CN101724753A - Low-temperature alkaline lead-smelting method - Google Patents
Low-temperature alkaline lead-smelting method Download PDFInfo
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- CN101724753A CN101724753A CN200910312440A CN200910312440A CN101724753A CN 101724753 A CN101724753 A CN 101724753A CN 200910312440 A CN200910312440 A CN 200910312440A CN 200910312440 A CN200910312440 A CN 200910312440A CN 101724753 A CN101724753 A CN 101724753A
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- lead
- smelting
- causticization
- low temperature
- alkali refining
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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
The invention discloses a low-temperature alkaline lead-smelting method, which is characterized by smelting lead sulphide concentrate and a secondary lead raw material at the temperature of between 600 and 900 DEG C under an alkaline condition to extract crude lead, and then using hydrometallurgy and a beneficiation method to process furnace slag to recover accompanying elements such as copper, zinc and the like and regenerate alkali for return use. The method comprises the processes such as alkaline smelting, water immersion, beneficiation of liquid leached residue, alkali regeneration from a water extract, sulfur recovery and the like. The method greatly reduces lead-smelting temperature, and reduces smelting cost due to the regeneration and the reuse of the alkali. CuS, Cu2S, ZnS, SiO2 and the like have no phase transformation during the smelting, so the beneficiation method can be used to recover the accompanying elements such as the copper, the zinc and the like, which has easy realization; and particularly, the method eliminates the pollution of lead dust, lead fog and sulfur dioxide flue gas to the environment seriously existing in conventional high-temperature lead smelting method. The method is a clean lead-smelting method with mild conditions and good environment, and has important significance and application prospect on the improvement of lead smelting technology.
Description
Technical field
The present invention relates to a kind of low temperature and mix alkali refining lead method, belong to field of metallurgy.
Background technology
Traditional lead smelting technology mainly is sinter machine sintering retailoring of blast furnace or bottom convertor melting technology, all be under 1250-1350 ℃ high temperature, to carry out, not only power consumption is high, and has following insoluble environmental problem: the plumbous mist that (1) plumbous smelting process produces a large amount of lead steams and disperse causes the severe contamination at factory's surrounding area air, soil and water source; (2) high-temperature process that produce copper dross slag in smelting process, contains zinc furnace cinder etc. also produces a large amount of lead dusts and low concentration SO
2Smoke pollution, the processing of lead matte and the recovery of copper are still unsolved at present difficult problems.
Summary of the invention
The object of the present invention is to provide a kind of low temperature to mix alkali refining lead method.This method significantly reduces temperature and realizes solid sulphur melting, directly smelts lead bullion, at utmost eliminates lead dust, plumbous mist and sulfur dioxide flue gas and pollutes, and reaches the plumbous purpose of cleaning refining.
The ultimate principle of the main process of the present invention is as follows:
(1) fusion process
2PbS+4NaOH+C=2Pb+2Na
2S+CO
2+2H
2O (1)
2PbSO
4+4NaOH+5C=2Pb+2Na
2S+5CO
2+2H
2O (2)
2PbO+C=2Pb+CO
2 (3)
2NaHCO
3=Na
2CO
3+H
2O+CO
2 (4)
2PbS+2Na
2CO
3+C=2Pb+2Na
2S+3CO
2 (5)
Na
2SO
4+2C=Na
2S+2CO
2 (6)
(2) causticization process
Na
2S+ZnO+H
2O=2NaOH+ZnS (7)
(3) roasting process
ZnS+1.5O
2=ZnO+SO
2 (8)
(4) carbonation
2NaOH+CO
2=NaHCO
3+H
2O (9)
Na
2CO
3+CO
2+H
2O=2NaHCO
3 (10)
(5) secondary causticization process
Na
2CO
3+Ca(OH)
2=2NaOH+CaCO
3 (11)
2Na
3AsO
4+3Ca(OH)
2=Ca
3(AsO
4)
2+6NaOH (12)
A kind of low temperature mixes alkali refining lead method: under 600-900 ℃ condition, add Na
2CO
3Or NaHCO
3And NaOH (equation according to above-mentioned reaction calculates consumption), smelt lead ore concentrate, secondary lead raw material or both mixtures and extract lead bullion; The water logging alkaline residue carries out ore dressing to the water logging slag then, obtains copper ore concentrates, zinc ore concentrate and lead ore concentrate.
Be 1~4 hour tap to tap time; The sodium mass ratio is Na
2CO
3Or NaHCO
3: NaOH=60~160: 5~80; The total alkali quality is 1.1~4.0 times of Theoretical Mass.And before smelting, earlier NaOH strong solution and lead ore concentrate and secondary lead raw material stirring are mixed, granulate remix or covering Na
2CO
3Or NaHCO
3, melting at last heats up.
