CN109112316A - A kind of method of copper in efficient selective separation of Bismuth slag - Google Patents
A kind of method of copper in efficient selective separation of Bismuth slag Download PDFInfo
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- CN109112316A CN109112316A CN201811199438.1A CN201811199438A CN109112316A CN 109112316 A CN109112316 A CN 109112316A CN 201811199438 A CN201811199438 A CN 201811199438A CN 109112316 A CN109112316 A CN 109112316A
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- CN
- China
- Prior art keywords
- copper
- bismuth
- bismuth slag
- slag
- selective separation
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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
- C22B7/04—Working-up slag
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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
- C22B1/06—Sulfating roasting
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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
- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/04—Extraction of metal compounds from ores or concentrates by wet processes by leaching
- C22B3/06—Extraction of metal compounds from ores or concentrates by wet processes by leaching in inorganic acid solutions, e.g. with acids generated in situ; in inorganic salt solutions other than ammonium salt solutions
- C22B3/08—Sulfuric acid, other sulfurated acids or salts thereof
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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
Abstract
The invention belongs to a kind of non-ferrous metal field of hydrometallurgy, the method for being specifically related to copper in a kind of efficient selective separation of Bismuth slag includes the following steps: to mix bismuth slag and the concentrated sulfuric acid, it is roasted under the conditions of 300-600 DEG C, fired slags are obtained, then mix the sulfuric acid solution of fired slags and 1-3mol/L, are separated by solid-liquid separation, finally the copper in liquid phase is separated, the technical matters route is simple, and processing cost is cheap, and reaction condition is mild, good separating effect, copper separation rate reach 99% or more.
Description
Technical field
The invention belongs to a kind of non-ferrous metal field of hydrometallurgy, are specifically related to a kind of efficient selective separation of Bismuth slag
The method of middle copper.
Background technique
Lead smelting process is the process of a synthetical recovery, not only to refine lead, it is often more important that separation and Extraction is therein
Valuable metal, in a kind of lead refinement oxide later period slag charge of output, this slag charge mainly contains the valuable metals such as lead, bismuth, copper, antimony, silver,
Its synthetical recovery value is considerable, but the presence of copper seriously affects subsequent vacuum distillation process in slag charge, makes subsequent operation can not
It carries out, so how the copper in efficient selective separation of Bismuth slag is just particularly important.
Chinese patent 200910038837.4 describes a kind of separating technology of material containing lead, antimony, copper, bismuth and silver, and the technique is in original
The soda ash and reducing agent of raw material weight 5-10% are incorporated in material, 1100-1200 DEG C at a temperature of carry out melting, in smelting furnace on
One layer of face is copper Silanca, below one layer be lead bismuth silver alloy, separate copper antimony and bismuth lead.
Chinese patent 201510630262.0 describes a kind of method that copper bismuth is recycled from bismuth slag, and this method uses salt first
Acid solution leaches bismuth slag, and leached mud is lead smelting gas after filtering, and lead smelting gas returns to the metals such as silver-colored smelting system recycling lead silver.
Filtrate adds copper extractant ZJ988 to be extracted, and obtains bismuth-containing extraction extraction raffinate and cupric organic phase.Bismuth-containing extracts extraction raffinate through eddy flow electricity
Solution obtains bismuth meal, and bismuth meal is refined to obtain product refined bismuth；The organic addition sulfuric acid solution of cupric is stripped, and copper-bath is obtained,
Copper-bath obtains cathode copper after cyclone electrolytic cell.
Techniques described above method has its deficiency, and first method has that energy consumption is high, and second method exists
It is at high cost, the problems such as technique stream is complicated.
Chinese patent 201610990078.1 describes the work that a kind of selectivity efficient from high-copper bismuth slag extracts copper, bismuth
Skill uses high-copper bismuth slag and dilute sulfuric acid (concentration 60-110g/L) to mix, in autoclave, is passed through oxygen or air, controls
Temperature is 75-90 DEG C, and pressure is 0.4-1MPa in kettle, leaches copper ion under stirring condition, then uses salt Ore Leaching, isolated
Copper.The present invention carries out in autoclave, needs to be passed through oxygen, and equipment requirement is higher, and investment is big, and the process is more complicated, the leaching of copper
Extracting rate is not high.
