CN107723473A - Comprehensive utilization method of high-arsenic-content polymetallic gold ore - Google Patents
Comprehensive utilization method of high-arsenic-content polymetallic gold ore Download PDFInfo
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- CN107723473A CN107723473A CN201710713917.XA CN201710713917A CN107723473A CN 107723473 A CN107723473 A CN 107723473A CN 201710713917 A CN201710713917 A CN 201710713917A CN 107723473 A CN107723473 A CN 107723473A
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- arsenic
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- comprehensive utilization
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Classifications
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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
- C22B11/00—Obtaining noble metals
- C22B11/04—Obtaining noble metals by wet processes
-
- 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
-
- 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
- C22B30/00—Obtaining antimony, arsenic or bismuth
- C22B30/04—Obtaining arsenic
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
- C25C1/00—Electrolytic production, recovery or refining of metals by electrolysis of solutions
- C25C1/22—Electrolytic production, recovery or refining of metals by electrolysis of solutions of metals not provided for in groups C25C1/02 - C25C1/20
-
- 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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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Mechanical Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Manufacture And Refinement Of Metals (AREA)
Abstract
The invention relates to a comprehensive utilization method of high-arsenic multi-metal gold ore, belonging to the technical field of comprehensive recycling of low-value precious metal ore resources. The method comprises the steps of realizing efficient separation of antimony and other valuable metals by a combined process of a wet method and a pyrogenic method and controlling the potential of a No. 1 efficient leaching reagent in the wet method process, obtaining crude antimony by electrodeposition of a leaching solution, removing impurities to obtain refined antimony, treating a waste electrolyte to obtain a byproduct of crystallized sodium sulfide, separating leaching residues by the pyrogenic method to obtain oxides of arsenic, and further reducing to obtain metallic arsenic. The waste liquid and slag generated in the process are recycled in a closed loop, and secondary pollution to the environment is avoided.
Description
Technical field
The invention belongs to non-ferrous metal metallurgy technical field, and in particular to a kind of comprehensive utilization of the high Polymetallic sulfide ore containing arsenic
Method.
Background technology
With the scarcity for the rich ore class nonferrous metal resource that grade is high, metal is single, the non-ferrous metal market price in addition
Continued downturn, carry out non-ferrous metal metallurgy using the difficult complicated ore of more metals and have become non-ferrous metal metallurgy industry raising effect
The effective way of benefit, and high-quality Precious Metals Resources, particularly lack containing high-grade gold ore resource in China seriously, in China
West area, high-grade gold mine is more, but this gold ore resource contains the metals such as the not low arsenic of grade, antimony, these metals member
Element has a great influence for the production process of traditional gold smelting, and traditional handicraft is roasting removing arsenic at present, antimony or utilizes letter
Either simplex skill is reclaimed or abandoned.But existing maximum safety and environment hidden danger are to reclaim not thoroughly, valuable metal wastes serious, antimony
Slag muck dis environment hidden danger is serious, and the arsenic oxide arsenoxide flue dust value for being calcined to obtain is not high, and sale is problem, and stores or transport easily
Cause large area safety or environmental accident.
Therefore, a kind of production technology that can handle the multi-metallic minerals containing arsenic, recovery and enterprise to valuable metal are developed
Core competitiveness tool is of great significance.
The content of the invention
For above-mentioned problems of the prior art and deficiency, present invention offer one kind will contain arsenic noble metal materials and pass through
Wet method pyrogenic process combines closed circuit technique, the method for making the valuable metals such as antimony, gold, lead be efficiently separated and utilized.
