CN109055719A - A method of recycling valuable metal from selenic acid mud - Google Patents
A method of recycling valuable metal from selenic acid mud Download PDFInfo
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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
- C22B1/00—Preliminary treatment of ores or scrap
- C22B1/02—Roasting processes
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B19/00—Selenium; Tellurium; Compounds thereof
- C01B19/02—Elemental selenium or tellurium
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G28/00—Compounds of arsenic
- C01G28/005—Oxides; Hydroxides; Oxyacids
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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
- C22B13/00—Obtaining lead
- C22B13/02—Obtaining lead by dry processes
- C22B13/025—Recovery from waste materials
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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
- C22B13/00—Obtaining lead
- C22B13/04—Obtaining lead by wet processes
- C22B13/045—Recovery from waste materials
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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
- C22B15/00—Obtaining copper
- C22B15/0002—Preliminary treatment
- C22B15/0004—Preliminary treatment without modification of the copper constituent
- C22B15/0006—Preliminary treatment without modification of the copper constituent by dry processes
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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
- C22B15/00—Obtaining copper
- C22B15/0063—Hydrometallurgy
- C22B15/0065—Leaching or slurrying
- C22B15/0067—Leaching or slurrying with acids or salts thereof
- C22B15/0071—Leaching or slurrying with acids or salts thereof containing sulfur
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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
- C22B15/00—Obtaining copper
- C22B15/0063—Hydrometallurgy
- C22B15/0084—Treating solutions
- C22B15/0089—Treating solutions by chemical methods
- C22B15/0091—Treating solutions by chemical methods 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
- 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
- C22B7/006—Wet processes
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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
- 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
- C22B7/006—Wet processes
- C22B7/007—Wet processes by acid leaching
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
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Abstract
The invention belongs to metallurgical slag comprehensive reutilization fields, disclose a kind of method that valuable metal is recycled from selenic acid mud.Comprising steps of A. low-temperature bake: carrying out low-temperature bake to selenic acid mud, roasting, 99% or more, obtains high stupp and high selenium calcining slag to selenic acid mud demercuration rate；B. fired slags acid one soaks；C. fired slags acid two soaks: sour two immersion liquid acid refluxes one leaching, slag are recovered to lead system；D. selenium restores: the immersion liquid that step C is obtained adds reducing agent progress selenium reduction to produce impure selenium；E. copper is replaced: liquid after the reduction that step D is obtained, and the heavy copper of iron replacement is added to obtain high-grade copper slag；F: step E obtained rear liquid, by reduction, evaporation, concentration, cooling, crystallization recycling arsenic, waste water send sewage plant to handle.Present invention process is easy to operate, non-environmental-pollution, recovery value are high, operating cost is low and the distinguishing features such as economic benefit.
Description
Technical field
The invention belongs to waste residue comprehensive reutilization fields, and in particular to a kind of that valuable metal is recycled from selenic acid mud
Method.
Technical background
Content of the selenium in the earth's crust is 0.05 × 10-6, it is general very difficult to form industrial concentration.The occurrence status of selenium can probably divide
For 3 classes: one kind exists in the form of Independent Mineral, secondly exists in the form of isomorphism, and third is deposited with clay mineral adsorption form
?.The primary raw material (90%) of industrial abstract selenium is the earth of positive pole caused by copper electrolyzing refining, remaining comes from lead, cobalt, nickel refining
Calcining and the residual mud of gas washing in SA production of output etc..Selenic acid mud valuable metal content described in this patent is high, and the taste containing selenium is also high,
Undoubtedly extract the fine raw material of selenium, but the powerful interference that arsenic and mercury content height are extracted at selenium in raw material.
