CN1046142C - Method for smelting sodium sulfate from refined complex antimony ore - Google Patents
Method for smelting sodium sulfate from refined complex antimony ore Download PDFInfo
- Publication number
- CN1046142C CN1046142C CN96118109A CN96118109A CN1046142C CN 1046142 C CN1046142 C CN 1046142C CN 96118109 A CN96118109 A CN 96118109A CN 96118109 A CN96118109 A CN 96118109A CN 1046142 C CN1046142 C CN 1046142C
- Authority
- CN
- China
- Prior art keywords
- antimony
- concentrate
- concentrates
- sodium sulfate
- gold
- 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.)
- Expired - Fee Related
Links
Images
Landscapes
- Manufacture And Refinement Of Metals (AREA)
Abstract
The present invention relates to a treatment method of complicated antimony concentrates, which comprises sodium sulfate smelting, extraction, antimony precipitation, iron removal, etc. and can produce sodium antimonate and other valuable metal (lead and gold) concentrates. Compared with the traditional sodium sulfide extraction methods, sodium sulfide is replaced by sodium sulfate and treatment cost is greatly reduced. The mineral structure of raw materials is destroyed by high temperature smelting processes, and the separation of antimony, arsenic, lead or silver is relatively complete. The present invention is favorable for the effective increase of the grade of other valuable metal, is favorable for the subsequent smelting processes and is favorable for the comprehensive treatment of waste water, and the purpose of treating waste with waste is achieved. The present invention is suitable for the treatment of the complicated antimony concentrates such as antimony gold concentrates whose antimony content is more than or equal to 20%, antimony gold concentrates, jamesonite concentrates, antimony lead concentrates, antimony lead silver concentrates, etc.
Description
The present invention relates to a kind of treatment process of complicated antimony concentrate, particularly the metallurgical process of pyrogenic process synthesizing soluble antimonic salt and diluted acid deironing.It is by steps such as sodium sulfate melting, leaching, heavy antimony, deironing, output sodium antimonate and other valuable metal (plumbous, gold) concentrate.
Complicated antimony concentrate is a sulfuration alkali lye leaching-electrodeposition flow process as the conventional wet method that contains arsenic antimony gold concentrate, jamesonite concentrate antimony regulus.This flow process mature and reliable, but long flow path, equipment complexity, cost height, and produce Sulfothiorine, sodium polysulphide during electrodeposition, this electrolytic solution returns when leaching that gold is lost in leach liquor and negative electrode antimony (Zhao Tiancong work " antimony ", 386 pages in the concentrate, 504 pages, metallurgical industry press, 1987).Developed recently from the Sodium Sulphide leach liquor the directly heavy antimony (with the sodium antimonate form) of atmospheric oxidation, though simplified technology greatly, exist sodium sulphite consumption big, shortcomings such as cost height, the leaded grade of leached mud is low simultaneously, is difficult to enrichment, do not reach the requirement of lead ore concentrate grade, can not make full use of resource.When containing the arsenic antimony gold concentrate, processing, makes and to take off that the gold in the slag still is difficult to leach behind the antimony that gold need dissociate with other preprocessing process because of the part gold is wrapped in pyrite and the mispickel.
In order to overcome above deficiency, the invention provides and a kind ofly replace sodium sulphite with sodium sulfate, by pyroprocessing mineral structure is changed, help valuable metals such as antimony, gold and silver, lead and reclaim, can handle the method that complicated antimony concentrate particularly contains arsenic antimony gold concentrate, jamesonite concentrate.
Solution of the present invention is with sodium sulfate (Na
2SO
4), also raw coal (C) and the melting at high temperature of complicated antimony concentrate, after the melting, emit melt and cooling, broken, fine grinding, leach with the molten aqueous solution of practicing flue dust merging water or NaOH then, after the leaching, plumbous (golden or silver-colored) and iron and a small amount of sulphur and reduction pit ash are stayed in the leached mud, antimony and arsenic and unreacted sodium sulfate enter leach liquor, leach liquor is through the blowing air oxidation, and antimony is with the form precipitation of sodium antimonate, and sulphur then forms sulfate radical, negatively charged ion such as thiosulfate anion, arsenic is oxidized to arsenate and still stays in the solution, form post precipitation liquid, as reagent Returning smelting process, handle with ferrous sulfate after the crystallization by mother liquor through condensing crystal recovery part sodium salt for liquid behind the heavy antimony, discharging.The iron that exists with the Iron sulfuret form in the leached mud leaches with dilute sulphuric acid again, and iron enters solution, and sulfonium ion is separated out with the hydrogen sulfide form, absorbs with liquid behind the heavy antimony, and the leached mud after deironing is high-grade valuable metal concentrate as lead ore concentrate, gold ore.