Summary of the invention
The technical problem to be solved in the present invention is to provide a kind of method of copper in efficient selective separation of Bismuth slag, the technical stafves
Skill route is simple, and processing cost is cheap, and reaction condition is mild, good separating effect, and copper separation rate reaches 99% or more.
The contents of the present invention include a kind of method of copper in efficient selective separation of Bismuth slag, are included the following steps: bismuth slag
It is mixed with the concentrated sulfuric acid, is roasted under the conditions of 300-600 DEG C, obtain fired slags, it is then that the sulfuric acid of fired slags and 1-3mol/L is molten
Liquid mixing, is separated by solid-liquid separation, finally separates the copper in liquid phase.
The weight item of the bismuth slag includes bismuth 15~45%, lead 15~40%, copper 4~25%, silver 0.6~1.2%, antimony
3~8%.
The weight ratio of the bismuth slag and the concentrated sulfuric acid is 1:0.1-0.5.
The sulfating roasting time is 1-3h.
The solid-to-liquid ratio of the bismuth slag and dilute sulfuric acid is 1:3-5.
The incorporation time of the dilute sulfuric acid and fired slags is 1-3h.
The method that copper in liquid phase is separated is cyclone electrolytic cell method.
Solid matter after the separation of solid and liquid contains bismuth, obtains thick bismuth by vacuum distillation.
When the sulfuric acid solution of fired slags and 1-3mol/L mix, copper ion is leached, and is carried out at normal temperatures and pressures.
The container of the roasting is Muffle furnace.
The mass concentration of the concentrated sulfuric acid of the invention is greater than 98%.
The invention has the advantages that in the prior art, generally to bismuth slag by the way of dilute sulfuric acid mixing air/oxygen
It being handled, is copper oxide or monovalence copper in the liquid phase, forms it into bivalent cupric ion, liquid phase reactor is slower, so using
The form of pressurization and heating accelerates reaction speed.The mode of the concentrated sulfuric acid and bismuth the slag mixing of the invention is not needing to add
Under conditions of oxygen, to aoxidize copper ion, the leaching rate of copper is higher for heating under higher temperature.In general, liquid phase reactor is than solid
Phase reaction is more abundant, and the contact between ion and ion is more frequently and close, but from the point of view of experiment effect, it is of the invention
The leaching rate of copper is higher instead, inventors believe that, it may be since the concentrated sulfuric acid has strong oxidation at high temperature, together
When at the temperature disclosed above, oxidation reaction is more abundant, has reached reaction effect more better than liquid phase reactor.
The present invention does not need the participation of oxygen or air, can carry out in closed environment, technique is simpler, and more
Add safety.The present invention does not have the participation of chloride ion, reduces corrosion of the chloride ion to equipment, reduces the cost of liquid waste processing.
After the present invention mixes at the cupric bismuth ground-slag end after crushing grinding with the concentrated sulfuric acid according to a certain ratio, it is placed in Muffle furnace
Sulfating roasting is carried out, in roasting process, elemental copper or monovalence copper in bismuth slag are oxidized to divalent Cu2+, then again with dilute
Sulfuric acid normal temperature and pressure leaches, and makes Cu2+Into liquid phase, bismuth is stayed in slag, is finally separated by solid-liquid separation, to realize copper in bismuth slag
Separation, cupric leachate can carry out cyclone electrolytic cell and extract copper therein, and the method recycling of remaining bismuth slag vacuum available distillation is wherein
Bismuth.
Present invention process route is simple, and processing cost is cheap, and reaction condition is mild, good separating effect, and copper separation rate reaches
95% or more.Compared with traditional handicraft, the present invention has significant economic benefit and is easily achieved industrialization.
Detailed description of the invention
Fig. 1 is process flow chart of the invention.
Specific embodiment
Embodiment 1
It takes 100g bismuth slag (cupric 10.68%) and the 20mL concentrated sulfuric acid to mix, then roasts 1h at 300 DEG C.Roasting
The dilute sulfuric acid 300mL that concentration is 1mol/L is added in bismuth slag, stirs 1h under normal temperature and pressure.After the completion of stirring, filtering solution cleans filter
Slag measures filter residue weight 86.5g, and filter residue cupric 0.11%, copper separation rate is up to 99.1%.
Embodiment 2
It takes 1000g bismuth slag (cupric 10.68%) and the 350mL concentrated sulfuric acid to mix, then roasts 2h at 500 DEG C.It is roasting
Bismuth slag the dilute sulfuric acid 3500mL that concentration is 1mol/L is added, stir 1.5h under normal temperature and pressure.After the completion of stirring, filtering solution,
Filter residue is cleaned, measures filter residue weight 850.5g, filter residue cupric 0.03%, copper separation rate is up to 99.9%.
Embodiment 3
It takes 5000g bismuth slag (cupric 4.18%) and the 2000mL concentrated sulfuric acid to mix, then roasts 3h at 500 DEG C.It is roasting
Bismuth slag the dilute sulfuric acid 20000mL that concentration is 1mol/L is added, stir 3h under normal temperature and pressure.After the completion of stirring, filtering solution is washed
Net filter residue measures filter residue weight 4321g, and filter residue cupric 0.05%, copper separation rate is up to 99.5%.
Comparative example 1
It takes 100g bismuth slag (cupric 10.68%) and 20mL dilute sulfuric acid (1mol/L) to mix, then roasts 1h at 300 DEG C.
The dilute sulfuric acid 300mL that concentration is 1mol/L is added in roasting bismuth slag, stirs 1h under normal temperature and pressure.After the completion of stirring, filter molten
Liquid cleans filter residue, measures filter residue weight 86.5g, filter residue cupric 5.31%, copper separation rate is 89.1%.
Comparative example 2
It takes 100g bismuth slag (cupric 10.68%) and the 20mL concentrated sulfuric acid to mix, then roasts 1h at 800 DEG C.Roasting
The dilute sulfuric acid 300mL that concentration is 1mol/L is added in bismuth slag, stirs 1h under normal temperature and pressure.After the completion of stirring, filtering solution cleans filter
Slag measures filter residue weight 86.5g, and filter residue cupric 1.71%, copper separation rate is 97.8%.
The comparative analysis of 1 and comparative example 1-2 through this embodiment finds that the oxidation effectiveness of dilute sulfuric acid is poor, cannot reach
Purpose, dilute sulfuric acid lead to oxygen or other oxidants dissolution copper are added to be the reaction of a solid phase and liquid phase, and effect is not under normal pressure
It is good.Meanwhile temperature is too high also not all right, it may be since temperature is too high that copper separation rate declines instead, and bismuth oxide dissolves completely,
Copper oxide is wrapped up, to substantially reduce copper separation rate.
Claims (10)
1. a kind of method of copper in efficient selective separation of Bismuth slag, characterized in that include the following steps: to mix bismuth slag and the concentrated sulfuric acid
It closes, is roasted under the conditions of 300-600 DEG C, obtain fired slags, then mix the sulfuric acid solution of fired slags and 1-3mol/L, solid-liquid
Separation, finally separates the copper in liquid phase.
2. the method for copper in efficient selective separation of Bismuth slag as described in claim 1, characterized in that the weight of the bismuth slag at
Dividing includes bismuth 15~45%, lead 15~40%, copper 4~25%, silver 0.6~1.2%, antimony 3~8%.
3. the method for copper in efficient selective separation of Bismuth slag as described in claim 1, characterized in that the bismuth slag and the concentrated sulfuric acid
Weight ratio be 1:0.1-0.5.
4. the method for copper in efficient selective separation of Bismuth slag as described in any one of claims 1-3, characterized in that calcining time
For 1-3h.
5. the method for copper in efficient selective separation of Bismuth slag as described in any one of claims 1-3, characterized in that the bismuth slag
Solid-to-liquid ratio with dilute sulfuric acid is 1:3-5.
6. the method for copper in efficient selective separation of Bismuth slag as described in any one of claims 1-3, characterized in that dilute sulphur
The incorporation time of acid and fired slags is 1-3h.
7. the method for copper in efficient selective separation of Bismuth slag as described in any one of claims 1-3, characterized in that will be in liquid phase
The method separated of copper be cyclone electrolytic cell method.
8. the method for copper in efficient selective separation of Bismuth slag as described in any one of claims 1-3, characterized in that the solid-liquid
Solid matter after separation contains bismuth, obtains thick bismuth by vacuum distillation.
9. the method for copper in efficient selective separation of Bismuth slag as described in any one of claims 1-3, characterized in that fired slags and
When the sulfuric acid solution mixing of 1-3mol/L, copper ion is leached, and carries out at normal temperatures and pressures.
10. the method for copper in efficient selective separation of Bismuth slag as described in any one of claims 1-3, characterized in that the roasting
The container of burning is Muffle furnace.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811199438.1A CN109112316A (en) | 2018-10-15 | 2018-10-15 | A kind of method of copper in efficient selective separation of Bismuth slag |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811199438.1A CN109112316A (en) | 2018-10-15 | 2018-10-15 | A kind of method of copper in efficient selective separation of Bismuth slag |
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| CN109112316A true CN109112316A (en) | 2019-01-01 |
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| CN201811199438.1A Pending CN109112316A (en) | 2018-10-15 | 2018-10-15 | A kind of method of copper in efficient selective separation of Bismuth slag |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113862464A (en) * | 2021-08-29 | 2021-12-31 | 中南大学 | Method for recovering copper and scattered metal in black copper sludge |
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| WO2007088010A1 (en) * | 2006-02-01 | 2007-08-09 | Lanxess Deutschland Gmbh | Monodisperse, macroporous chelating resins in metal winning |
| CN103643037A (en) * | 2013-12-25 | 2014-03-19 | 昆明理工大学 | Separating method of copper and iron-lead in complex copper-iron-lead mixed sulphide ores |
| CN104762483A (en) * | 2015-03-27 | 2015-07-08 | 云南驰宏锌锗股份有限公司 | Method for producing copper sulfate from copper-bismuth scum |
| CN105821215A (en) * | 2016-04-19 | 2016-08-03 | 浙江亚栋实业有限公司 | Method for recycling metal bismuth from anode slime |
| CN105905874A (en) * | 2016-04-19 | 2016-08-31 | 浙江亚栋实业有限公司 | Method of recycling tellurium from anode mud |
-
2018
- 2018-10-15 CN CN201811199438.1A patent/CN109112316A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2007088010A1 (en) * | 2006-02-01 | 2007-08-09 | Lanxess Deutschland Gmbh | Monodisperse, macroporous chelating resins in metal winning |
| CN103643037A (en) * | 2013-12-25 | 2014-03-19 | 昆明理工大学 | Separating method of copper and iron-lead in complex copper-iron-lead mixed sulphide ores |
| CN104762483A (en) * | 2015-03-27 | 2015-07-08 | 云南驰宏锌锗股份有限公司 | Method for producing copper sulfate from copper-bismuth scum |
| CN105821215A (en) * | 2016-04-19 | 2016-08-03 | 浙江亚栋实业有限公司 | Method for recycling metal bismuth from anode slime |
| CN105905874A (en) * | 2016-04-19 | 2016-08-31 | 浙江亚栋实业有限公司 | Method of recycling tellurium from anode mud |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113862464A (en) * | 2021-08-29 | 2021-12-31 | 中南大学 | Method for recovering copper and scattered metal in black copper sludge |
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| PB01 | Publication | ||
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Application publication date: 20190101 |