Substantially having and being divided into pyrogenic attack and wet-treating is also had been reported that the research of processing selenic acid mud at present, at wet process
Also aerobic pressure method handles point with normal pressure processing in reason.Chinese invention patent publication number CN201410119100.6 is public within 2014
A kind of method for having opened the pyrogenic process chloridizing volatilization of the earth of positive pole containing selenium copper separation selenium, although chloridizing volatilization can isolate selenium, pyrogenic process band
Come operating environment is poor, environmental pollution greatly, equipment seriously corroded, maintenance cost height etc. the problems such as come one after another, undoubtedly pyrogenic process is not
It is optimal processing method.It is high that Chinese invention patent publication number CN201310468734.8 in 2013 discloses a kind of oxygen pressure treatment
The high selen-tellurjum earth of positive pole of arsenic, Chinese invention patent publication number 201110370361.1 in 2011 disclose a kind of from low-grade selenium-containing object
The technique that selenium is extracted in material, such wet-treating selenic acid mud what is common is that selenium is soaked as far as possible by acid with oxidant
Then feed liquor out recycles selenium in pickle liquor.
Summary of the invention
The method that the present invention provides a kind of to recycle valuable metal from selenic acid mud, this method solve the prior arts pair
The difficult problem of the recycling of high arsenic mercury selenic acid mud valuable metal and arsenic, and dispose these dangers of mercury, arsenic properly, cost
Unit consumption is low, and removal process is environmentally friendly, easy to operate, is suitable for large-scale industrial application.
A method of recycling valuable metal from selenic acid mud, method includes the following steps:
A low-temperature bake: low-temperature bake is carried out to selenic acid mud, roasting, 99% or more, is obtained to selenic acid mud demercuration rate
High stupp and high selenium calcining slag；
B fired slags acid one soaks: the high selenium fired slags that step A is obtained are carried out by liquid-solid ratio (L/kg) 4~5:1 enriching sulfuric acid
Acid one soaks, and controls 30~80g/L of acid eventually and is leached, a leached mud and a leachate is obtained by filtration；
C fired slags acid two soaks: the leached mud that step B is generated carries out acid two by liquid-solid ratio (L/kg) 4~5:1 enriching sulfuric acid
Leaching, is obtained by filtration two leached muds and two leachates；
The reduction of D selenium: the leachate that step C is obtained adds sodium sulfite to carry out selenium reduction, obtains liquid after impure selenium and reduction；
The displacement of E copper: liquid after the reduction that step D is obtained adds iron replacement also native copper, obtains blister copper and displaced liquid.
Wherein, the above-mentioned method that valuable metal is recycled from selenic acid mud, selenic acid mud described in step A includes element
(by percentage to the quality): Pb 35~55%, Cu 3~10%, As 6~15%, Se 1~10%, Hg 0.05~5%.
Wherein, the above-mentioned method that valuable metal is recycled from selenic acid mud, the condition of low-temperature bake described in step A are as follows:
Maturing temperature is 300~500 DEG C, and calcining time is 4~6h.Such as maturing temperature be 350~450 DEG C, calcining time be 5~
6h.After roasting raw material demercuration rate 99% or more and other element loss that need to be recycled it is smaller.
Wherein, the above-mentioned method that valuable metal is recycled from selenic acid mud, high stupp described in step A send to mercury recycling
Processing is taken out.
Wherein, the above-mentioned method that valuable metal is recycled from selenic acid mud is carrying out a sour leaching to fired slags in step B
Before, it also needs to carry out ball milling to fired slags, is milled to granularity more than 100 mesh.
Wherein, the above-mentioned method that valuable metal is recycled from selenic acid mud, the leaching condition of the leaching of acid one described in step B
Are as follows: reaction temperature is 70~90 DEG C, 1~4h of reaction time.For example, reaction temperature is 80~86 DEG C, 2~4h of reaction time.
Wherein, the above-mentioned method that valuable metal is recycled from selenic acid mud, the leaching condition of the leaching of acid two described in step C
Are as follows: reaction temperature is 70~90 DEG C, 1~4h of reaction time.For example, reaction temperature is 80~86 DEG C, 2~4h of reaction time.
Wherein, the above-mentioned method that valuable metal is recycled from selenic acid mud, two leachates described in step C return to acid one
Leaching, two leached mud return to lead system.
Wherein, the above-mentioned method that valuable metal is recycled from selenic acid mud, the grade of impure selenium described in step D 90% with
On, such as 92% or more, 94% or more.
Wherein, the above-mentioned method that valuable metal is recycled from selenic acid mud, the additive amount of iron powder described in step E is copper
1.1~1.3 times of amount；The grade of the blister copper is up to 80% or more, such as 85% or more, 90% or more.
