CN101328539A - Oxidation oven ash hydrometallurgical leaching process - Google Patents
Oxidation oven ash hydrometallurgical leaching process Download PDFInfo
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- CN101328539A CN101328539A CNA2008100319632A CN200810031963A CN101328539A CN 101328539 A CN101328539 A CN 101328539A CN A2008100319632 A CNA2008100319632 A CN A2008100319632A CN 200810031963 A CN200810031963 A CN 200810031963A CN 101328539 A CN101328539 A CN 101328539A
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Abstract
The invention provides a leaching process of the oxidation oven soot wet method, belonging to the treatment on side products of soot generated in the smelting process technical field. In the process, antimony oxide and arsenic oxide in the oxidation oven soot are simultaneously leached out by the reducing capacity of sodium sulphide first, and generated sodium thioadtimonate and sodium sulfarsenate enter leaching liquid; filter residues are returned for silver smelting reduction smelting; the leaching liquid is passed through air, the sodium thioadtimonate is oxidized into sodium antimonate, free sulfurs in the sodium antimonate are separated by filtering; the mixed filtrate of the sodium antimonate and the sodium sulfarsenate has coarse sodium antimonate crystals extracted by condensed crystallization; and the remained sodium sulfarsenate liquid is taken as waste liquid for reclaiming treatment, so that the effective separation of Pb and Ag and Sb and As is realized. The process of the invention can effectively reduce the quantity of soot returned to the oven for smelting, improving the capability of a reducing furnace for treating anode mud and achieving the double-win aims of improving the efficiency of the reducing furnace and reducing environmental pollution.
Description
Technical field
The present invention relates to smelt the treatment process of the cigarette ash by product that is produced in the precious metal product processes such as silver, bismuth, be specifically related to oxidation oven ash hydrometallurgical leaching process.
Background technology
At present, rare precious metal products such as China's most of precious metal smelting silver that enterprise produces, bismuth, all be that pyrogenic process extraction processing makes from the electrolytic lead anode sludge, the electrolytic lead anode sludge will be through changeing the reduction furnace melting in the production process, technological processs such as oxidized still is concise, these processes all have a large amount of cigarette ash to produce, and wherein the cigarette ash of oxidized still generation claims oxidized still cigarette ash.This cigarette ash is made up of the oxide compound of multiple metal, and wherein argentiferous contains arsenic about 9～12% 1.8%, contains antimony 30～40%, because argentiferous is higher, is unsuitable for direct export trade (valuation of cigarette ash argentiferous is lower); Directly discharging was both uneconomical, can pollute environment again.In order to improve the rate of recovery of precious metal silver, present oxidized still cigarette ash all returns reduction furnace and returns production, has taken reduction furnace charging space, and it is about 1/4 to have reduced the input amount of the anode sludge, makes the ANODE SLIME TREATMENT amount can not reach design requirements.And the harmful oxide compound such as arsenic, antimony that returns reduction furnace with cigarette ash can cause secondary pollution to environment in the retailoring process.
About oxidation oven ash hydrometallurgical leaching process, relevant report is not arranged as yet at present in relevant document.
Summary of the invention
Technical problem to be solved by this invention is: a kind of novel oxidation oven ash hydrometallurgical leaching process is provided, environmental pollutant such as arsenic, antimony are extracted, reclaim as the valuable metal oxide compound, reduce the quantity that cigarette ash returns the stove melting simultaneously, improve the ANODE SLIME TREATMENT ability of reduction furnace, improve reduction furnace efficient and reduce environmental pollution and improve three of comprehensive recovery ability and win purposes by improving the value that antimony quality in the cigarette ash improves part for export cigarette ash, reaching.
Thinking of the present invention is: because oxidized still cigarette ash is made up of multiple oxide compounds such as lead, silver, copper, bismuth, antimony and arsenic, (wherein trivalent antimony accounts for about 80%, more easily leaches with weisspiessglanz; Other has about 20% to be quinquevalence antimony and tetravalence antimony, difficult the leaching) be main, utilize the reducing power of sodium sulphite to leach simultaneously earlier weisspiessglanz in the oxidized still cigarette ash and arsenic oxide arsenoxide, generate schlippe's salt and thioarsenic acid sodium and enter leach liquor; And the oxide compound of lead, silver, copper and bismuth can not leach, and enters filter residue after filtration, returns silver-colored smelting reducing melting and reclaims lead, silver, copper, bismuth.Again with leach liquor bubbling air or interpolation oxygenant, schlippe's salt is oxidized into sodium antimonate and elemental sulfur cosedimentation, and thioarsenic acid sodium is not oxidized, once more after filtration separate sulfur for sodium arseniate, sodium antimonate and elemental sulfur mixing slag are through diluting sulfur deposition, with behind the diluent filtering separation sulphur, the sodium antimonate condensation-crystallization becomes white crystal again, extracts this white crystal and purifies as thick sodium antimonate international sale or continuation; Remaining thioarsenic acid sodium solution is done the waste liquid recycling, and realization Pb, Ag effectively separate with Sb, As's.