Details are as follows about process and condition:
1. melting
The consisting of of each material (weight ratio) in the fusion process: sodium sulfate: go back raw coal: complicated antimony concentrate=1～1.5: 0.1～0.3: 1, smelting temperature is 650～1000 ℃, the time is 0.5～3 hour; The melt of emitting is through cooling, and fragmentation is finely ground to below the 0.175mm, enters leaching process.
The principal reaction of fusion process has:
The n value gets 1～3 in the formula (4), and the thioantimoniate of corresponding generation is NaSbS
2, Na
4Sb
2S
5And Na
3SbS
3When generating thioantimoniate, pyrite and mispickel decompose:
2. leach
Extraction temperature is 20～100 ℃, and NaOH concentration is 0～50g/L, and leaching liquid-solid ratio (weight ratio) is 1.5～3: 1, and the time is 0.25～4 hour, and filter residue returns to do to leach next time and uses with clear water washing 3 times, wash water.
The principal reaction that leaching process takes place has:
3. heavy antimony
Bubbling air oxidation precipitation antimony in leach liquor, the pressure of blowing air is 0.2～1MPa, and the time is 5～20 hours, and temperature is 20～50 ℃.The principal reaction that heavy antimony process takes place has:
4. deironing
Iron in the leached mud exists with Iron sulfuret, and the present invention is removed as leaching agent with dilute sulphuric acid,
Extraction temperature during deironing is 10～30 ℃, and the time is 0.25～2 hour, and the sulfuric acid consumption is 5～15% of the antimony leaching quantity of slag (weight percent), H
2Liquid absorbed gained FeSO after S gas was used heavy antimony
4Solution be used for and evaporative crystallization sodium sulfate after mother liquor or produce the ferrous sulfate product.
Described sodium sulfate can be technical pure sodium sulfate, also can be the Na that closed that the liquid evaporative crystallization returns behind the heavy antimony
2S
2O
3Na
2SO
3, Na
2The Na of S
2SO
4
The present invention is applicable to the processing that contains complicated antimony concentrates such as arsenic antimony gold concentrate, antimony Jin Caokuang, jamesonite concentrate, antimony lead concentrate, antimony lead silver preparation concentrate that contains antimony 〉=20%.
The present invention and traditional sodium sulphite lixiviation process comparison have following advantage: replace sodium sulphite with sodium sulfate, reduce processing costs significantly; The high melt process is destroyed the mineral structure of thick material, and it is more thorough that antimony, arsenic, lead (or gold) are separated, and can improve the grade of valuable metal effectively, helps the subsequent smelting process of valuable metal; Wastewater comprehensive treatment reaches the purpose of the treatment of wastes with processes of wastes against one another.Compare with chlorination process, the present invention need not be special anticorrosion, and facility investment and maintenance cost are low, and agents useful for same is cheap and easy to get, and for containing the arsenic antimony gold concentrate, the higher-grade gold ore of output can be directly cyanidation gold-extracted.Compare with pyrogenic process, the rate of recovery of valuable metal increases substantially, good product quality.
Description of drawings:
Fig. 1: process flow diagram of the present invention.
The present invention is further illustrated below in conjunction with accompanying drawing.
1. Guangxi jamesonite concentrate, its main component is (%):
Sb:25.31,Pb:24,S:20,Fe:8.1。
Melting is raw materials used with proportioning (weight ratio) reagent to be: sodium sulfate: jamesonite concentrate: going back raw coal is 1: 1: 0.2, smelting temperature is 1000 ℃, time is 2 hours, the antimony and the lead that are retained in after the melting in the melt are respectively 81% and 80%, 19% antimony and the volatilization of 20% lead enter flue dust, the melt cooling, broken, be finely ground to below the 0.175mm, merging with liquid-solid ratio with the melting flue dust then is that 2.85: the 1 usefulness 20g/L NaOH aqueous solution leaches, extraction time is 2 hours, and extraction temperature is 80 ℃.Leach liquor is through the blowing air oxidation, and oxidizing condition is that air pressure is 0.3MPa, and temperature is 40 ℃, and the time is 10 hours, and the sodium antimonate product that obtains contains antimony 47.4%, and post precipitation liquid contains antimony 0.06g/L.Leached mud is at 30 ℃ down to leach 1 hour at 3: 1 with the sulphuric acid soln of 30g/L with liquid-solid ratio, obtains deferrization lead-in-dreg 53%, as lead ore concentrate.The rate of recovery from jamesonite concentrate to sodium antimonate antimony is 94%.