Described secondary lead raw material refers to scrap battery clay or sulfuric acid lead skim or plumbous oxide cigarette ash.
Water logging alkaline residue process temperature is 30~100 ℃, and the time is 0.5~5 hour, and liquid-solid volume mass ratio is 1~6: 1; Water washing leached mud 3~5 times is to PH=7~8.
Infusion behind water logging alkaline residue ZnO causticization is with most of causticization liquid carbonating precipitation regeneration NaHCO
3, remainder causticization liquid secondary causticization, concentrated, regeneration NaOH solution; Causticization slag desulfurization with roasting technique regeneration causticizing agent ZnO, the SO that roasting produces
2Flue gas acid preparing.
ZnO is 1.1~3.0 times of Theoretical Mass in the causticization process; Temperature is 10~100 ℃; Time is 0.5~10.0 hour; Washing causticization slag 3-5 time.
In the carbonation temperature 10-95 ℃, the time is 0.5-10h, CO
2Volumetric usage is 1.05-2 a times of theoretical amount, reacts to 1H=3~8.
Temperature is 10-100 ℃ in the secondary causticization concentration process, and the time is 0.5-8h, Ca (OH)
2The quality consumption is 1.2-2.5 a times of theoretical amount, is concentrated into NaOH concentration 400-1500g/L.
The flow process of whole invention forms closed cycle, and the sodium loss in the working cycle replenishes by add saltcake in fusion process.
Tradition refining splicer plants and must earlier concentrate of lead sulfide ore be carried out oxygen-enriched air smelting or bake with agglomeration, and makes metallic sulfide be converted into oxide compound;
MeS+2/3O
2=MeO+SO
2 (13)
In the formula: Me represents Pb, Cu, Zn, Fe, Cd.
During oxygen-enriched air smelting, partial vulcanization lead is converted into metallic lead:
PbS+2PbO=3Pb+SO
2 (14)
Formula (13) and formula (14) show that sulphur is oxidized to sulfurous gas, and during oxygen-enriched air smelting, sulfurous gas is used for relieving haperacidity, but general melting is mostly with low concentration sulphur dioxide flue gas emptying, contaminate environment.
Follow rich lead skim of retailoring or agglomerate under 1250-1350 ℃ temperature, output lead bullion, Cu enter lead bullion and lead matte, and Zn is scattered in flue dust and the slag, makes copper and zinc be difficult to reclaim; On the other hand, at high temperature, plumbous volatility is very strong, as under the temperature of 973 ℃, 1162 ℃, 1234 ℃, 1309 ℃ and 1358 ℃, plumbous vapour pressure is respectively 0.133mmHg, 1.33mmHg, 13.3mmHg, 133mmHg and 1330mmHg, therefore, tradition refining splicer skill, no matter be oxygen-enriched air smelting, or the sintering and reducing melting, its production process all produces the severe contamination that a large amount of lead steams and the plumbous mist of disperse in the high-altitude cause factory's surrounding area air, soil and water source.
Carry out in the alkaline melt of the present invention under 600-900 ℃, reduced by 350~500 ℃, do not produce lead dust and plumbous mist than traditional method; Effectively eliminated plumbous pollution to the surrounding area.By formula (1), (2), (5) and (6), the sulphur in the furnace charge all is converted into sodium sulphite and is fixed in the smelted product, therefore, does not also produce sulfurous gas.
At Na
2CO
3For carrying out the alkaline reduction melting, CuS, Cu in the melt of main component and under 600~900 ℃ the temperature
2S, ZnS and SiO
2Deng being stable on thermodynamics, the thing phase change does not take place.Therefore, be easy to reclaim associated metals such as copper, zinc with beneficiation method.In a word, the present invention is the good cleaning lead smelting process of a kind of mild condition, environment, to the significant and application prospect of plumbous smelting technology progress.
Description of drawings
Fig. 1 is a process flow diagram of the present invention.
Embodiment
Following examples are intended to further specify the present invention, rather than restriction the present invention.
Embodiment 1
With the 1# concentrate of lead sulfide ore is that raw material carries out low-temperature alkaline lead-smelting, and the concentrate composition is (%): Pb70.12, Fe6.08, S15.04, Zn2.84, Cu0.40, SiO
20.79.
A. caustic fusion process
Take by weighing 21.66 gram caustic soda with 30ml water-soluble it, with 100 gram 1# lead ore concentrates and 5 gram reduction fine coal mixings, granulate, place plumbago crucible to take by weighing 76.07 gram soda ash again and be covered in the material surface of granulating, rise to 850 ℃ of insulation melting 60min; Obtain the heavy 65.68g of lead bullion, plumbous direct yield is 92%, basic slag 83.5 grams.
B. water logging process
Add entry 350mL and slag 82.3 grams in the 1000ml beaker, 60 ℃ are leached 2 hours after-filtration down, wash filter residue 3 times with 100mL, and pH value is 7.5.Filter residue dry weight 31.1g wherein contains Pb18.04%, Zn9.13%, Cu1.29%, Fe19.55%; Filtrate 500mL contains Na
2S 70.2/L, Na
2CO
3103.8g/L.
C. causticization process
Get above-mentioned immersion liquid 500mL and add the secondary zinc oxide 46.33g that contains Zn76.32%,, filter 80~85 ℃ of following causticizations 2 hours, ZnS
3Slag 54.9g, sulfur-bearing 26.18%; Causticization liquid 550ml contains NaOH 71.86g/L, Na
2CO
396.44g/L.
D. carbonation
Get an above-mentioned causticization liquid 353ml, feed CO down at 70-75 ℃
23h to pH value is 5.8, after the liquid-solid separation, obtains NaHCO
384.93g mother liquor 350ml contains NaHCO
360.5g/L.
E. secondary causticization process
Get an above-mentioned causticization liquid 197ml, at 60-70 ℃ of Ca (OH) with 85% content
223g causticization 2.5h obtains secondary causticization liquid 195ml, contains NaOH144.6g/L.
F. concentration process
With above-mentioned secondary causticization liquid 195ml, to 40ml, high alkali liquid contains NaOH 705g/L 95-110 ℃ of following evaporation concentration.
Embodiment 2
With 2# concentrate of lead sulfide ore and sulfuric acid lead skim is raw material, and its mass ratio is 1: 1.2# lead ore concentrate composition is (%): Pb51.55, Fe5.34, S18.52, Zn11.53, SiO
22.69, Cu0.11; Sulfuric acid lead skim composition (%) is Pb65, S10.04; Compound contains Pb58.27%, S14.28%.
A. fusion process
Take by weighing 34.6 gram caustic soda with 30ml water-soluble it, with 100 gram mixed lead raw materials and 15 gram reduction fine coal mixed pelletizations, place plumbago crucible, take by weighing 75.70 gram soda ash again, being covered in the material surface of granulating, rise to 850 ℃ of insulation melting 60min; Obtain the heavy 54.11g of lead bullion, plumbous direct yield is 92.8%, basic slag 131.04 grams.
B. water logging process
Water 350mL is added in the 1000ml beaker, above-mentioned slag 125 grams is soaked in wherein, loose after, be warming up to 90 ℃, 1 hour after-filtration of agitation leach is pressed embodiment 1 washing, gets infusion 600ml, water logging slag 20.70g, wherein contain Pb25.33%, Zn13.93%, Cu0.27%, Fe12.90%, infusion contains Na
2S 46.43/L, Na
2CO
3126.22g/L.
C. causticization process
Get above-mentioned immersion liquid 600mL and add the secondary zinc oxide 36.71g that contains Zn76.32%,, filter 80~85 ℃ of following causticizations 1.5 hours, ZnS
3Slag 43.5g, sulfur-bearing 26.22%; A causticization liquid 680ml contains NaOH 42.02g/L, Na
2CO
3111.37g/L.
D. carbonation
Get an above-mentioned causticization liquid 450 and feed CO down at 70-80 ℃
22.5h to the pH value be 6.0, after the liquid-solid separation, obtain NaHCO
392.14g mother liquor 450ml contains NaHCO
360g/L.
E. secondary causticization process
Get an above-mentioned causticization liquid 230ml,, obtain secondary causticization liquid 220ml, contain NaOH 131.8g/L at 75-80 ℃ of slaked lime 33.53g causticization 3h with 80% content.
F. concentration process
With above-mentioned secondary causticization liquid 220ml, to 40ml, high alkali liquid contains NaOH 725g/L 95-110 ℃ of following evaporation concentration.
Embodiment 3
Be that raw material carries out low-temperature alkaline lead-smelting still with the 1# concentrate of lead sulfide ore.
A. caustic fusion process
Take by weighing 40.5 gram caustic soda with 50ml water-soluble it, take by weighing 56.00 gram soda ash, 5 gram reduction fine coal again, with 100 gram 1# lead ore concentrate mixings, place plumbago crucible, rise to 650 ℃ of insulation melting 90min; Obtain the heavy 64.61g of lead bullion, plumbous direct yield is 90.5%, basic slag 93.8 grams.
B, C, D, E, F process such as embodiment 1.
Claims (10)
1. a low temperature mixes alkali refining lead method, it is characterized in that: under 600-900 ℃ condition, add Na
2CO
3Or NaHCO
3And NaOH, smelt lead ore concentrate, secondary lead raw material or both mixtures and extract lead bullion; The water logging alkaline residue carries out ore dressing to the water logging slag then, obtains copper ore concentrates, zinc ore concentrate and lead ore concentrate.
2. low temperature according to claim 1 mixes alkali refining lead method, it is characterized in that: be 1~4 hour tap to tap time; Na
2CO
3Or NaHCO
3: the sodium mass ratio is 60~160:5~80 among the NaOH; The total alkali quality is 1.1~4.0 times of Theoretical Mass.
3. low temperature according to claim 1 mixes alkali refining lead method, it is characterized in that: earlier NaOH strong solution and lead ore concentrate and secondary lead raw material stirring are mixed, granulate, remix or covering Na
2CO
3Or NaHCO
3, heat up at last and smelt.
4. mix alkali refining lead method according to claim 1 or 3 described low temperature, it is characterized in that: described secondary lead raw material comprises scrap battery clay or sulfuric acid lead skim or plumbous oxide cigarette ash.
5. low temperature according to claim 1 mixes alkali refining lead method, it is characterized in that: water logging alkaline residue process temperature is 30~100 ℃, and the time is 0.5~5 hour, and liquid-solid volume mass ratio is 1~6: 1; Water washing leached mud 3~5 times is to PH=7~8.
6. low temperature according to claim 1 mixes alkali refining lead method, it is characterized in that: with the infusion behind the ZnO causticization water logging alkaline residue, with most of causticization liquid carbonating precipitation regeneration NaHCO
3, remainder causticization liquid secondary causticization, concentrated, regeneration NaOH solution; Causticization slag desulfurization with roasting technique regeneration causticizing agent ZnO, the SO that roasting produces
2Flue gas acid preparing.
7. low temperature according to claim 6 mixes alkali refining lead method, it is characterized in that: ZnO is 1.1~3.0 times of Theoretical Mass in the causticization process; Temperature is 10~100 ℃; Time is 0.5~10.0 hour; Washing causticization slag 3-5 time.
8. low temperature according to claim 6 mixes alkali refining lead method, it is characterized in that: in the carbonation temperature 10-95 ℃, the time is 0.5-10h, CO
2Volumetric usage is 1.05-2 a times of theoretical amount, reacts to pH=3~8.
9. low temperature according to claim 6 mixes alkali refining lead method, it is characterized in that: temperature is 10-100 ℃ in the secondary causticization concentration process, and the time is 0.5-8h, Ca (OH)
2The quality consumption is 1.2-2.5 a times of theoretical amount, is concentrated into NaOH concentration 400-1500g/ L.
10. low temperature according to claim 6 mixes alkali refining lead method, it is characterized in that: the sodium loss in the working cycle replenishes by add saltcake in fusion process.
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CN102586584A (en) * | 2012-04-01 | 2012-07-18 | 大冶有色金属有限责任公司 | Method for selectively separating valuable metals from complex lead-containing precious metal material |
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CN106282588A (en) * | 2016-08-25 | 2017-01-04 | 安徽华铂再生资源科技有限公司 | Alkali regeneration method in reviver refine alkaline residue |
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CN101864522A (en) * | 2010-06-28 | 2010-10-20 | 中南大学 | Clean metallurgical method for low-temperature molten salt of lead |
CN101864522B (en) * | 2010-06-28 | 2012-07-25 | 中南大学 | Clean metallurgical method for low-temperature molten salt of lead |
CN102586584A (en) * | 2012-04-01 | 2012-07-18 | 大冶有色金属有限责任公司 | Method for selectively separating valuable metals from complex lead-containing precious metal material |
CN102776377A (en) * | 2012-08-23 | 2012-11-14 | 湖南中燎科技有限公司 | Method for conducting sulfur fixation treatment on lead-contained waste residues to recover valuable metal by side-blown smelting furnace |
CN103266226A (en) * | 2013-04-27 | 2013-08-28 | 中南大学 | Method for extracting silver from silver-containing zinc concentrate and improving quality of zinc concentrate |
CN104498716A (en) * | 2014-11-27 | 2015-04-08 | 合肥工业大学 | Energy-conserving and environment-protecting regenerated lead smelting and paper pulp cogeneration technology |
CN104498716B (en) * | 2014-11-27 | 2016-08-31 | 合肥工业大学 | A kind of secondary lead smelting co-producing paper pulp technology of energy-conserving and environment-protective |
CN106282588A (en) * | 2016-08-25 | 2017-01-04 | 安徽华铂再生资源科技有限公司 | Alkali regeneration method in reviver refine alkaline residue |
CN107142376A (en) * | 2017-04-01 | 2017-09-08 | 中南大学 | A kind of method that efficiently concentrating separates valuable metals from complex lead-containing precious metal material |
CN111100989A (en) * | 2019-12-13 | 2020-05-05 | 潘爱芳 | Method for activating metal tailings |
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