CN106756039A - A kind of wet processing process of Treatment of Copper nickel tin antimony complex materials - Google Patents
A kind of wet processing process of Treatment of Copper nickel tin antimony complex materials Download PDFInfo
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- CN106756039A CN106756039A CN201611154135.9A CN201611154135A CN106756039A CN 106756039 A CN106756039 A CN 106756039A CN 201611154135 A CN201611154135 A CN 201611154135A CN 106756039 A CN106756039 A CN 106756039A
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- sulfuric acid
- concentrated sulfuric
- nickel
- water logging
- antimony
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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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- 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
- C22B11/042—Recovery of noble metals from waste materials
- C22B11/044—Recovery of noble metals from waste materials from pyrometallurgical residues, e.g. from ashes, dross, flue dust, mud, skim, slag, sludge
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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
- C22B23/00—Obtaining nickel or cobalt
- C22B23/04—Obtaining nickel or cobalt by wet processes
- C22B23/0407—Leaching processes
- C22B23/0415—Leaching processes with acids or salt solutions except ammonium salts solutions
- C22B23/043—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
- C22B25/00—Obtaining tin
- C22B25/04—Obtaining tin by 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
- C22B25/00—Obtaining tin
- C22B25/06—Obtaining tin from scrap, especially tin scrap
-
- 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
- C22B30/02—Obtaining antimony
-
- 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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- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Manufacture And Refinement Of Metals (AREA)
Abstract
The present invention relates to a kind of wet processing process of Treatment of Copper nickel tin antimony complex materials, including first time concentrated sulfuric acid digestion operation, first time water logging operation, second concentrated sulfuric acid digestion operation, second water logging operation, the heavy tin antimony of hydrolysis, it is characterized in that the concentrated sulfuric acid according to heat has strong oxidizer and highly acid, its sulphate cpd very easily corresponding with the reaction generation of cuprum-nickel-stannum antimony, according to the relation of solubility of the cuprum-nickel-stannum antimony sulfate in sulfuric acid system, make and precious metal separation, reach the purpose of enriching noble metals.And cupro-nickel is returning to next procedure treatment, to reach the elements such as energy synthetical recovery cupro-nickel tin antimony, this technological process is short, and operating cost is small, easy to operate simple, energy-saving.
Description
Technical field
The present invention is applied to Treatment of Copper nickel tin antimony complex materials, such as tin anode mud that thick tin is electrolysed out, composition brass electrolysis
The earth of positive pole of output, the flue dust of part pyrometallurgical smelting, lead anode slurry etc., the invention belongs to field of hydrometallurgy.
Background technology
Existing most of domestic treatment earth of positive pole producers apply the wet method combined technique of pyrogenic process, and pyrogenic process mainly uses sulfating roasting
Technique, the purpose of sulfating roasting soluble in water is made and precious metal separation using the sulfate of the heavy metals such as cupro-nickel zinc.So as to
Reach the heavy metal of earth of positive pole decopper(ing) nickel zinc and the bullion content purpose of the enrichment earth of positive pole.Sulfating roasting is material and dense sulphur
After acid mixing, by being manually added in charging tray with spoon material, afterwards charging tray is built, Muffle furnace is delivered to fork truck, set
500-700 DEG C of high temperature, sulfuric acid is thermally decomposed into a large amount of gases such as sulfur dioxide and sulfur trioxide.Muffle furnace roasting is static, is received
Heat is uneven to be easily caused the removal of cupro-nickel zinc not totally, influences next procedure index.Muffle furnace roasting chief drawback is that material turns
Chemical conversion sulfate needs longer time, and energy utilization rate is low, and labour intensity is big, is also easy to produce substantial amounts of poisonous and hazardous gas,
Need huge device for absorbing tail gas.