2. the Hunan contains the arsenic antimony gold concentrate, and its main component is (%):
Sb:29.31,As:6.5,S:22.55,Fe:13.73,Au:50g/T
Melting is raw materials used with proportioning (weight ratio) reagent to be: sodium sulfate: contain the arsenic antimony gold concentrate: going back raw coal is 1: 1: 0.15, smelting temperature is 1000 ℃, time is 2 hours, the antimony and the arsenic that are retained in the melt are respectively 79% and 81%, 21% antimony and the volatilization of 19% arsenic enter flue dust, the melt cooling, broken, be finely ground to below the 0.175mm, merging with liquid-solid ratio with the melting flue dust then is that 2.5: the 1 usefulness 50g/L NaOH aqueous solution leaches, extraction time is 1 hour, and extraction temperature is 80 ℃.Leach liquor is through the blowing air oxidation, and oxidizing condition is that air pressure is 0.3MPa, and temperature is 40 ℃, and the time is 10 hours, and the sodium antimonate product that obtains contains antimony 46%, and liquid contains antimony 0.08g/L behind the heavy antimony, contains arsenic 15g/l.Leached mud is at 30 ℃ down to leach 1.5 hour at 3: 1 with the sulphuric acid soln of 40g/L with liquid-solid ratio, obtains the deferrization slag and contains golden 150g/T, and antimony 1.5%, arsenic 0.4%, the rate of recovery of antimony is 92%, the rate of recovery of gold is 98%.
Claims (3)
1. method of handling complicated antimony concentrate output sodium antimonate and other valuable metal concentrate is characterized in that:
A: the consisting of of each material (weight ratio) in the fusion process: sodium sulfate: go back raw coal: complicated antimony concentrate=1～1.5: 0.1～0.3: 1, smelting temperature is 650～1000 ℃, the time is 0.5～3 hour; The melt of emitting is through cooling, and fragmentation is finely ground to below the 0.175mm, enters leaching process;
B: extraction temperature is 20～100 ℃, and NaOH concentration is 20～50g/L, and leaching liquid-solid ratio (weight ratio) is 1.5～3: 1, and the time is 0.25～4 hour, and filter residue is done to leach next time and used with clear water washing 3 times, wash water;
C: bubbling air oxidation precipitation antimony in soaking antimony liquid, the pressure of blowing air is 0.2～1MPa, and the time is 5～20 hours, and temperature is 20～50 ℃;
D: do the leaching agent deironing with dilute sulphuric acid, the extraction temperature during deironing is 10～30 ℃, and the time is 0.25～2 hour, and the sulfuric acid consumption is 5～15% of the antimony leaching quantity of slag, output H
2Liquid absorbed gained FeSO after S gas was used heavy antimony
4Solution is used to handle the mother liquor behind the sodium sulfate crystal or produces the ferrous sulfate product.