Chemical principle of the present invention is as follows: leach reaction Sb
2O
3+ 6Na
2S+3H
2O=2Na
3SbS
3+ 6NaOH
As
2O
3+6Na
2S+3H
2O＝2Na
3AsS
3+6NaOH
Oxidizing reaction 2Na
3SbS
3+ O
2→ Na
3SbO
3+ S ↓
According to above-mentioned thinking, the technical scheme that the present invention deals with problems is as follows:
A kind of oxidation oven ash hydrometallurgical leaching process is characterized in that adopting following steps:
A, oxidized still cigarette ash and sodium sulfide solution, the sodium hydroxide solution that reclaims mixed in reactor and heat, after reaction is finished, filtration; Processing condition are: the solvent and solute weight ratio of oxidized still cigarette ash and sodium sulfide solution and sodium hydroxide solution=5～10: 1; Sodium sulfide solution concentration 150～350g/L; Concentration of sodium hydroxide solution 20～50g/L; 95～130 ℃ of reactor controlled temperature; 1～3 hour reaction times;
B, the filter residue of getting the A step return silver-colored smelting reducing melting and reclaim plumbous, silver, copper and bismuth;
C, get the filtrate in the A step, adjust the surplus temperature of filtrate and keep 80 ℃, in filtrate bubbling air or and interpolation Potcrate, SODIUMNITRATE oxygenant, separate elemental sulfur once more after filtration;
D, the filtrate cooling that the C step is separated behind the elemental sulfur are condensed to 28～30 ℃, and crystallization is extracted the white crystals body and got thick sodium antimonate product; Remaining thioarsenic acid sodium solution gives other operation waste liquid recycling.
Hydro-oxidation sodium of the present invention can suppress the hydrolysis of sodium sulphite.
The leaching yield that the present invention adopts oxidation oven ash hydrometallurgical leaching process to realize is: antimony 〉=80%, arsenic 〉=95% has reached the effect that removes cigarette ash antimony, arsenic preferably.Leaching product is the mixing solutions of schlippe's salt and thioarsenic acid sodium, obtains sodium antimonate and thioarsenic acid sodium through the inflation oxidation again, and after filtration, the condensation-crystallization separation, realization Pb, Ag effectively separate with Sb, As, S's.The weight and volume that returns the leached mud of valuable metals such as reduction furnace melting recovery silver, bismuth has only about half of original oxidized still cigarette ash, reduced the fusion process smoke pollution, alleviated the reduction furnace load, promptly improved the processing power of reduction furnace antianode mud, reduced the production cost of this technology, improve production production efficiency and economic benefit, meet the requirement that ecotope is produced.
Description of drawings
Illustrate in greater detail the present invention below with reference to accompanying drawing with concrete experimental data.
Fig. 1 is for being schematic flow sheet of the present invention.
Embodiment
The oxidized still cigarette ash raw material that present embodiment adopted is to be to oxidized still cigarette ash sampling result according to my company scene:
Pb?22.30％；Ag?1.8124％；Bi?6.61％；Cu?0.51％；Sb?33.79％；As?9.35％。
Present embodiment adopts following steps: referring to accompanying drawing 1
A, oxidized still cigarette ash and sodium sulfide solution, the sodium hydroxide solution that reclaims mixed in reactor and heat, after reaction is finished, filtration; Processing condition are: the solvent and solute weight ratio of oxidized still cigarette ash and sodium sulfide solution and sodium hydroxide solution=8: 1; Sodium sulfide solution concentration 300g/L; Concentration of sodium hydroxide solution 30g/L; 130 ℃ of reactor controlled temperature; 3 hours reaction times;
B, the filter residue of getting the A step return silver-colored smelting reducing melting and reclaim plumbous, silver, copper and bismuth;
C, get the filtrate in the A step, adjust the surplus temperature of filtrate and keep 80 ℃, bubbling air in filtrate separates elemental sulfur once more after filtration;
D, the filtrate cooling that the C step is separated behind the elemental sulfur are condensed to 28～30 ℃, and crystallization is extracted the white crystals body and got thick sodium antimonate product; Remaining thioarsenic acid sodium solution gives other operation waste liquid recycling.
