CN101265520A - Treatment method for refining lead slag-removed by antimony fire refining process - Google Patents
Treatment method for refining lead slag-removed by antimony fire refining process Download PDFInfo
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- CN101265520A CN101265520A CNA200810031207XA CN200810031207A CN101265520A CN 101265520 A CN101265520 A CN 101265520A CN A200810031207X A CNA200810031207X A CN A200810031207XA CN 200810031207 A CN200810031207 A CN 200810031207A CN 101265520 A CN101265520 A CN 101265520A
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- antimony
- lead slag
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- 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
A method for removing lead skim from antimony during fire refining comprises the following steps of: (1) performing primary leaching with water and ammonium salt as leaching agent at room temperature to 100 DEG C, and filtering to obtain filter residue containing valuable metals such as antimony and lead and a phosphorus-containing filtrate; (2) adding 1-3 times of water into the filter residue, performing secondary leaching at 50-100 DEG C for 30-90 min, filtering, recycling the filtrate to the primary leaching process, and recycling the filter residue into refining process to recover valuable metals; (3) reaching with ammonium salt; and (4) precipitating lead and arsenic. The inventive method can integrally recover various valuable components in the lead skim; and has the advantages of low cost, and no waste secondary pollution.
Description
Technical field
The present invention relates to a kind of treatment process of phosphorous material, particularly relate to a kind of treatment process of phosphorous material refining lead slag-removed by antimony fire refining process.
Background technology
Lead extensively is present in the natural various mineral, and people smelt in exploitation, extracts in the process of other various valuable metals, and lead wishes to be removed with regard to becoming unwanted impurity.The character easily oxidized according to lead, the general method deleading that adds the phosphoric acid salt oxidation that adopts.In the fire refining of antimony process, also be to adopt to add phosphoric acid salt, with the method that lead is removed from base metal, lead enters in the slag, forms the refining lead slag-removed by antimony fire refining process of leaded, antimony, phosphorus and other small amount of impurities (as arsenic etc.) and ash etc.The contained lead of this lead slag-removed material exists with lead phosphate or the plumbous form of metaphosphoric acid, and antimony exists simultaneously with metallic antimony, weisspiessglanz, phosphoric acid antimony or metaphosphoric acid antimony form, all is insoluble in water.Xikuangshan Shanxing Antimony Industry Co., Ltd once proposed two kinds of treatment processs: first kind is to utilize ferro element than antimony, character that the lead element chemical activity is strong, in the antimony regulus reverberatory furnace with after the lead slag-removed intensification fusing, in melt, add iron filings again, antimony just cements out, plumbous, iron generates phosphoric acid salt and enters in the slag and discard, and produces secondary residue again; Second method is to enter blast furnace with antimony regulus alkaline residue, melt cinder and antimong-containing material and carry out retailoring lead slag-removed, and antimony lead forms alloy, and phosphorus enters slag and discards, and produces secondary residue equally again.These two kinds of treatment process metal recovery rates are all low, and raw materials consumption is many, the processing cost height, and deficiency in economic performance, and " three wastes " secondary pollution is arranged.
Summary of the invention
The object of the present invention is to provide a kind of processing cost low, can comprehensively reclaim the valence component that has in the material, and not produce the treatment process of the refining lead slag-removed by antimony fire refining process of " three wastes ".
The objective of the invention is to be achieved through the following technical solutions: it may further comprise the steps:
(1) once leach: leaching agent is water and ammonium salt; Water and lead slag-removed weight proportion are 1-5: 1, the ammonium salt consumption is 0.4-0.8 with the ratio of lead slag-removed weight: 1, can leach at normal temperature, but for improving leaching efficiency, should be 50-100 ℃ of leaching, preferred extraction temperature is 60-90 ℃, preferred extraction temperature is 70-80 ℃ (can improve leaching efficiency though improve extraction temperature, but energy consumption also can improve thereupon, thereby is not high more good more); Extraction time is 30-90 minute (preferred 40-80 minute; More preferably 50-70 minute); To leach material filtering, obtain containing the filter residue and the phosphorous filtrate of valuable metals such as antimony, lead;
The leaching principle is: utilize the reaction of phosphate radical or metaphosphate ion and ammonium ion to generate water-soluble ammonium phosphate salt, and other compositions are that valuable metals such as antimony, weisspiessglanz, plumbous oxide and ash etc. are water insoluble, thus, by leaching, the phosphorous composition of solubility is separated with insoluble other compositions;
(2) secondary leaches: phosphorus content reduces as far as possible in the filter residue in order to make, can in leached mud, add water again, amount of water is 1-3 times (preferred 2 times) of the quantity of slag, under 50-100 ℃ temperature, leached 30-90 minute, filter, secondary filtrate is used for once leaching, and filter residue returns smelts Production Flow Chart recovery valuable metal;
(3) inhaling ammonification closes: with NH
3Fed phosphorous filtrate 40-60 minute, according to the NH in the phosphorous filtrate
3Concentration and free PO
4 3-Ionic concn adds phosphoric acid or Vanadium Pentoxide in FLAKES 50-80kg/m in phosphorous filtrate
3Filtrate is mixed, and adjusts pH value of solution value≤5, is warming up under normal pressure≤100 ℃, and the combination reaction time is 30-60 minute, and the ammonium ion reaction in phosphate anion and the filtrate obtains phosphoric acid ammonium salt filtrate:
NH
4 ++PO
4 3-+2H
+→NH
4H
2PO
4
NH
4H
2PO
4+NH
3→(NH
4)
2HPO
4
(4) heavy plumbous, arsenic: also contain impurity elements such as a spot of lead, arsenic in the phosphoric acid ammonium salt phosphorus filtrate, be deleading arsenic, the precipitation agent that need add deleading arsenic again, when precipitation agent is dissolvable sulfide (as sodium sulphite, hydrogen sulfide, ammonium sulfide etc.), adjust pH value of solution≤5, the precipitation agent add-on is 1-2kg/m
3Solution, temperature of reaction 70-80 ℃, time 50-70 minute; Filtrate behind heavy plumbous, the arsenic is by filtering once more, and is heavy clear, obtains the very low phosphate solution of leaded arsenic, and its lead, arsenic content can be low to moderate≤0.005%, filters the lead skim that obtains and contain arsenic less than 1%, leaded about 5%, still returns to smelt Production Flow Chart and reclaim plumbous; With phosphatic solution concentration, crystallization obtains phosphoric acid salt (as Secondary ammonium phosphate, primary ammonium phosphate, tertiary sodium phosphate, phosphoric acid five sodium etc.) product, and filtrate returning is used for once leaching.
In the above step, (2), (3), (4) step is the selectivity preferred steps.As do not carry out (2), (3), (4) step, the phosphorous first-time filtrate of (1) step gained can concentrate, crystallization obtains phosphoric acid salt; Filter residue returns valuable metals such as smelting Production Flow Chart recovery antimony.
Processing cost of the present invention is low, has valence component comprehensively to reclaim to various in the phosphorous material refining lead slag-removed by antimony fire refining process, and does not produce " three wastes " secondary pollution.
Embodiment
Below in conjunction with embodiment, the invention will be further described.