2. method according to claim 1 is characterized in that: described sodium sulfate is technical pure sodium sulfate, or contains Na
2S
2O
3, Na
2SO
3, Na
2The Na of S
2SO
4
3. method according to claim 1 is characterized in that: described complicated antimony concentrate comprise contain antimony 〉=20% contain arsenic antimony gold concentrate, antimony gold concentrate, jamesonite concentrate, antimony lead concentrate, antimony lead silver preparation concentrate.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN96118109A CN1046142C (en) | 1996-04-12 | 1996-04-12 | Method for smelting sodium sulfate from refined complex antimony ore |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN96118109A CN1046142C (en) | 1996-04-12 | 1996-04-12 | Method for smelting sodium sulfate from refined complex antimony ore |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1162650A CN1162650A (en) | 1997-10-22 |
| CN1046142C true CN1046142C (en) | 1999-11-03 |
Family
ID=5124801
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN96118109A Expired - Fee Related CN1046142C (en) | 1996-04-12 | 1996-04-12 | Method for smelting sodium sulfate from refined complex antimony ore |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1046142C (en) |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102517459A (en) * | 2012-01-11 | 2012-06-27 | 湖南娄底华星锑业有限公司 | Method for removing cadmium and ferrum from crude antimony by using metaphosphoric acid |
| CN102747229B (en) * | 2012-07-31 | 2013-11-27 | 中南大学 | Method for separating and recycling valuable metals in powder rich in multiple metals of waste circuit board |
| CN104073644B (en) * | 2014-06-26 | 2016-03-02 | 湖南生力新材料有限公司 | Refining lead slag-removed by antimony fire refining process reduction smelting method synchronous with arsenic alkali slag proportioning |
| CN110790238B (en) * | 2019-10-09 | 2022-08-30 | 山东恒邦冶炼股份有限公司 | Treatment method for recycling comprehensive utilization of antimony wool crystal salt |
| CN112779425A (en) * | 2020-05-20 | 2021-05-11 | 昆明冶金研究院有限公司 | Method for preparing sodium antimonate from stibnite |
| CN113444875B (en) * | 2021-06-28 | 2022-11-29 | 贵州理工学院 | Resource utilization method for synergistic treatment of antimony sulfide concentrate and aluminum industrial waste residues |
| CN114388773B (en) * | 2021-12-31 | 2023-07-21 | 华南师大(清远)科技创新研究院有限公司 | High-performance Sb-based sodium ion battery anode material and preparation method and application thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1007179B (en) * | 1985-07-12 | 1990-03-14 | 国际地区测量和地球科学学院 | Apparatus for deriving 3-d quantitative information from at least one steropair |
-
1996
- 1996-04-12 CN CN96118109A patent/CN1046142C/en not_active Expired - Fee Related
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1007179B (en) * | 1985-07-12 | 1990-03-14 | 国际地区测量和地球科学学院 | Apparatus for deriving 3-d quantitative information from at least one steropair |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1162650A (en) | 1997-10-22 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US7892505B2 (en) | Hydrometallurgical process for the treatment of metal-bearing sulfide mineral concentrates | |
| CN102191391B (en) | Method for extracting germanium from high-impurity low-grade complex zinc oxide powder | |
| CN102994747B (en) | Technology for recovering metallic copper from high-lead copper matte | |
| CN103276206B (en) | Method for leaching gold in alkaline thiourea system efficiently and stably | |
| CN101029353A (en) | Comprehensive extraction of valent metal from bismuth-containing polymetallic material | |
| CN1126498A (en) | Recovery of metals from sulphidic material | |
| CN106967884B (en) | A kind of method of silver separating residue of copper anode slime step by step arithmetic | |
| CN105543479B (en) | A kind of comprehensive recovering process of bismuth matte | |
| CN104017991A (en) | Process for efficiently and selectively separating copper in lead copper matte | |
| CN105349791A (en) | Method for selectively extracting copper from iron-copper-matte materials | |
| CN111519026B (en) | Method for leaching secondary coated gold hematite | |
| CN108220624B (en) | Method for treating caustic sludge in crude lead refining | |
| CN102586584B (en) | Method for selectively separating valuable metals from complex lead-containing precious metal material | |
| CN1204278C (en) | Arsenic smoke dust treating method | |
| US3981962A (en) | Decomposition leach of sulfide ores with chlorine and oxygen | |
| CN1046142C (en) | Method for smelting sodium sulfate from refined complex antimony ore | |
| CN103237909A (en) | Selective leach recovery of zinc from a composite sulphide ore deposit, tailings, crushed ore or mine sludge | |
| CN107739841A (en) | A kind of method for separating arsenic from containing the high copper dross slag of arsenic, reclaiming copper | |
| Parga et al. | Copper and cyanide recovery in cyanidation effluents | |
| CN1266908A (en) | Process for separating metallurgical materials of Zn, Cu, Cd and Pb by wet method and its application | |
| CN101914681B (en) | Pollution-free method for treating copper, lead and silver-containing material | |
| CN1236082C (en) | Wet method copper-extracting process | |
| CA1238192A (en) | Method for the recovery of germanium | |
| CN1173077C (en) | Method for producing antimony by electrolyzing antimony-containing sulfide mineral pulp | |
| CN111647750B (en) | Resource utilization method of tailings |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C06 | Publication | ||
| PB01 | Publication | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C19 | Lapse of patent right due to non-payment of the annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |