 0.98 mg/L.
Example 2
The method for deeply removing selenium in zinc sulfate solution is characterized by comprising the following steps:
(1) preparing alloy powder: mixing metals containing Mn, Ag, Pt, Re, Bi, Au and the like, adding the mixture into melting equipment for melting, controlling the temperature of the melting equipment to be 1000 ℃, stirring and alloying, cooling, grinding the alloy into powder, and collecting the alloy powder after passing through a 120-mesh screen; the metal comprises the following components in parts by weight:
mn 100 parts
15 portions of Ag
Pt 12 parts
Re 7.5 parts
6 portions of Bi
3 parts of Au;
(2) and (3) replacement: adding the alloy powder into a zinc sulfate solution according to the addition of 0.35g/L, and stirring the solution for 15min under the ultrasonic condition by controlling the rotating speed of a stirrer to be 220 rpm; the ultrasonic condition is intermittent ultrasonic, and the ultrasonic is stopped for 5s after 10 s; in the zinc sulfate solution, the selenium content is 1.5 g/L;
(3) and (3) reduced pressure heating: placing the solution in a reaction kettle, and adding organic acid to adjust the pH value to 4; closing the kettle cover, decompressing and heating, controlling the pressure to be 0.075Mpa and the temperature to be 200 ℃, and reacting for 2 hours; the organic acid is a mixture of oxalic acid and tartaric acid, and the molar ratio of the oxalic acid to the tartaric acid is 2: 1;
(4) filtering and deslagging: and (3) performing pressure filtration on the solution by using a filter press to obtain filtrate for deep selenium removal.
Detection shows that the selenium content in the final filtrate is 1.98 mg/L.
Example 3
A method for deeply removing selenium in a zinc sulfate solution comprises the following steps:
(1) preparing alloy powder: mixing metals containing Mn, Ag, Pt, Re, Bi, Au and the like, adding the mixed metals into melting equipment for melting, controlling the temperature of the melting equipment to be 1200 ℃, stirring and alloying, cooling, grinding the alloy into powder, and collecting the alloy powder after passing through a 100-mesh and 150-mesh screen; preferably, the metals are as follows in parts by weight:
mn 100 parts
20 portions of Ag
Pt 16 parts
Re 10 parts
8 portions of Bi
4 parts of Au;
(2) and (3) replacement: adding the alloy powder into zinc sulfate solution according to the addition of 0.5g/L, and stirring the solution for 20min under the ultrasonic condition by controlling the rotating speed of a stirrer to be 250 rpm; preferably, the ultrasonic condition is intermittent ultrasonic, and ultrasonic treatment is stopped for 5s after 10 s; preferably, the content of selenium in the zinc sulfate solution is 3 g/L;
(3) and (3) reduced pressure heating: placing the solution in a reaction kettle, and adding organic acid to adjust the pH value to 5; closing the kettle cover, decompressing and heating, controlling the pressure to be 0.1Mpa and the temperature to be 250 ℃, and reacting for 3 hours; the organic acid is sulfamic acid;
(4) filtering and deslagging: and (3) performing pressure filtration on the solution by using a filter press to obtain filtrate for deep selenium removal.
Detection shows that the selenium content in the final filtrate is 2.51 mg/L.
According to the data of the embodiment, the method can reduce the selenium content in the zinc sulfate solution to be less than one thousandth of the original selenium content, and has good purification effect and low cost.
The foregoing is only a preferred embodiment of the present invention. However, the present invention is not limited to the above embodiment. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (7)
1. The method for deeply removing selenium in zinc sulfate solution is characterized by comprising the following steps:
(1) preparing alloy powder: mixing metals containing Mn, Ag, Pt, Re, Bi, Au and the like, adding the mixture into melting equipment for melting, controlling the temperature of the melting equipment to be 800-plus-1200 ℃, stirring and alloying, cooling, grinding the alloy into powder, and collecting the alloy powder after passing through a 100-plus-150-mesh screen;
(2) and (3) replacement: adding the alloy powder into zinc sulfate solution according to the addition of 0.2-0.5g/L, and stirring the solution for 10-20min under the ultrasonic condition by controlling the rotation speed of a stirrer to be 200-250 rpm;
(3) and (3) reduced pressure heating: placing the solution in a reaction kettle, and adding organic acid to adjust the pH value to be 3-5; closing the kettle cover, decompressing and heating, controlling the pressure to be 0.05-0.1Mpa and the temperature to be 150-;
(4) filtering and deslagging: and (3) performing pressure filtration on the solution by using a filter press to obtain filtrate for deep selenium removal.
2. The method for deeply removing selenium in zinc sulfate solution according to claim 1, wherein in the step 1, the metals are calculated by weight:
mn 100 parts
10-20 parts of Ag
8-16 parts of Pt
Re 5-10 parts
4 to 8 portions of Bi
And 2-4 parts of Au.
3. The method for deeply removing selenium in zinc sulfate solution as claimed in claim 1, wherein in step 2, the organic acid is selected from one or more of oxalic acid, maleic acid, tartaric acid and sulfamic acid.
4. The method for deeply removing selenium in zinc sulfate solution as claimed in claim 1, wherein the organic acid is a mixture of oxalic acid and tartaric acid, and the molar ratio of oxalic acid to tartaric acid is 2: 1.
5. The method for deeply removing selenium in zinc sulfate solution according to claim 1, characterized in that the ultrasonic condition is intermittent ultrasonic, and ultrasonic treatment is stopped for 5s after 10 s.
6. The method for deeply removing selenium in zinc sulfate solution as claimed in claim 1, wherein the content of selenium in zinc sulfate solution in step 2 is 0.5-3 g/L.
7. The method for deeply removing selenium in zinc sulfate solution according to claim 1, characterized by comprising the following steps:
(1) preparing alloy powder: mixing metals containing Mn, Ag, Pt, Re, Bi, Au and the like, adding the mixture into melting equipment for melting, controlling the temperature of the melting equipment to be 1000 ℃, stirring and alloying, cooling, grinding the alloy into powder, and collecting the alloy powder after passing through a 120-mesh screen;
(2) and (3) replacement: adding the alloy powder into a zinc sulfate solution according to the addition of 0.35g/L, and stirring the solution for 15min under the ultrasonic condition by controlling the rotating speed of a stirrer to be 220 rpm;
(3) and (3) reduced pressure heating: placing the solution in a reaction kettle, and adding organic acid to adjust the pH value to 4; closing the kettle cover, decompressing and heating, controlling the pressure to be 0.075Mpa and the temperature to be 200 ℃, and reacting for 2 hours;
(4) filtering and deslagging: and (3) performing pressure filtration on the solution by using a filter press to obtain filtrate for deep selenium removal.
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| CN202011033373.0A CN111961852A (en) | 2020-09-27 | 2020-09-27 | Method for deeply removing selenium in zinc sulfate solution |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105018729A (en) * | 2015-08-18 | 2015-11-04 | 云南驰宏锌锗股份有限公司 | Composite additive for removing selenium and tellurium in zinc sulfate solution for purification and use method of composite additive |
| CN105132684A (en) * | 2015-08-18 | 2015-12-09 | 云南驰宏锌锗股份有限公司 | Method for extracting selenium and tellurium in zinc sulfate solution through high aluminum alloy zinc powder |
| WO2019178654A1 (en) * | 2018-03-22 | 2019-09-26 | "Kcm"Ad | Method for chemical extraction of metals by means of processing of industrial waste and modular installation for its implementation |
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- 2020-09-27 CN CN202011033373.0A patent/CN111961852A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105018729A (en) * | 2015-08-18 | 2015-11-04 | 云南驰宏锌锗股份有限公司 | Composite additive for removing selenium and tellurium in zinc sulfate solution for purification and use method of composite additive |
| CN105132684A (en) * | 2015-08-18 | 2015-12-09 | 云南驰宏锌锗股份有限公司 | Method for extracting selenium and tellurium in zinc sulfate solution through high aluminum alloy zinc powder |
| WO2019178654A1 (en) * | 2018-03-22 | 2019-09-26 | "Kcm"Ad | Method for chemical extraction of metals by means of processing of industrial waste and modular installation for its implementation |
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Application publication date: 20201120 |
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