To achieve the above object, the present invention provides following technical scheme：
A kind of method of comprehensive utilization of the high Polymetallic sulfide ore containing arsenic, this method are carried out as steps described below：
Step 1：Ball milling 1-3h is carried out to raw ore using existing ore grinding device, when the ore particle of granularity in ore grinding ore pulp≤200 mesh
When percentage by weight reaches more than the 85% of ore pulp gross weight, liquid-solid ratio 3-5 is pressed in container is leached:1 adds water and ore grinding ore deposit
Slurry, low whipping speed 40-60r/min, temperature be 45-65 DEG C under the conditions of add 1# leaching agents, leach 1-2h, filtering to soak
Slag tap A and leachate B, and the percentage composition ratio of each element is wherein in raw ore：As is 0.5-15%, Sb 20-50%, Pb 0.2-
10%, Au content are 15-300g/t；
Step 2：The leachate B obtained in step 1 is obtained into sponge antimony using conventional electrodeposition process electrodeposition, added in sponge antimony
The impurity removal reagents that sponge antimony mass ratio is 0.1-0.5% are accounted for, cool melting, separates out sulfuric acid lead skim, star metal of casting；
Electrodeposition analysis antimony key reaction be：
4Na3SbS3 + 12NaOH=4Sb+12Na2S+ 6H2O+3O2↑
Step 3：The leached mud A low-temperature bakes that will be obtained in step 1, obtain arsenic oxide arsenoxide flue dust C, and concentration of precious metal obtains Gold Concentrate under Normal Pressure；
Step 4：The arsenic oxide arsenoxide flue dust C obtained in step 3 is added into reducing agent reduction, the addition of reducing agent in closed electric furnace
For 5-10 times of theoretical amount reacted completely with arsenic oxide arsenoxide flue dust C, metallic arsenic product is obtained.
Further, the addition of 1# leaching agents is the 5-30% of ore pulp quality in step 1.
Further, 1# leaching agents are vulcanized sodium, sodium hydroxide, the mixture of sodium carbonate in step 1, are vulcanized in mixture
Sodium, sodium hydroxide, the mass ratio of sodium carbonate are 10-20:40-50:30-60.
Further, the cleaner in step 2 is phosphorus pentoxide, ammonium sulfide, ammonium carbonate, the mixture of ammonium sulfate, is mixed
Phosphorus pentoxide, ammonium sulfide, ammonium carbonate, the mass ratio of ammonium sulfate are 5-10 in compound:10-20:50-60:10-30.
Further, the reducing agent in step 4 is the one of which in charcoal, coke, coal dust.
Compared with prior art, the beneficial effects of the invention are as follows：
The present invention will contain arsenic noble metal materials and combine closed circuit technique by wet method pyrogenic process, obtain the valuable metals such as antimony, gold, lead
Efficiently separate and utilize, elemental arsenic is made using reducing process in arsenic（Metallic arsenic）, semi-conducting material can be used as（GaAs etc.）'s
Raw material, and completely eliminate arsenic and influence to gold smelting is remained in noble metal materials, also completely eliminate traditional handicraft
Safety and environment hidden danger existing for the arsenic oxide arsenoxide class product produced, the process are a typical recycling economy production moulds
Formula, meet country and Gansu Province's recycling economy overall planning, in the intractability and the processing procedure that greatly reduce this kind of material
Pollution to environment, to country, there is good economic and social benefit to enterprise.The application of this method, can be fully sharp
With the resources advantage in Gansu and surrounding area.
Embodiment
With reference to embodiment, the present invention is described in detail.
The present invention is a kind of method of comprehensive utilization of the high Polymetallic sulfide ore containing arsenic, and this method is carried out as steps described below：
Step 1：Ball milling 1-3h is carried out to raw ore using existing ore grinding device, when the ore particle of granularity in ore grinding ore pulp≤200 mesh
When percentage by weight reaches more than the 85% of ore pulp gross weight, liquid-solid ratio 3-5 is pressed in container is leached:1 adds water and ore grinding ore deposit
Slurry, low whipping speed 40-60r/min, temperature be 45-65 DEG C under the conditions of add 1# leaching agents, leach 1-2h, filtering to soak
Slag tap A and leachate B, and the percentage composition ratio of each element is wherein in raw ore：As is 0.5-15%, Sb 20-50%, Pb 0.2-
10%, Au content are 15-300g/t, and the addition of 1# leaching agents is the 5-30% of ore pulp quality, and wherein 1# leaching agents are vulcanization
Sodium, sodium hydroxide, the mixture of sodium carbonate, vulcanized sodium, sodium hydroxide, the mass ratio of sodium carbonate are 10-20 in mixture:40-
50:30-60；
Step 2：The leachate B obtained in step 1 is obtained into sponge antimony using conventional electrodeposition process electrodeposition, added in sponge antimony
The impurity removal reagents that sponge antimony mass ratio is 0.1-0.5% are accounted for, cool melting, separates out sulfuric acid lead skim, cast star metal, wherein cleaner
For phosphorus pentoxide, ammonium sulfide, ammonium carbonate, ammonium sulfate mixture, phosphorus pentoxide, ammonium sulfide, ammonium carbonate, sulphur in mixture
The mass ratio of sour ammonium is 5-10:10-20:50-60:10-30；
Electrodeposition analysis antimony key reaction be：
4Na3SbS3 + 12NaOH=4Sb+12Na2S+ 6H2O+3O2↑
Step 3：The leached mud A low-temperature bakes that will be obtained in step 1, obtain arsenic oxide arsenoxide flue dust C, and concentration of precious metal obtains Gold Concentrate under Normal Pressure；
Step 4：The arsenic oxide arsenoxide flue dust C obtained in step 3 is added into reducing agent reduction, the addition of reducing agent in closed electric furnace
For 5-10 times of theoretical amount reacted completely with arsenic oxide arsenoxide flue dust C, metallic arsenic product is obtained, wherein reducing agent is charcoal, coke, coal
One of which in powder.
Embodiment 1
As 3.6%, Sb 26%, Pb 3.2%, Au 126g/t mineral aggregate 1kg, moisture 5%, ball milling 1h, when in ore grinding ore pulp will be contained
When the percentage by weight of the ore particle of the mesh of granularity≤200 reaches more than the 85% of ore pulp gross weight, 5%1# leaching agents, liquid-solid ratio are added
3:1, low whipping speed 40r/min, 45 DEG C of extraction temperature is controlled, leach 2h, be filtrated to get leached mud A and leachate B, leached
Liquid B reaches sponge antimony using conventional electrodeposition process, adds 0.1% impurity removal reagents, by the way of the melting that cools, separates out sulfuric acid
Lead skim, star metal of casting；Leached mud A is obtaining arsenic oxide arsenoxide flue dust and Gold Concentrate under Normal Pressure using low-temperature bake, and arsenic oxide arsenoxide flue dust utilizes electric furnace,
Add 5 times of coke to be reduced, obtain metallic arsenic product.
Implementation result：Antimony leaching rate is more than 98%, and lead sulfate antimony content in slag is less than 0.1%, and Gold Concentrate under Normal Pressure is less than 0.01% containing arsenic, contains
Antimony is less than 0.02%, and metallic arsenic reaches GB standard.
Embodiment 2
As 12.5%, Sb 15.6%, Pb 5.2%, Au 225g/t mineral aggregate 1kg, moisture 8%, ball milling 3h, when ore grinding ore pulp will be contained
When the percentage by weight of the ore particle of the mesh of middle granularity≤200 reaches more than the 85% of ore pulp gross weight, 10%1# leaching agents are added, liquid is solid
Than 4:1, low whipping speed 50r/min, 65 DEG C of extraction temperature is controlled, leach 1h, be filtrated to get leached mud A and leachate B, soaked
Go out liquid B and reach sponge antimony using conventional electrodeposition process, add 0.3% impurity removal reagents, by the way of the melting that cools, separate out sulphur
Lead plumbate slag, star metal of casting；Leached mud A obtains arsenic oxide arsenoxide flue dust and Gold Concentrate under Normal Pressure using low-temperature bake, and arsenic oxide arsenoxide flue dust utilizes electric furnace,
Add 8 times of charcoals to be reduced, obtain metallic arsenic product.
Implementation result：Antimony leaching rate is more than 97.5%, and lead sulfate antimony content in slag is less than 0.2%, and Gold Concentrate under Normal Pressure is less than 0.03% containing arsenic,
It is less than 0.05% containing antimony, metallic arsenic reaches GB standard.
Embodiment 3
As 2.5%, Sb 25.4%, Pb 7.5%, Au 175g/t mineral aggregate 1kg, moisture 10%, ball milling 2h, when ore grinding ore pulp will be contained
When the percentage by weight of the ore particle of the mesh of middle granularity≤200 reaches more than the 85% of ore pulp gross weight, 30%1# leaching agents are added, liquid is solid
Than 5:1, low whipping speed 60r/min, 60 DEG C of extraction temperature is controlled, leaches 1.5h, be filtrated to get leached mud A and leachate B,
Leachate B reaches sponge antimony using conventional electrodeposition process, adds 0.5% impurity removal reagents, by the way of the melting that cools, separates out
Sulfuric acid lead skim, star metal of casting；Leached mud A obtains arsenic oxide arsenoxide flue dust and Gold Concentrate under Normal Pressure using low-temperature bake, and arsenic oxide arsenoxide flue dust utilizes electricity
Stove, add 10 times of coal dusts and reduced, obtain metallic arsenic product.
Implementation result：Antimony leaching rate is more than 96.5%, and lead sulfate antimony content in slag is less than 0.5%, and Gold Concentrate under Normal Pressure is less than 0.15% containing arsenic,
It is less than 0.25% containing antimony, metallic arsenic reaches GB standard.
Embodiment 4
Remaining step of embodiment 4 is not all uniquely the mixing that 1# leaching agents are vulcanized sodium, sodium hydroxide, sodium carbonate with embodiment 1
Thing, mixing quality ratio are：10:50:30；Cleaner is phosphorus pentoxide, ammonium sulfide, ammonium carbonate, the mixture of ammonium sulfate, is mixed
Mass ratio is：5:10:60:10.
Implementation result：Antimony leaching rate is more than 98.5%, and lead sulfate antimony content in slag is less than 0.3%, and Gold Concentrate under Normal Pressure is less than 0.25% containing arsenic,
It is less than 0.15% containing antimony, metallic arsenic reaches GB standard.
Embodiment 5
Remaining step of embodiment 5 is not all uniquely the mixing that 1# leaching agents are vulcanized sodium, sodium hydroxide, sodium carbonate with embodiment 2
Thing, mixing quality ratio are：15:40:40；Cleaner is phosphorus pentoxide, ammonium sulfide, ammonium carbonate, the mixture of ammonium sulfate, is mixed
Mass ratio is：10:20:50:20.
Implementation result：Antimony leaching rate is more than 97.5%, and lead sulfate antimony content in slag is less than 0.8%, and Gold Concentrate under Normal Pressure is less than 0.35% containing arsenic,
It is less than 0.65% containing antimony, metallic arsenic reaches GB standard.
Embodiment 6
Remaining step of embodiment 6 is not all uniquely the mixing that 1# leaching agents are vulcanized sodium, sodium hydroxide, sodium carbonate with embodiment 3
Thing, mixing quality ratio are：20:45:60；Cleaner is phosphorus pentoxide, ammonium sulfide, ammonium carbonate, the mixture of ammonium sulfate, is mixed
Mass ratio is：8:15:55:30.
Implementation result：Antimony leaching rate is more than 98.5%, and lead sulfate antimony content in slag is less than 0.2%, and Gold Concentrate under Normal Pressure is less than 0.05% containing arsenic,
It is less than 0.15% containing antimony, metallic arsenic reaches GB standard.
Claims (5)
1. a kind of method of comprehensive utilization of the high Polymetallic sulfide ore containing arsenic, it is characterised in that this method is carried out as steps described below：
Step 1：Ball milling 1-3h is carried out to raw ore using existing ore grinding device, when the ore particle of granularity in ore grinding ore pulp≤200 mesh
When percentage by weight reaches more than the 85% of ore pulp gross weight, liquid-solid ratio 3-5 is pressed in container is leached:1 adds water and ore grinding ore deposit
Slurry, low whipping speed 40-60r/min, temperature be 45-65 DEG C under the conditions of add 1# leaching agents, leach 1-2h, filtering to soak
Slag tap A and leachate B, and the percentage composition ratio of each element is wherein in raw ore：As is 0.5-15%, Sb 20-50%, Pb 0.2-
10%, Au content are 15-300g/t；
Step 2：The leachate B obtained in step 1 is obtained into sponge antimony using conventional electrodeposition process electrodeposition, added in sponge antimony
The impurity removal reagents that sponge antimony mass ratio is 0.1-0.5% are accounted for, cool melting, separates out sulfuric acid lead skim, star metal of casting；
Step 3：The leached mud A low-temperature bakes that will be obtained in step 1, obtain arsenic oxide arsenoxide flue dust C, and concentration of precious metal obtains Gold Concentrate under Normal Pressure；
Step 4：The arsenic oxide arsenoxide flue dust C obtained in step 3 is added into reducing agent reduction, the addition of reducing agent in closed electric furnace
For 5-10 times of theoretical amount reacted completely with arsenic oxide arsenoxide flue dust C, metallic arsenic product is obtained.
2. a kind of method of comprehensive utilization of the high Polymetallic sulfide ore containing arsenic as claimed in claim 1, it is characterised in that in step 1
The addition of 1# leaching agents is the 5-30% of ore pulp quality.
A kind of 3. method of comprehensive utilization of the high Polymetallic sulfide ore containing arsenic as claimed in claim 1 or 2, it is characterised in that step 1
Middle 1# leaching agents are vulcanized sodium, sodium hydroxide, the mixture of sodium carbonate, vulcanized sodium, sodium hydroxide, the matter of sodium carbonate in mixture
It is 10-20 to measure ratio:40-50:30-60.
A kind of 4. method of comprehensive utilization of the high Polymetallic sulfide ore containing arsenic as claimed in claim 1 or 2, it is characterised in that step 2
In cleaner be phosphorus pentoxide, ammonium sulfide, ammonium carbonate, the mixture of ammonium sulfate, phosphorus pentoxide, vulcanization in mixture
Ammonium, ammonium carbonate, the mass ratio of ammonium sulfate are 5-10:10-20:50-60:10-30.
A kind of 5. method of comprehensive utilization of the high Polymetallic sulfide ore containing arsenic as claimed in claim 1 or 2, it is characterised in that step 4
In reducing agent be charcoal, coke, the one of which in coal dust.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201710713917.XA CN107723473A (en) | 2017-08-18 | 2017-08-18 | Comprehensive utilization method of high-arsenic-content polymetallic gold ore |
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| CN201710713917.XA CN107723473A (en) | 2017-08-18 | 2017-08-18 | Comprehensive utilization method of high-arsenic-content polymetallic gold ore |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110790238A (en) * | 2019-10-09 | 2020-02-14 | 山东恒邦冶炼股份有限公司 | Treatment method for recycling comprehensive utilization of antimony wool crystalline salt |
| CN112023987A (en) * | 2020-09-15 | 2020-12-04 | 西北矿冶研究院 | Recycling method of deactivated denitration catalyst |
| CN113089025A (en) * | 2021-03-10 | 2021-07-09 | 广西启日矿业有限公司 | Method for recovering antimony from antimony ore containing gold antimony oxide |
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| CN110790238A (en) * | 2019-10-09 | 2020-02-14 | 山东恒邦冶炼股份有限公司 | Treatment method for recycling comprehensive utilization of antimony wool crystalline salt |
| CN112023987A (en) * | 2020-09-15 | 2020-12-04 | 西北矿冶研究院 | Recycling method of deactivated denitration catalyst |
| CN113089025A (en) * | 2021-03-10 | 2021-07-09 | 广西启日矿业有限公司 | Method for recovering antimony from antimony ore containing gold antimony oxide |
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Application publication date: 20180223 |
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