Embodiment 1:
(1) once leach: get the 100kg of antimony smeltery lead slag-removed (containing antimony 35%, lead 10%, phosphorus 10%), fragmentation adds 200 liters in water, ammonium phosphate 50kg, put into 300 liters of retort, stir, logical steam-heated cal(l)andria, solution is warming up to 90 ℃, reacted 30 minutes, filter for the first time;
(2) once leach: filter residue adds 200 liters in water again, and reaction is 30 minutes under 90 ℃ temperature, filters for the second time, the heavy 71.93kg of filter residue, wherein moisture 16.59%, dried antimony content in slag 57.17%, plumbous 16.60%, phosphorus 1.05%, secondary filtrate is used for once leaching, and first-time filtrate contains solubility Vanadium Pentoxide in FLAKES 150.28g/l, antimony 3.58g/l, plumbous 0.52g/l, arsenic 0.10g/l, filter residue return to smelt in the Production Flow Chart and reclaim valuable metal;
(3) inhaling ammonification closes: get 1 liter of the first-time filtrate (leach liquor) that (1) step mentioned, put into 2 liters of containers, feed NH
350 minutes, add phosphatase 24 0mg, adjusting the pH value of solution value is 4.5, stirs and is warming up to 80 ℃, reacts 30 minutes, obtains the phosphoric acid salts solution;
(4) deleading, arsenic: get and inhale the phosphoric acid salts solution 500ml that obtains after ammonification is closed, add hydrogen sulfide, adjust pH value 4.5, stirring is warming up to 80 ℃, reacted 30 minutes, after treating to produce red precipitate in the solution, vacuum filtration, the residue washing oven dry, heavy 5.12g contains antimony 4.49%, and plumbous 4.83%, arsenic 0.73% returns to smelt in the Production Flow Chart and reclaims valuable metal; Solution is heated to 100 ℃, is concentrated into 275ml, crystallisation by cooling, and filtering drying gets phosphate product 125g, wherein contains Vanadium Pentoxide in FLAKES 59.28%, antimony 1.25%, lead 0.01%, arsenic 0.01%, solution return and are used for once leaching.
Embodiment 2:
Get phosphorous, ammonia solution 500ml that embodiment 1 obtains, add Vanadium Pentoxide in FLAKES 30mg, adjusting the pH value is 4.8, logical steam-heated cal(l)andria is warming up to 90 ℃, reacts 40 minutes, obtain the phosphoric acid ammonium solution after, add ammonium sulfide solution 5g again, adjusting the pH value again is 4.8, filters the residue washing oven dry, heavy 5.68g, contain antimony 1.80%, lead 4.31%, arsenic 0.64% return to smelt in the Production Flow Chart and reclaim valuable metal; Filtrate is heated to 100 ℃, is concentrated into 275ml, and crystallisation by cooling filters, dries, and gets phosphate product 125g, wherein contains Vanadium Pentoxide in FLAKES 59.68%, antimony 1.35%, and lead 0.012%, arsenic 0.001%, solution return and are used for once leaching.
Embodiment 3
Get lead slag-removed (containing antimony 35%, lead 10%, phosphorus 10%) 5kg, fragmentation.Add 2 liters in water in retort, ammonium nitrate 0.06kg drops into broken lead slag-removed 0.1kg again, stirs, and logical steam heating is warming up to 60 ℃, reacts 90 minutes, filters; Filter residue adds 2 liters in water again, and reaction is 40 minutes under 80 ℃ temperature, filters for the second time, the heavy 70.89g of filter residue, wherein moisture 15.8%, dried antimony content in slag 60.08%, leaded 17.16%, phosphorus 0.98%, secondary filtrate is used for once leaching, first-time filtrate contains solubility Vanadium Pentoxide in FLAKES 149.89g/l, antimony 3.68g/l, plumbous 0.56g/l, arsenic 0.09g/l concentrates crystallisation by cooling, oven dry gets phosphate product; Filter residue returns smeltery's Production Flow Chart and reclaims valuable metal.
Embodiment 4:
Get the lead slag-removed 1kg of embodiment 3 fragmentations, add 2 liters in water, ammonium chloride 0.5kg, put into 3 liters retort, logical steam heats up and stirs, and solution is warming up to 70 ℃, reacted 60 minutes, and filtered (the heavy 718.5g of filter residue, wherein moisture 16.52% for the first time, dried antimony content in slag 58.16%, lead 16.03%, phosphorus 1.02%), filter residue adds 2 liters in water, reaction is 50 minutes under 90 ℃ temperature, filters (the heavy 718.5g of filter residue, wherein moisture 16.52% for the second time, dried antimony content in slag 58.16%, lead 16.03%, phosphorus 1.02%), secondary filtrate is used for once leaching, first-time filtrate contains solubility Vanadium Pentoxide in FLAKES 149.96g/l, antimony 3.28g/l, plumbous 0.58g/l, arsenic 0.12g/l, concentrate, crystallisation by cooling, oven dry gets phosphate product; Filter residue returns in smeltery's Production Flow Chart and reclaims valuable metal.
Embodiment 5:
Get the broken lead slag-removed 1.5kg of embodiment 3, add 3 liters in water, ammonium sulfate 0.75kg puts into 5 liters retort, and logical steam heats up, and stirs, and solution is warming up to 90 ℃, reacts 40 minutes, filters for the first time; Filter residue adds 3 liters in water again, and reaction is 40 minutes under 80 ℃ of temperature, filters for the second time, the heavy 7192g of filter residue, wherein moisture 16.58%, dried antimony content in slag 57.18%, lead 16.62%, phosphorus 1.04%, secondary filtrate is used for once leaching, first-time filtrate contains solubility Vanadium Pentoxide in FLAKES 150.29g/l, antimony 3.36g/l, plumbous 0.51g/l, arsenic 0.12g/l concentrates crystallisation by cooling, oven dry gets phosphate product; Filter residue returns in time refining Production Flow Chart and reclaims valuable metal.
The described per-cent of this specification sheets all is weight percentage.
Claims (6)
1, a kind of treatment process of refining lead slag-removed by antimony fire refining process, it is characterized in that, leach processing to lead slag-removed, leaching agent is water and ammonium salt, water and lead slag-removed weight proportion are 1-5: 1, the ammonium salt consumption is 0.4-0.8 with the ratio of lead slag-removed weight: 1, and extraction temperature is a room temperature-100 ℃, extraction time is 30-90 minute; To leach material filtering, obtain containing the filter residue and the phosphorous filtrate of valency metal.
2, the treatment process of refining lead slag-removed by antimony fire refining process according to claim 1 is characterized in that, described extraction temperature is 60-90 ℃, and extraction time is 40-80 minute.
3, the treatment process of refining lead slag-removed by antimony fire refining process according to claim 2 is characterized in that, described extraction temperature is 70-80 ℃, and extraction time is 50-70 minute.
4, according to the treatment process of one of claim 1-3 described refining lead slag-removed by antimony fire refining process, it is characterized in that, in the gained filter residue, add water, amount of water is 1-3 a times of filter residue weight, under 50-100 ℃ temperature, leached 30-90 minute, filter, filtrate is used for once leaching, and filter residue returns smelts Production Flow Chart recovery valuable metal.
5, according to the treatment process of one of claim 1-3 described refining lead slag-removed by antimony fire refining process, it is characterized in that, NH
3Fed phosphorous filtrate 40-60 minute, and added phosphoric acid or Vanadium Pentoxide in FLAKES 50-80kg/m then
3Filtrate is mixed, and adjusts pH value of solution value≤5, is warming up under normal pressure≤100 ℃, and the combination reaction time is 30-60 minute, gets phosphoric acid ammonium salt filtrate.
6, the treatment process of refining lead slag-removed by antimony fire refining process according to claim 5 is characterized in that, adds the precipitation agent of deleading arsenic in described phosphoric acid ammonium salt filtrate, and described precipitation agent is a dissolubility sulfide, adjusts pH value of solution≤5, and the precipitation agent add-on is 1-2kg/m
3Solution, temperature of reaction 70-80 ℃, time 50-70 minute; Filtrate behind heavy lead, the arsenic passes through to filter once more, and is heavy clear, obtains the very low phosphate solution of leaded arsenic, and the lead skim that filtration obtains returns the smelting Production Flow Chart and reclaims plumbous; Phosphatic filtrate is concentrated, and crystallization obtains phosphate product, and filtrate the returning after the crystallization is used for once leaching.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102251127A (en) * | 2011-07-04 | 2011-11-23 | 邹光平 | Comprehensive wet recovery method for removing lead slag from stibium through pyrorefining |
| CN103555933A (en) * | 2013-11-18 | 2014-02-05 | 中南大学 | Method for extracting molybdenum and nickel and enriching precious metals from nickel and molybdenum ores |
| CN103740950A (en) * | 2014-01-24 | 2014-04-23 | 锡矿山闪星锑业有限责任公司 | Processing method of lead removing slags generated by antimony smelting |
| CN103864041A (en) * | 2014-03-31 | 2014-06-18 | 锡矿山闪星锑业有限责任公司 | Integrated recovery processing process of deleading slag generated by smelting antimony |
| CN106222424A (en) * | 2016-08-29 | 2016-12-14 | 锡矿山闪星锑业有限责任公司 | A kind of from noble antimonial alloy, synthetical recovery is expensive, the method for base metal |
| CN112169971A (en) * | 2020-08-19 | 2021-01-05 | 新疆众和股份有限公司 | Method for recovering aluminum in primary aluminum ash |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1349041A (en) * | 1971-12-30 | 1974-03-27 | Occidental Petroleum Corp | Hydro metallurgical preparation of the oxides of antimony and antimonic acid |
| CN1042653C (en) * | 1994-08-19 | 1999-03-24 | 锡矿山矿务局 | Stibium fire refining deleading agent, its preparation and application |
| CN1123335A (en) * | 1994-11-25 | 1996-05-29 | 刘伯龙 | Lead-removing method for ammonium salt refined by antimony affination process |
| IT1282959B1 (en) * | 1996-05-06 | 1998-04-02 | Engitec Spa | PROCESS OF HYDROMETALLURGIC AND ELECTROCHEMICAL TREATMENT OF ANTIMONY SULFURATED MINERALS WITH ANTIMONIUM PRODUCTION |
-
2008
- 2008-05-06 CN CN200810031207XA patent/CN101265520B/en active Active
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102251127A (en) * | 2011-07-04 | 2011-11-23 | 邹光平 | Comprehensive wet recovery method for removing lead slag from stibium through pyrorefining |
| CN103555933A (en) * | 2013-11-18 | 2014-02-05 | 中南大学 | Method for extracting molybdenum and nickel and enriching precious metals from nickel and molybdenum ores |
| CN103555933B (en) * | 2013-11-18 | 2015-10-07 | 中南大学 | A kind of method extracting molybdenum and nickel and enriching noble metals from nickel-molybdenum ore |
| CN103740950A (en) * | 2014-01-24 | 2014-04-23 | 锡矿山闪星锑业有限责任公司 | Processing method of lead removing slags generated by antimony smelting |
| CN103864041A (en) * | 2014-03-31 | 2014-06-18 | 锡矿山闪星锑业有限责任公司 | Integrated recovery processing process of deleading slag generated by smelting antimony |
| CN103864041B (en) * | 2014-03-31 | 2016-04-13 | 锡矿山闪星锑业有限责任公司 | The lead slag-removed synthetical recovery treatment process that a kind of antimony regulus produces |
| CN106222424A (en) * | 2016-08-29 | 2016-12-14 | 锡矿山闪星锑业有限责任公司 | A kind of from noble antimonial alloy, synthetical recovery is expensive, the method for base metal |
| CN112169971A (en) * | 2020-08-19 | 2021-01-05 | 新疆众和股份有限公司 | Method for recovering aluminum in primary aluminum ash |
| CN112169971B (en) * | 2020-08-19 | 2022-03-11 | 新疆众和股份有限公司 | Method for recovering aluminum in primary aluminum ash |
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