CN109182765A - A method of star metal is prepared with antimony cigarette ash - Google Patents
A method of star metal is prepared with antimony cigarette ash Download PDFInfo
- Publication number
- CN109182765A CN109182765A CN201811218577.4A CN201811218577A CN109182765A CN 109182765 A CN109182765 A CN 109182765A CN 201811218577 A CN201811218577 A CN 201811218577A CN 109182765 A CN109182765 A CN 109182765A
- Authority
- CN
- China
- Prior art keywords
- antimony
- cigarette ash
- filtrate
- antimony cigarette
- star metal
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
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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
- 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
- C22B7/02—Working-up flue dust
-
- 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
-
- 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
-
- 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
Abstract
It the invention belongs to the product refining art after metal smelt, is specifically related to a kind of method for preparing star metal with antimony cigarette ash, includes the following steps: 1, mixes antimony cigarette ash and water, hydrofluoric acid and ammonium fluoride is added, stirs, filtering obtains filtrate 1；2, the concentrated sulfuric acid is added into filtrate 1, stirs, filtering obtains filtrate 2；3, filtrate 2 is handled, prepares star metal, the rate of recovery of the product that method of the invention obtains, antimony is high, purity is high.
Description
Technical field
The invention belongs to the product refining arts after a kind of metal smelt, are specifically related to a kind of antimony cigarette ash preparation essence
The method of antimony.
Background technique
A large amount of cigarette ash can be all generated when lead anode slurry reduction melting and precious metals containing lead refinement oxide, this cigarette ash mainly contains
Antimony, lead, arsenic, mainly exist in the form of the oxide, and antimony content, in 1-10%, is recycling in 5-20%, arsenic in 35-70%, lead
The important source material of antimony.The recycling of previous this antimony cigarette ash usually first carries out reduction melting and generates needle antimony, then is obtained by coarse antimony refining
To star metal, coarse antimony refining divides pyrogenic process and wet process.
The pyro-refining of needle antimony be generally based on make foreign metal preferential oxidation in antimony or vulcanization form dross and and antimony
The methods of separation, cooling liquate, vacuum distillation can also be used, generate intermetallic compound, so that certain impurity is reduced to industry and wants
It asks.Pyro-refining use copper removal, iron removing reagent be usually antimony trisulfide, sodium sulphate and sodium carbonate: dearsenification, desulfurizing agent be caustic soda and
Sodium carbonate.The pyro-refining of antimony is a conventional method, although there are many problems using relatively wide.(1) reaction be 800~
It is carried out at a high temperature of 1000 DEG C, in-depth study can not be carried out to it, the related data much reacted is still unknown.Meanwhile it is high
Temperature also makes plant produced bad environments.(2) either oxidizing process, chloridising or vulcanization, antimony are likely to evaporate, or
Person is dissolved in slag liquid, keeps the loss of antimony high.(3) slag formed is usually stable metal eutectic, and valuable metal is difficult in slag
It recycles.(4) all removal steps are intended to that cleaner or slag former is added, and may introduce new impurity.(5) arsenic, lead exist
More difficult removing in pyro-refining.It must be strictly controlled reaction condition, or need melt back, can be only achieved removal of impurities and require.
The wet-process refining of needle antimony is mainly electrolysis method, needle antimony (mixture containing antimony simple substance and impurity) aqueous solution electrolysis essence
Refining can be used to the metallic antimony of high-purity, and gold, silver therein and other in electrification can be recycled by the processing of the earth of positive pole
The metal being positive in sequence compared with antimony；It can also be used to handle impure more needle antimony, obtain preferable comprehensive recovery.Electrolysis method
It needs antimony oxide being reduced to simple substance antimony first, increases reaction process, and electrolysis method very power consumption, energy consumption is high, not environmentally.
The centralized system of processing antimony cigarette ash is disclosed in the background technique that Chinese Patent Application No. is 201710728026.1
With its present in difficulty, purifying and separation are that metal handles existing two very important aspects, only this two side always
Face, which is all carried out, can be only achieved requirement.
Summary of the invention
The technical problem to be solved in the present invention is to provide a kind of method for preparing star metal with antimony cigarette ash, the rate of recovery of antimony is high,
Purity is high.
The contents of the present invention include the following steps:
1, antimony cigarette ash and water are mixed, hydrofluoric acid and ammonium fluoride is added, stirred, filtering obtains filtrate 1；It is above-mentioned to react
Temperature be room temperature, reaction time 1-3h.
2, the concentrated sulfuric acid is added into filtrate 1, stirs, filtering obtains filtrate 2；Reaction temperature is room temperature, reaction time 0.5-
1h。
3, filtrate 2 is handled, prepares star metal.
It include antimony, lead and arsenic in the antimony cigarette ash, weight item and content are antimony 35-70%, lead 5-20%, arsenic 1-
10%.
The weight ratio of the antimony cigarette ash and water is 1:2-6.
The weight of the hydrofluoric acid is the 40%-60% of antimony cigarette ash weight.
The w/v of ammonium fluoride and water is 70-120g/L.
The w/v of the concentrated sulfuric acid and water is 70-120g/L.
It is cyclone electrolytic cell method to the processing method that filtrate 2 is handled.
The cell body of cyclone electrolytic cell is lead bath, and cathode is stainless steel material, tank voltage 1.5-3V, current density 200-
500mA/m2, electrolysing period 36-56h, electric effusion basis is Sb3+20-130g/L, NH4 +35-60g/L, F-50-85g/L,
SO4 2-300-400g/L, Pb2+﹤ 3g/L, As3+﹤ 8g/L.
The invention has the advantages that most of three oxidations, two ladder and hydrogen fluorine in the first step, in antimony cigarette ash of the invention
Acid effect generates antimony trifluoride soluble easily in water, Sb2O3+ 6HF=2SbF3+3H2O, and lead oxide and arsenic oxide arsenoxide substantially not with hydrogen
Fluoric acid reaction generates and is insoluble in the substance of water, to reach the initial gross separation of antimony Yu lead arsenic, the addition of second sulfuric acid can be with
The lead ion (lead sulfate that generation is insoluble in water) in solution is further removed, present invention adds ammonium fluorides, can be improved most
The purity (being greater than 99.9%) of final product antimony, traces it to its cause, it may be possible to which ammonium fluoride forms complex compound in solution system, complexing
Effect is conducive to separate antimony and other metallic elements.
Specific embodiment
Embodiment 1
Arsenic material containing antimony used contains antimony 59.35%, arsenic 8.21%, lead 10.34%.
It weighs 500g antimony cigarette ash to pour into polytetrafluoroethylene (PTFE) slot, 2.5L water slurry is added, 1.5 times of theoretical amount hydrogen fluorine are added
Acid is added 250g ammonium fluoride solid, is stirred to react 2h, filters, is slowly added to the 800g concentrated sulfuric acid into filtrate under agitation,
It is stirred to react 0.5h, is filtered, filtrate injects antimony cyclone electrolytic cell equipment, and electrodeposition 3h obtains cathode antimony, antimony content 99.94%.
Embodiment 2
Arsenic material containing antimony used contains antimony 36.34%, arsenic 9.18%, lead 19.21%.
It weighs 500g antimony cigarette ash to pour into polytetrafluoroethylene (PTFE) slot, 2.5L water slurry is added, 1.2 times of theoretical amount hydrogen fluorine are added
Acid is added 300g ammonium fluoride solid, is stirred to react 2.5h, filters, is slowly added to the dense sulphur of 1000g into filtrate under agitation
Acid is stirred to react 1h, and filtering, filtrate injects antimony cyclone electrolytic cell equipment, and electrodeposition 2.5h obtains cathode antimony, antimony content 99.95%.
Comparative example 1
Arsenic material containing antimony used contains antimony 59.35%, arsenic 8.21%, lead 10.34%.
It weighs 500g antimony cigarette ash to pour into polytetrafluoroethylene (PTFE) slot, 2.5L water slurry is added, 1.5 times of theoretical amount hydrogen fluorine are added
Acid is stirred to react 2h, and filtering is slowly added to the 800g concentrated sulfuric acid into filtrate under agitation, is stirred to react 0.5h, filters,
Filtrate injects antimony cyclone electrolytic cell equipment, and electrodeposition 3h obtains cathode antimony, antimony content 88.32%.
Comparative example 2
Arsenic material containing antimony used contains antimony 59.35%, arsenic 8.21%, lead 10.34%.
It weighs 500g antimony cigarette ash to pour into polytetrafluoroethylene (PTFE) slot, 2.5L water slurry is added, 1.5 times of theoretical amount hydrogen fluorine are added
Acid is added 250g ammonium fluoride solid, is stirred to react 2h, filters, is slowly added to 1500g dilute sulfuric acid into filtrate under agitation
(volumetric concentration 40%) is stirred to react 0.5h, and filtering, filtrate injects antimony cyclone electrolytic cell equipment, and electrodeposition 3h obtains cathode antimony, antimony
Content 91.27%.
From the point of view of the analysis of embodiment 1 and comparative example 1-2, the present invention is common hydrofluoric acid, ammonium fluoride and the concentrated sulfuric acid
Under effect, the antimony oxide in antimony cigarette ash is reduced to antimony, the other impurities in antimony cigarette ash are effectively excluded, it is effective to improve
The purity of product antimony.
Claims (8)
1. a kind of method for preparing star metal with antimony cigarette ash, characterized in that include the following steps:
1, antimony cigarette ash and water are mixed, hydrofluoric acid and ammonium fluoride is added, stirred, filtering obtains filtrate 1；
2, the concentrated sulfuric acid is added into filtrate 1, stirs, filtering obtains filtrate 2；
3, filtrate 2 is handled, prepares star metal.
2. the method for preparing star metal with antimony cigarette ash as described in claim 1, characterized in that include antimony, lead in the antimony cigarette ash
And arsenic, weight item and content are antimony 35-70%, lead 5-20%, arsenic 1-10%.
3. the method for preparing star metal with antimony cigarette ash as claimed in claim 1 or 2, characterized in that the weight of the antimony cigarette ash and water
Amount is than being 1:2-6.
4. the method for preparing star metal with antimony cigarette ash as claimed in claim 1 or 2, characterized in that the weight of the hydrofluoric acid is
The 40%-60% of antimony cigarette ash weight.
5. the method for preparing star metal with antimony cigarette ash as claimed in claim 1 or 2, characterized in that the weighing body of ammonium fluoride and water
Product is than being 70-120g/L.
6. the method for preparing star metal with antimony cigarette ash as claimed in claim 1 or 2, characterized in that the weight of the concentrated sulfuric acid and water
Amount volume ratio is 70-120g/L.
7. the method for preparing star metal with antimony cigarette ash as claimed in claim 1 or 2, characterized in that the processing side handled filtrate 2
Method is cyclone electrolytic cell method.
8. the method for preparing star metal with antimony cigarette ash as claimed in claim 7, characterized in that the cell body of cyclone electrolytic cell is lead
Slot, cathode are stainless steel material, tank voltage 1.5-3V, current density 200-500mA/m2, electrolysing period 36-56h, electric effusion
Basis is Sb3+20-130g/L, NH4 +35-60g/L, F-50-85g/L, SO4 2-300-400g/L, Pb2+﹤ 3g/L, As3+﹤
8g/L。
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811218577.4A CN109182765A (en) | 2018-10-18 | 2018-10-18 | A method of star metal is prepared with antimony cigarette ash |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811218577.4A CN109182765A (en) | 2018-10-18 | 2018-10-18 | A method of star metal is prepared with antimony cigarette ash |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN109182765A true CN109182765A (en) | 2019-01-11 |
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ID=64945605
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201811218577.4A Pending CN109182765A (en) | 2018-10-18 | 2018-10-18 | A method of star metal is prepared with antimony cigarette ash |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110106525A (en) * | 2019-06-18 | 2019-08-09 | 中国科学院过程工程研究所 | A kind of method that low dense mercury antimony solution intensified electrolysis extracts mercury antimony |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2008184653A (en) * | 2007-01-30 | 2008-08-14 | Dowa Metals & Mining Co Ltd | Method for producing antimony oxide and method for producing metal antimony |
| CN101909770A (en) * | 2008-01-10 | 2010-12-08 | 学校法人芝浦工业大学 | Method of recycling useful metal |
| CN102031381A (en) * | 2010-11-28 | 2011-04-27 | 郴州市金贵银业股份有限公司 | Process for preparing sodium pyroantimonate from arsenic- and stibium-containing smoke ash |
| CN102534225A (en) * | 2012-02-27 | 2012-07-04 | 牛辉 | Treatment method for anode mud |
| CN104911364A (en) * | 2015-06-26 | 2015-09-16 | 郴州市金贵银业股份有限公司 | Environment-friendly and high-efficiency production method of antimony white by using Sb and As-containing ash |
-
2018
- 2018-10-18 CN CN201811218577.4A patent/CN109182765A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2008184653A (en) * | 2007-01-30 | 2008-08-14 | Dowa Metals & Mining Co Ltd | Method for producing antimony oxide and method for producing metal antimony |
| CN101909770A (en) * | 2008-01-10 | 2010-12-08 | 学校法人芝浦工业大学 | Method of recycling useful metal |
| CN102031381A (en) * | 2010-11-28 | 2011-04-27 | 郴州市金贵银业股份有限公司 | Process for preparing sodium pyroantimonate from arsenic- and stibium-containing smoke ash |
| CN102534225A (en) * | 2012-02-27 | 2012-07-04 | 牛辉 | Treatment method for anode mud |
| CN104911364A (en) * | 2015-06-26 | 2015-09-16 | 郴州市金贵银业股份有限公司 | Environment-friendly and high-efficiency production method of antimony white by using Sb and As-containing ash |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110106525A (en) * | 2019-06-18 | 2019-08-09 | 中国科学院过程工程研究所 | A kind of method that low dense mercury antimony solution intensified electrolysis extracts mercury antimony |
| CN110106525B (en) * | 2019-06-18 | 2021-06-08 | 中国科学院过程工程研究所 | Method for extracting mercury and antimony through intensified electrolysis of low-concentration mercury and antimony solution |
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Application publication date: 20190111 |
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