Wherein, the above-mentioned method that valuable metal is recycled from selenic acid mud, further includes step F: after the displacement that step E is obtained
Liquid obtains As by reduction, evaporation, concentration, cooling, crystallization recycling arsenic2O3, waste liquid send sewage plant to handle.
By carrying out elemental analysis and Experimental comparison to material, the optimum process process of final choice is the method for the present invention:
Low-temperature bake is carried out to selenic acid mud first, there are two purposes for roasting, first is that demercuration separates and recovers mercury, second is that oxidation material, keeps away
Exempt from material next step acidleach addition oxidant and increases cost.Followed by acidleach, pickle liquor are recycled twice to roasting material
In mainly contain selenium, arsenic, copper, lead, which further be enriched with, in acid leaching residue returns pyrometallurgical smelting of lead system and recycles lead.It is finally point of arsenic, copper and selenium
From with recycling, using iron replacement obtain GOOD TASTE copper ashes recycling copper, then with sodium sulfite reduction selenium obtain impure selenium recycling selenium,
Finally evaporate, be concentrated, crystallizing out arsenic recycling arsenic, remaining liquid blowdown water station handles qualified outlet, whole flow process do not generate exhaust gas,
Waste residue, valuable metal are recycled entirely, and whole flow process is short, easy to operate.
Compared with prior art, the beneficial effects of the present invention are:
1. being avoided using wet processing process, thermal process bring operating environment is poor, environmental pollution is big, equipment corrosion
Seriously, the problems such as maintenance cost is high；
2. not only having been separated well as first step process flow using low-temperature bake and having recycled mercury but also carried out to material
Oxidation processes have saved the cost that acidleach needs oxidizer to improve leaching rate；
3. operation of the present invention is easy, process flow is short, recovery rate of valuable metals high (the arsenic rate of recovery reaches 95% or more), no
The dangerous wastes such as exhaust gas waste residue are generated, are a kind of environmental protection and economy type technologies.
Detailed description of the invention
Fig. 1 is the process flow chart for recycling copper, mercury, lead, selenium, arsenic in the embodiment of the present invention 1 from selenic acid mud.
Specific embodiment
Further detailed description is done to technical solution of the present invention below in conjunction with specific embodiment.The following example
It is merely illustrative the ground description and interpretation present invention, and is not necessarily to be construed as limiting the scope of the invention.It is all to be based on this hair
In the range of the technology that bright above content is realized is encompassed by the present invention is directed to protect.
Unless otherwise indicated, raw materials and reagents used in the following embodiment are commercial goods, or can be by
Perception method preparation.
Embodiment 1
Low-temperature bake: take selenic acid mud 500g (Pb 38%, Cu5.76%, As8.5%, Se3.6%, Hg0.55%) in
It is roasted in crucible, maturing temperature is 360 DEG C, keeps the temperature 6h, mercury removal rate 99% after roasting, the almost free of losses of selenium, copper, lead.
Acid one soaks: taking above-mentioned roasting sample 200g, sulfuric acid solution or sour two immersion liquid, liquid-solid ratio 5:1,80 DEG C of water-bath is added
At a temperature of react 2h, control terminal acidity is 50g/L, filtering and sampling chemical examination, liquid ingredient are as follows: H+51.27g/L、As 14.45g/
L, Cu 10.05g/L, Se 4.67g/L, solution are chemically examined without mercury ion.
Acid two soaks: sulfuric acid solution is added by liquid-solid ratio (L/kg) 5:1 in an above-mentioned sour phase analysis, control terminal acidity to 80g/L,
It is filtered after reacting 2h under 80 DEG C of bath temperature, sampling chemical conversion point contains H+80.16g/L、As 2.75g/L、Cu 0.94g/L、
Se 1.25g/L, solution are chemically examined without mercury ion, and liquid returns leaching processing, and slag recycles lead, two step acidleach into pyrogenic process lead recovery circuit
Arsenic leaches 95%, copper leaching 96%, selenium leaches 96%, lead and enters slag entirely.
Selenium reduction: liquid 1000mL after one leaching of acid is taken, is added sodium sulfite (2.0 times of theoretical amount), in 60 DEG C of bath temperature
It is filtered after lower reaction 2h, samplingization H+48.29g/L, Cu 9.89g/L, Se 0.051g/L, impure selenium grade 96.87%, selenium reduction
Rate 97.8%, copper enter slag 1.5%.
Displacement copper: liquid 1000mL after taking selenium to restore, with sodium hydroxide solution tune pH to 1.5, addition iron powder be (theoretical amount
1.1 times), it is filtered after reacting 0.5h under 65 DEG C of bath temperature, liquid ingredient contains As14.33g/L, Cu0.05g/L, and heavy copper rate reaches
98%, copper ashes grade 87%.
Arsenic reduction-crystallization: liquid 1000mL after displacement copper is taken, is added anhydrous sodium sulfite (1.2 times of theoretical amount), at 70 DEG C
Bath temperature under react 1h after, liquid, which is evaporated, has been concentrated into most of crystal is precipitated, and three oxygen are crystallized out after being cooled to room temperature
Change two arsenic recycling arsenic, the arsenic rate of recovery is 96%, and waste liquid send sewage plant to handle qualified discharge.
Embodiment 2
Low-temperature bake: selenic acid mud 500g (Pb47%, Cu 3.76%, As 6.5%, Se 4.6%, Hg 1.77%) is taken
It is roasted in crucible, maturing temperature is 400 DEG C, keeps the temperature 5h, mercury removal rate 99% after roasting, the almost free of losses of selenium, copper, lead.
Acid one soaks: taking above-mentioned roasting sample 200g, sulfuric acid solution or sour two immersion liquid, liquid-solid ratio 4:1,80 DEG C of water-bath is added
At a temperature of react 2h, add sulfuric acid control terminal acidity be 60g/L, filtering and sampling chemical examination, liquid ingredient are as follows: H+60.27g/L、As
15.05g/L, Cu 7.33g/L, Se 10.08g/L, solution are chemically examined without mercury ion.
Acid two soaks: sulfuric acid solution is added by liquid-solid ratio 4:1 in an above-mentioned sour phase analysis, and then enriching sulfuric acid tune terminal acidity is extremely
95g/L is filtered after reacting 2h under 80 DEG C of bath temperature, and sampling chemical conversion point contains H+94.27g/L、As 1.66g/L、Cu
1.13g/L, Se 0.95g/L, solution are chemically examined without mercury ion, and liquid returns leaching processing, and slag recycles lead into pyrogenic process lead recovery circuit,
Two step acidleach arsenic leach 96%, copper leaching 96%, selenium leaches 95%, lead and enters slag entirely.
Selenium reduction: liquid 1000mL after one leaching of acid is taken, is added sodium sulfite (1.8 times of theoretical amount), in 60 DEG C of bath temperature
It is filtered after lower reaction 2h, samplingization H+88.79g/L, Cu 6.95g/L, Se 0.032g/L, impure selenium grade 95.35%, selenium reduction
Rate 98.2%, copper enter slag 1.6%.
Displacement copper: liquid 1000mL after taking selenium to restore, with sodium hydroxide solution tune pH to 1.5, addition iron powder be (theoretical amount
1.2 times), it is filtered after reacting 0.5h under 65 DEG C of bath temperature, liquid ingredient 14.88g/L containing As, Cu 0.03g/L, heavy copper rate
Up to 98.6%, copper ashes grade 85%.
Arsenic reduction-crystallization: liquid 1000mL after displacement copper is taken, is added anhydrous sodium sulfite (1.3 times of theoretical amount), at 70 DEG C
Bath temperature under react 1h after, liquid, which is evaporated, has been concentrated into most of crystal is precipitated, and recycling is crystallized after being cooled to room temperature
Arsenic, the arsenic rate of recovery are 95%, and waste liquid send sewage plant to handle qualified discharge.
Embodiment 3
Low-temperature bake: selenic acid mud 500g (Pb 53%, Cu 4.76%, As 7.5%, Se 5.3%, Hg are taken
3.04%) roasted in crucible, maturing temperature be 500 DEG C, keep the temperature 4h, mercury removal rate 99% after roasting, selenium, copper, lead almost without
Loss.
Acid one soaks: taking above-mentioned roasting sample 200g, sulfuric acid solution or sour two immersion liquid, liquid-solid ratio 4:1,80 DEG C of water-bath is added
At a temperature of react 2h, add sulfuric acid control terminal acidity be 80g/L, filtering and sampling chemical examination, liquid ingredient are as follows: H+79.27g/L、As
16.11g/L, Cu 8.43g/L, in Se 10.66g/L solution chemical examination without mercury ion.
Acid two soaks: sulfuric acid solution is added by liquid-solid ratio 4:1 in an above-mentioned sour phase analysis, and then enriching sulfuric acid tune terminal acidity is extremely
120g/L is filtered after reacting 2h under 80 DEG C of bath temperature, and sampling chemical conversion point contains H+120.09g/L、As 2.03g/L、Cu
Without mercury ion, liquid returns leaching processing for chemical examination in 0.98g/L, Se 1.01g/L solution, and slag recycles lead into pyrogenic process lead recovery circuit,
Two step acidleach arsenic leach 96%, copper leaching 97%, selenium leaches 97%, lead and enters slag entirely.
Selenium reduction: liquid 1000mL after one leaching of acid is taken, is added sodium sulfite (2.0 times of theoretical amount), in 60 DEG C of bath temperature
It is filtered after lower reaction 2h, samplingization H+77.97g/L, Cu 8.32g/L, Se 0.022g/L, impure selenium grade 94.89%, selenium reduction
Rate 98.7%, copper enter slag 1.3%.
Displacement copper: liquid 1000mL after taking selenium to restore, with sodium hydroxide solution tune PH to 1.5, addition iron powder be (theoretical amount
1.3 times), it is filtered after reacting 0.5h under 65 DEG C of bath temperature, liquid ingredient 15.89g/L containing As, Cu 0.01g/L, heavy copper rate
Up to 99.5%, copper ashes grade 88%.
Arsenic reduction-crystallization: liquid 1000mL after displacement copper is taken, is added anhydrous sodium sulfite (1.2 times of theoretical amount), at 70 DEG C
Bath temperature under react 1h after, liquid, which is evaporated, has been concentrated into most of crystal is precipitated, and recycling is crystallized after being cooled to room temperature
Arsenic, the arsenic rate of recovery are 95%, and waste liquid send sewage plant to handle qualified discharge.
More than, embodiments of the present invention are illustrated.But the present invention is not limited to above embodiment.It is all
Within the spirit and principles in the present invention, any modification, equivalent substitution, improvement and etc. done should be included in guarantor of the invention
Within the scope of shield.
Claims (10)
1. a kind of method for recycling valuable metal from selenic acid mud, which is characterized in that method includes the following steps:
A low-temperature bake: low-temperature bake is carried out to selenic acid mud, roasting, 99% or more, obtains high mercury to selenic acid mud demercuration rate
Flue dust and high selenium calcining slag；
B fired slags acid one soaks: the high selenium fired slags that step A is obtained carry out acid one by liquid-solid ratio (L/kg) 4~5:1 enriching sulfuric acid
Leaching controls 30~80g/L of acid eventually and is leached, a leached mud and a leachate is obtained by filtration；
C fired slags acid two soaks: the leached mud that step B is generated carries out acid two by liquid-solid ratio (L/kg) 4~5:1 enriching sulfuric acid and soaks,
Two leached muds and two leachates are obtained by filtration；
The reduction of D selenium: the leachate that step C is obtained adds sodium sulfite to carry out selenium reduction, obtains liquid after impure selenium and reduction；
The displacement of E copper: liquid after the reduction that step D is obtained adds iron replacement also native copper, obtains blister copper and displaced liquid.
2. the method according to claim 1 for recycling valuable metal from selenic acid mud, which is characterized in that institute in step A
Stating selenic acid mud includes element (by percentage to the quality): Pb 35~55%, Cu 3~10%, As 6~15%, Se 1~
10%, 0.05~5% Hg.
3. the method according to claim 1 for recycling valuable metal from selenic acid mud, which is characterized in that institute in step A
State the condition of low-temperature bake are as follows: maturing temperature is 300~500 DEG C, and calcining time is 4~6h.
4. the method according to claim 1 for recycling valuable metal from selenic acid mud, which is characterized in that institute in step A
High stupp is stated to send to mercury recovery processing or take out.
5. it is according to claim 1 from selenic acid mud recycle valuable metal method, which is characterized in that in step B
Before carrying out one leaching of acid to fired slags, also needs to carry out ball milling to fired slags, be milled to granularity more than 100 mesh.
6. the method according to claim 1 for recycling valuable metal from selenic acid mud, which is characterized in that institute in step B
State the leaching condition that acid two described in one leaching of acid and step C soaks are as follows: reaction temperature is 70~90 DEG C, 1~4h of reaction time.
7. the method according to claim 1 for recycling valuable metal from selenic acid mud, which is characterized in that institute in step C
It states two leachates and returns to one leaching of acid, two leached mud returns to lead system.
8. the method according to claim 1 for recycling valuable metal from selenic acid mud, which is characterized in that institute in step D
The grade of impure selenium is stated 90% or more, such as 92% or more, 94% or more.
9. the method according to claim 1 for recycling valuable metal from selenic acid mud, which is characterized in that institute in step E
The additive amount for stating iron powder is 1.1~1.3 times of copper mass；The grade of the blister copper is up to 80% or more.
10. described in any item methods for recycling valuable metal from selenic acid mud according to claim 1~9, which is characterized in that
Further include step F: the displaced liquid that step E is obtained obtains As by reduction, evaporation, concentration, cooling, crystallization recycling arsenic2O3,
Waste liquid send sewage plant to handle.
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Cited By (6)
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| CN109748249A (en) * | 2019-03-12 | 2019-05-14 | 湖南工业大学 | A method of the oxygen-enriched fluidized bed roasting of the earth of positive pole containing selenium-organic reducing extracts selenium |
| CN111057852A (en) * | 2019-12-04 | 2020-04-24 | 昆明理工大学 | Method for synchronously recycling selenium and mercury by treating acid sludge at low temperature through microwaves |
| CN111235396A (en) * | 2020-04-02 | 2020-06-05 | 河南中原黄金冶炼厂有限责任公司 | Wet processing method for copper smelting acid making sludge |
| CN112430739A (en) * | 2020-11-30 | 2021-03-02 | 中南大学 | Method for recovering mercury in nonferrous smelting solid waste |
| CN112795774A (en) * | 2020-12-26 | 2021-05-14 | 黑龙江紫金铜业有限公司 | Method for separating and recovering polymetallic acid mud containing copper, selenium, mercury and lead |
| CN115094252A (en) * | 2021-03-12 | 2022-09-23 | 昆明理工大学 | Method for recovering mercury from non-ferrous smelting low-mercury acid sludge by adopting hydrometallurgy technology |
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| CN109748249A (en) * | 2019-03-12 | 2019-05-14 | 湖南工业大学 | A method of the oxygen-enriched fluidized bed roasting of the earth of positive pole containing selenium-organic reducing extracts selenium |
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| CN111057852A (en) * | 2019-12-04 | 2020-04-24 | 昆明理工大学 | Method for synchronously recycling selenium and mercury by treating acid sludge at low temperature through microwaves |
| CN111235396A (en) * | 2020-04-02 | 2020-06-05 | 河南中原黄金冶炼厂有限责任公司 | Wet processing method for copper smelting acid making sludge |
| CN111235396B (en) * | 2020-04-02 | 2021-07-30 | 河南中原黄金冶炼厂有限责任公司 | Wet processing method for copper smelting acid making sludge |
| CN112430739A (en) * | 2020-11-30 | 2021-03-02 | 中南大学 | Method for recovering mercury in nonferrous smelting solid waste |
| CN112795774A (en) * | 2020-12-26 | 2021-05-14 | 黑龙江紫金铜业有限公司 | Method for separating and recovering polymetallic acid mud containing copper, selenium, mercury and lead |
| CN115094252A (en) * | 2021-03-12 | 2022-09-23 | 昆明理工大学 | Method for recovering mercury from non-ferrous smelting low-mercury acid sludge by adopting hydrometallurgy technology |
| CN115094252B (en) * | 2021-03-12 | 2023-10-24 | 昆明理工大学 | Method for recycling mercury from nonferrous smelting low-mercury acid sludge by adopting hydrometallurgy technology |
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Application publication date: 20181221 |