Partly there is research concentrated sulfuric acid digestion both at home and abroad, its field is mainly in the cupro-nickel earth of positive pole, such as Jinchuan Non-ferrous Metals Company two
Secondary concentrated sulfuric acid digestion nickel sulfide anode mud, cupro-nickel generation sulfuric acid cupro-nickel enters liquid phase and precious metal separation, afterwards from a point cupro-nickel slag
Middle refinement noble metal, and digestion tin antimony is not yet studied.Concentrated sulfuric acid digestion tin antimony element is mainly using the Strong oxdiative of hot concentrated sulfuric acid
Property and highly acid, tin antimony and its oxide change into corresponding sulfate.And the concentrated sulfuric acid or dilute sulfuric acid under normal temperature be difficult it is molten
Tin antimony and its oxide are solved, its main cause is：Tin antimony easily forms the diaphragm of oxide, strong acid, the acid of highly basic and oxidisability
All it is difficult to destroy its diaphragm.Only in high temperature, diaphragm could be destroyed under high pressure specific condition.Hot concentrated sulfuric acid can not only dissolve
Tin oxide, sulfide and simple substance tin, can also dissolve antimony oxide, sulfide and simple substance antimony formed corresponding sulfate enter it is molten
In liquid, and during noble metal and lead sulfate remain in leached mud, now bullion content is enriched with more than 8 times, is that next procedure is extracted
Gold and silver creates condition.The technological process that gold and silver is extracted not only is shortened by sulphur Acid Digestion, and improves the direct yield of gold and silver
And the rate of recovery, babbit nickel also synthetical recovery.
The content of the invention
Heavy metal the invention aims to solve earth of positive pole decopper(ing) nickel zinc in the prior art collects existing lacking
Fall into, there is provided a kind of wet processing process of Treatment of Copper nickel tin antimony complex materials.
To achieve these goals, the technical solution adopted by the present invention is：
A kind of wet processing process of Treatment of Copper nickel tin antimony complex materials, including first time concentrated sulfuric acid digestion operation, for the first time
Water logging operation, second concentrated sulfuric acid digestion operation, second water logging operation, first time concentrated sulfuric acid digestion operation includes following step
Suddenly：
Quantitative tin anode mud, and 1-2 times of concentrated sulfuric acid of its weight are added, 150-200 DEG C of temperature control is reacted 0.5-2h, obtained
Concentrated sulfuric acid mixed liquor；
First time water logging operation includes：Weight portion in being added in the concentrated sulfuric acid mixed liquor that first time concentrated sulfuric acid digestion operation is produced
5-6 times of water and quantitative sodium chloride, 50-60 DEG C of temperature control react 1h, obtain mixed liquor, and cold filtration obtains water logging slag
With the solution of sulfur acid cupro-nickel.
A kind of wet processing process of above-mentioned Treatment of Copper nickel tin antimony complex materials, second concentrated sulfuric acid digestion work
Sequence includes：The concentrated sulfuric acid of 3-4 times of its weight portion is added in the water logging slag, temperature control reacts 2-3h at 200-280 DEG C,
Obtain mixed serum.
A kind of wet processing process of above-mentioned Treatment of Copper nickel tin antimony complex materials, second water logging operation bag
Include：The water and quantitative sodium chloride of 3-4 times of its weight portion are added in the mixed serum, 60-80 DEG C of temperature control reacts 2-
3h, obtains the solution of concentration of precious metal thing and tin-antimony.
Beneficial effects of the present invention are：The chemical property, tin such as the strong oxidizing property and strong acid of the concentrated sulfuric acid of technology utilization heat
Antimony cupro-nickel all changes into corresponding sulfate soluble in water, and noble metal is stayed in leached mud, bullion content be enriched with 8 times with
On, it is that the extraction of next procedure gold and silver creates condition.The technological process that gold and silver is extracted not only is shortened by sulphur Acid Digestion, and
The direct yield and the rate of recovery of gold and silver are improved, sulfuric acid digestion process of the invention sets stirring transmission device, and material mixes with sulfuric acid
Uniformly, reaction speed is fast, and energy utilization rate is high, and reaction temperature is low, environmentally friendly, and labour intensity is small, and gold and silver product quality is high.
Brief description of the drawings
Fig. 1 is process chart of the invention.