Below be the determination data analysis of the change of processing condition to the leaching yield influence:
Table 1
As can be seen from Table 1: at sodium sulphite 300g/L; Sodium hydroxide 30g/L; 130 ℃ of temperature; Under the processing condition in 3 hours reaction times, the three was with the solvent and solute weight ratio of oxidized still cigarette ash and sodium sulfide solution, sodium hydroxide solution=10: 1, and Sb leaching yield effect is best, but from the economic and technical norms analysis, liquid-solid ratio was advisable with 8: 1.Because the leaching yield mean value of As is 94.36%, almost all leach, this leaching condition is little to the leaching yield influence of As.
Table 2
Learn from table 2: the solvent and solute weight ratio of oxidized still cigarette ash and sodium sulfide solution, sodium hydroxide solution 8: 1; Sodium hydroxide 30g/L; 130 ℃ of temperature; Under the processing condition in 3 hours reaction times: be analyzed by amount of sodium sulfide: concentration is that the 300g/L effect is best, is lower than this and is worth then Sb leaching yield reduction, is higher than this value Sb leaching yield and does not raise.Equally, this leaching condition also influences not quite the leaching yield of As.
Table 3
Learn from table 3: the solvent and solute weight ratio of oxidized still cigarette ash and sodium sulfide solution, sodium hydroxide solution 8: 1; Sodium sulphite 300g/L; 130 ℃ of temperature; Under the processing condition in 3 hours reaction times, the leaching yield concentration of sodium hydroxide solution of Sb, As is best with the 50g/L effect, and from the economic technology angle, 30g/L also is desirable.
Table 4
Learn from table 4: the solvent and solute weight ratio of oxidized still cigarette ash and sodium sulfide solution, sodium hydroxide solution 8: 1; Sodium sulphite 300g/L; Sodium hydroxide 30g/L; Under the processing condition in 3 hours reaction times, 130 ℃ of leaching effects of leaching yield temperature are best, and the antimony leaching yield is up to 81.55%.
Table 5
Learn from table 5: the solvent and solute weight ratio of oxidized still cigarette ash and sodium sulfide solution, sodium hydroxide solution 8: 1; Sodium sulphite 300g/L; Sodium hydroxide 30g/L; Under the processing condition that temperature is 130 ℃, it is best to leach 3 hours reaction times effect.
Comprehensive above-mentioned statistical study, best leaching-out technique condition is as follows:
The solvent and solute weight ratio of oxidized still cigarette ash and sodium sulfide solution, sodium hydroxide solution 8: 1; Sodium sulphite 300g/L; Sodium hydroxide 30g/L; 130 ℃ of temperature; Leach 3 hours reaction times.
Claims (3)
1, a kind of oxidation oven ash hydrometallurgical leaching process is characterized in that adopting following steps:
A, oxidized still cigarette ash and sodium sulfide solution, the sodium hydroxide solution that reclaims mixed in reactor and heat, after reaction is finished, filtration; Processing condition are: the solvent and solute weight ratio of oxidized still cigarette ash and sodium sulfide solution and sodium hydroxide solution=5～10: 1; Sodium sulfide solution concentration 150～350g/L; Concentration of sodium hydroxide solution 20～50g/L; 95～130 ℃ of reactor controlled temperature; 1～3 hour reaction times;
B, the filter residue of getting the A step return silver-colored smelting reducing melting and reclaim plumbous, silver, copper and bismuth;
C, get the filtrate in the A step, adjust the surplus temperature of filtrate and keep 80 ℃, in filtrate bubbling air or and the interpolation oxygenant, separate elemental sulfur once more after filtration;
D, the filtrate cooling that the C step is separated behind the elemental sulfur are condensed to 28～30 ℃, and crystallization is extracted the white crystals body and got thick sodium antimonate product; Remaining thioarsenic acid sodium solution gives other operation waste liquid recycling.
2, oxidation oven ash hydrometallurgical leaching process according to claim 1 is characterized in that: described processing condition are: the solvent and solute weight ratio of oxidized still cigarette ash and sodium sulfide solution and sodium hydroxide solution=8: 1; Sodium sulfide solution concentration 300g/L; Concentration of sodium hydroxide solution 30g/L; 130 ℃ of reactor controlled temperature; 3 hours reaction times.
3, oxidation oven ash hydrometallurgical leaching process according to claim 1 is characterized in that: the oxygenant that described step C selects to add is that Potcrate is or/and SODIUMNITRATE.
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Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103290221A (en) * | 2012-02-28 | 2013-09-11 | 兰州理工大学 | Method for recovering copper, arsenium and antimony from black copper sludge |
| CN103484693A (en) * | 2013-10-10 | 2014-01-01 | 郴州市金贵银业股份有限公司 | Harmlessness method for treating arsenic in antimony oxide |
| CN105624412A (en) * | 2016-01-18 | 2016-06-01 | 中南大学 | Copper soot smelting and separation combined treatment method |
| CN105648226A (en) * | 2014-11-15 | 2016-06-08 | 中国科学院过程工程研究所 | Method for separating antimony from arsenic in antimony-arsenic soot |
| CN105648227A (en) * | 2014-11-15 | 2016-06-08 | 中国科学院过程工程研究所 | Method for separating antimony and arsenic from antimony and arsenic-containing ash through oxidation and alkaline leaching |
| CN108455669A (en) * | 2018-04-23 | 2018-08-28 | 长沙烨星锑业有限公司 | A kind of preparation method of schlippe's salt |
| CN109173340A (en) * | 2018-11-08 | 2019-01-11 | 中南大学 | A method of the adsorbing and removing chlorine from strongly acidic solution |
| CN109763000A (en) * | 2018-12-10 | 2019-05-17 | 六盘水中联工贸实业有限公司 | A method of from height containing air oxidation removal arsenic in arsenic, zinc acid solution |
| CN110607452A (en) * | 2019-09-09 | 2019-12-24 | 攀枝花火凤凰再生资源回收利用有限责任公司 | Comprehensive utilization method of iron ore sintering smoke dust leaching solution |
| CN114574716A (en) * | 2022-02-28 | 2022-06-03 | 中南大学 | Method for removing arsenic from antimony-containing high-arsenic soot and recovering valuable antimony |
| CN116121543A (en) * | 2023-02-14 | 2023-05-16 | 东华大学 | Method for recycling antimony lead and noble metal by sulfuration reduction smelting of dearsenified lead anode slime |
-
2008
- 2008-07-27 CN CNA2008100319632A patent/CN101328539A/en active Pending
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103290221A (en) * | 2012-02-28 | 2013-09-11 | 兰州理工大学 | Method for recovering copper, arsenium and antimony from black copper sludge |
| CN103484693A (en) * | 2013-10-10 | 2014-01-01 | 郴州市金贵银业股份有限公司 | Harmlessness method for treating arsenic in antimony oxide |
| CN105648226A (en) * | 2014-11-15 | 2016-06-08 | 中国科学院过程工程研究所 | Method for separating antimony from arsenic in antimony-arsenic soot |
| CN105648227A (en) * | 2014-11-15 | 2016-06-08 | 中国科学院过程工程研究所 | Method for separating antimony and arsenic from antimony and arsenic-containing ash through oxidation and alkaline leaching |
| CN105624412A (en) * | 2016-01-18 | 2016-06-01 | 中南大学 | Copper soot smelting and separation combined treatment method |
| CN108455669A (en) * | 2018-04-23 | 2018-08-28 | 长沙烨星锑业有限公司 | A kind of preparation method of schlippe's salt |
| CN109173340A (en) * | 2018-11-08 | 2019-01-11 | 中南大学 | A method of the adsorbing and removing chlorine from strongly acidic solution |
| CN109173340B (en) * | 2018-11-08 | 2020-11-17 | 中南大学 | Method for removing chlorine from strong acidic solution by adsorption |
| CN109763000A (en) * | 2018-12-10 | 2019-05-17 | 六盘水中联工贸实业有限公司 | A method of from height containing air oxidation removal arsenic in arsenic, zinc acid solution |
| CN110607452A (en) * | 2019-09-09 | 2019-12-24 | 攀枝花火凤凰再生资源回收利用有限责任公司 | Comprehensive utilization method of iron ore sintering smoke dust leaching solution |
| CN114574716A (en) * | 2022-02-28 | 2022-06-03 | 中南大学 | Method for removing arsenic from antimony-containing high-arsenic soot and recovering valuable antimony |
| CN116121543A (en) * | 2023-02-14 | 2023-05-16 | 东华大学 | Method for recycling antimony lead and noble metal by sulfuration reduction smelting of dearsenified lead anode slime |
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Open date: 20081224 |