Specific embodiment
As shown in figure 1, a kind of wet processing process of Treatment of Copper nickel tin antimony complex materials, including the leaching of the first time concentrated sulfuric acid
Boiling procedure, first time water logging operation, second concentrated sulfuric acid digestion operation, second water logging operation, first time concentrated sulfuric acid digestion work
Sequence comprises the following steps：
Quantitative tin anode mud, and 1-2 times of concentrated sulfuric acid of its weight are added, 150-200 DEG C of temperature control is reacted 0.5-2h, obtained
Concentrated sulfuric acid mixed liquor；
First time water logging operation includes：Weight portion in being added in the concentrated sulfuric acid mixed liquor that first time concentrated sulfuric acid digestion operation is produced
5-6 times of water and quantitative sodium chloride, 50-60 DEG C of temperature control react 1h, obtain mixed liquor, and cold filtration obtains water logging slag
With the solution of sulfur acid cupro-nickel.
Second concentrated sulfuric acid digestion operation includes：The concentrated sulfuric acid of 3-4 times of its weight portion, temperature are added in the water logging slag
Control reacts 2-3h at 200-280 DEG C, obtains mixed serum.
Second water logging operation includes：The water of 3-4 times of its weight portion and quantitative chlorination are added in the mixed serum
Sodium, 60-80 DEG C of temperature control reacts 2-3h, obtains the solution of concentration of precious metal thing and tin-antimony.
It is specific as follows：
Organic matter first in the rinsing earth of positive pole obtains the clean earth of positive pole, surveys its chemical composition：Tin 42%, antimony 19%, copper 5%, nickel
4%, golden 196g/t, silver 2%, palladium 120g/t.Wherein tin is main with tin simple substance（Solid solution）, stannous oxide, tin oxide its distribution ratio
5:3:2；Antimony is main with antimony simple substance（Solid solution）, antimony trioxide, antimony pentoxide its distribution ratio 15:4:1；Copper is main with copper simple substance
（Solid solution）, cupric oxide, copper sulfide presence, its distribution ratio 13:1:6；Nickel is main with nickel simple substance（Solid solution）, nickel oxide, vulcanization
Nickel, its distribution ratio 12:5:1；Gold-palladium silver is main to have the earth of positive pole with simple substance.
（2）The tin anode mud of the dry weight of 1000g is taken out, 500g water and 2000g sulfuric acid is added, mixes pulp 30min, temperature
150-200 DEG C of control, after reaction 1h, material is cooled to normal temperature.
（3）Mixed material is added into 5L water and 10g sodium chloride, 70-80 DEG C of temperature control after reaction 1h, is cooled to normal temperature
Filtering, obtains infusion（Volume 5.2L, copper 8.2g/l, nickel 6.3g/l, draw copper leaching rate 85%, nickel leaching rate 81.9%）And water
Phase analysis 1690g（Copper in Slag 0.79%, nickel 0.8%, moisture 45%）.
Wet sample 1690g obtained above is added the sulfuric acid of 3000g, 250-260 DEG C of temperature control after reaction 3h, is cooled down
To room temperature, the water of 1.5L and the sodium chloride of 12g are added afterwards, 80-90 DEG C of intensification obtains infusion（Volume 2L, tin 193.2g/
L, antimony 85.5g/l, copper：3.13g/L, nickel：3.15g/l calculates tin leaching rate 92%, antimony leaching rate 90%, copper leaching rate 85%, nickel
Leaching rate 85%）With water logging slag 124.3g（Dry weight）, gold and silver palladium（Golden 1536g/t, silver 15.68%, palladium 960g/t, tin 27%, antimony
15.12%, copper 0.88%, nickel：0.89%）.
The chemical property such as the strong oxidizing property and strong acid of the concentrated sulfuric acid of technology utilization heat, babbit nickel all changes into corresponding easy
The sulfate of water is dissolved in, and noble metal is stayed in leached mud, bullion content is enriched with more than 8 times, is that next procedure gold and silver is extracted
Create condition.The technological process that gold and silver is extracted not only is shortened by sulphur Acid Digestion, and is improved the direct yield of gold and silver and is returned
Yield, sulfuric acid digestion process of the invention sets stirring transmission device, and material is well mixed with sulfuric acid, and reaction speed is fast, the energy
Utilization rate is high, and reaction temperature is low, environmentally friendly, and labour intensity is small, and gold and silver product quality is high.
The present invention is not limited to above-mentioned preferred forms, and anyone can show that other are various under enlightenment of the invention
The product of form, however, make any change in its shape or structure, it is every with skill identical or similar to the present application
Art scheme, is within the scope of the present invention.
Claims (3)
1. a kind of wet processing process of Treatment of Copper nickel tin antimony complex materials, including first time concentrated sulfuric acid digestion operation, first
Secondary water logging operation, second concentrated sulfuric acid digestion operation, second water logging operation, it is characterised in that first time concentrated sulfuric acid digestion work
Sequence comprises the following steps：
Quantitative tin anode mud, and 1-2 times of concentrated sulfuric acid of its weight are added, 150-200 DEG C of temperature control is reacted 0.5-2h, obtained
Concentrated sulfuric acid mixed liquor；
First time water logging operation includes：Weight portion in being added in the concentrated sulfuric acid mixed liquor that first time concentrated sulfuric acid digestion operation is produced
5-6 times of water and quantitative sodium chloride, 50-60 DEG C of temperature control react 1h, obtain mixed liquor, and cold filtration obtains water logging slag
With the solution of sulfur acid cupro-nickel.
2. the wet processing process of a kind of Treatment of Copper nickel tin antimony complex materials according to claim 1, it is characterised in that
Second concentrated sulfuric acid digestion operation includes：The concentrated sulfuric acid of 3-4 times of its weight portion, temperature control are added in the water logging slag
At 200-280 DEG C, 2-3h is reacted, obtain mixed serum.
3. the wet processing process of a kind of Treatment of Copper nickel tin antimony complex materials according to claim 2, it is characterised in that
Second water logging operation includes：The water and quantitative sodium chloride of 3-4 times of its weight portion are added in the mixed serum, temperature
60-80 DEG C of degree control, reacts 2-3h, obtains the solution of concentration of precious metal thing and tin-antimony.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201611154135.9A CN106756039B (en) | 2016-12-14 | 2016-12-14 | A kind of wet processing process of Treatment of Copper nickel tin antimony complex materials |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201611154135.9A CN106756039B (en) | 2016-12-14 | 2016-12-14 | A kind of wet processing process of Treatment of Copper nickel tin antimony complex materials |
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| CN106756039A true CN106756039A (en) | 2017-05-31 |
| CN106756039B CN106756039B (en) | 2019-05-24 |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101575674A (en) * | 2001-06-28 | 2009-11-11 | 贵研铂业股份有限公司 | Method for recovering platinum metal from melting trapped material |
| CN103966451A (en) * | 2014-05-23 | 2014-08-06 | 江西理工大学 | Method for preparing sodium stannate from copper anode mud silver separation residue |
| CN103966456A (en) * | 2014-05-23 | 2014-08-06 | 江西理工大学 | Method for comprehensively recovering valuable metals from copper anode sludge silver separating slag |
-
2016
- 2016-12-14 CN CN201611154135.9A patent/CN106756039B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101575674A (en) * | 2001-06-28 | 2009-11-11 | 贵研铂业股份有限公司 | Method for recovering platinum metal from melting trapped material |
| CN103966451A (en) * | 2014-05-23 | 2014-08-06 | 江西理工大学 | Method for preparing sodium stannate from copper anode mud silver separation residue |
| CN103966456A (en) * | 2014-05-23 | 2014-08-06 | 江西理工大学 | Method for comprehensively recovering valuable metals from copper anode sludge silver separating slag |
Non-Patent Citations (1)
| Title |
|---|
| 黄礼煌: "《金银提取技术》", 31 May 2012, 冶金工业出版社 * |
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