CN107447112B - A method of the enriched lead from low-grade lead skim - Google Patents

A method of the enriched lead from low-grade lead skim Download PDF

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CN107447112B
CN107447112B CN201710681742.9A CN201710681742A CN107447112B CN 107447112 B CN107447112 B CN 107447112B CN 201710681742 A CN201710681742 A CN 201710681742A CN 107447112 B CN107447112 B CN 107447112B
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liquid
lead
calcium
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skim
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CN107447112A (en
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王群
洪斌
杨桂芬
赵阔
王辉
张怡
彭锐
杨龙
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Chongqing Hongbo New Materials Technology Co ltd
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Yunnan Dragon Science And Technology Environmental Protection Ltd By Share Ltd
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    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22BPRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B7/00Working 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
    • C22B7/006Wet processes
    • C22B7/007Wet processes by acid leaching
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22BPRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B13/00Obtaining lead
    • C22B13/04Obtaining lead by wet processes
    • C22B13/045Recovery from waste materials
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02PCLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P10/00Technologies related to metal processing
    • Y02P10/20Recycling

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  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Metallurgy (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Organic Chemistry (AREA)
  • Geology (AREA)
  • General Life Sciences & Earth Sciences (AREA)
  • Environmental & Geological Engineering (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Processing Of Solid Wastes (AREA)
  • Manufacture And Refinement Of Metals (AREA)

Abstract

The invention discloses a kind of methods of enriched lead from low-grade lead skim, including the following steps: 1) low-grade lead skim is added to liquid after washing calcium chlorine, filter to obtain washing lotion and washery slag;2) washing lotion is heated up and adjusts PH, liquid after zinc calcium and magnesium slag and dezincification calcium and magnesium is filtered to obtain in reaction;3) washery slag is added to liquid after adjusting acid, leachate and leached mud are filtered to obtain in heating stirring;4) leachate is heated up, is stirred, adjusted pH value, obtain liquid and lead skim after de- lead;Liquid and calcium chloride solution adjust PH into after adjusting sour pond together again after de- lead, and liquid after tune acid is made, liquid after acid is adjusted to return step 3) use;5) liquid and a small amount of water after decalcification magnesium is added in the lead skim obtained in the step 4) with liquid-solid ratio 5:1, agitation and filtration obtains high lead slag and washes liquid after calcium chlorine, and liquid PH after calcium chlorine is washed in adjusting, washes liquid after calcium chlorine and returns in step 1) and uses;Invention bioaccumulation efficiency is high, and lead recovery is high;Lead recovery and treatment method after enrichment improves content is more, and technology difficulty is low, and development space is big.

Description

A method of the enriched lead from low-grade lead skim
Technical field
The present invention relates to zinc metallurgy recycling fields, more specifically, being a kind of method of enriched lead from low-grade lead skim.
Background technique
Sulfuric acid lead skim is that zinc metallurgy and zinc product produce and use the waste residue being discharged in the process, it is both the nocuousness for polluting environment Substance is also the secondary resource for extracting valuable constituent, it is therefore necessary to integrated treatment is carried out to it, to reach " increasing income and decreasing expenditure ", prevent The purpose of pollution.At present to being difficult to ore dressing and complicated component, the lead-containing material for being unsuitable for pyrogenic attack, pyrogenic process directly recycle sky Gas pollution is big, and energy consumption is high, and employment injuries is also larger, and hydrometallurgic recovery is avoided that the above problem, but technical difficulty is big.
Summary of the invention
In order to make up the above deficiency, the present invention provides a kind of methods of enriched lead from low-grade lead skim.
The scheme of the invention is:
A method of the enriched lead from low-grade lead skim, including the following steps:
1) low-grade lead skim is added to liquid after washing calcium chlorine with liquid-solid ratio 5:1,40~60 DEG C is heated up to, stirs 30 minutes, mistake Filter to obtain washing lotion and washery slag;
2) washing lotion is warming up to 65~70 DEG C, lime is added and adjusts pH > 12, zinc calcium and magnesium slag and de- is filtered to obtain in reaction for 30 minutes Liquid after zinc calcium and magnesium;
3) washery slag is added to liquid after adjusting acid with 6~5:1 of liquid-solid ratio, 70~90 DEG C is warming up to, stirs 1 hour, control terminal PH is 4~4.5, filters to obtain leachate and leached mud;
4) leachate is warming up to 80~90 DEG C or more, be added with stirring purification deleading reagent adjust pH value, half an hour it Interior adjusting pH to 7, after stablizing 30 minutes, it is 12 that a small amount of deleading reagent, which is added, to adjust pH according to pH value, and reaction is filtered after 30 minutes, is obtained Liquid and lead skim after de- lead;Liquid and calcium chloride saturated solution add a small amount of HCl adjusting into after adjusting sour pond together after the de- lead PH is 2~3, liquid after the tune acid is made, liquid returns the use of step 3) extracting stage after the tune acid;
5) liquid and a small amount of water after decalcification magnesium is added in the lead skim obtained in the step 4) with liquid-solid ratio 5:1, stirs 30 minutes, It filters high lead slag and to wash liquid after calcium chlorine, uses H2SO4It is 3~4 that liquid pH after calcium chlorine is washed in adjusting, and washing liquid after calcium chlorine and returning in step 1) makes With.
Taking off lead temperature in the step 4) as a preferred technical solution, is 80~90 DEG C, and deleading reagent is various alkalinity examinations Agent.
Deleading reagent is milk of lime in the step 4) as a preferred technical solution,.
The reaction principle that the invention is related to
PbSO4+CaCl2+ 2NaCl=CaSO4+Na2PbCl4
2Na2PbCl4+Ca(OH)2=2PbClOH+CaCl2+4NaCl
2PbClOH+Ca(OH)2=2PbO+2H2O+CaCl2
By adopting the above-described technical solution, a kind of method of the enriched lead from low-grade lead skim, including the following steps: 1) Low-grade lead skim is washed into liquid after calcium chlorine with liquid-solid ratio 5:1 addition, 40~60 DEG C is heated up to, stirs 30 minutes, filter washing lotion and Washery slag;2) washing lotion is warming up to 65~70 DEG C, lime is added and adjusts pH > 12, reaction filters to obtain zinc calcium and magnesium slag and dezincification in 30 minutes Liquid after calcium and magnesium;3) washery slag is added to liquid after adjusting acid with 6~5:1 of liquid-solid ratio, 70~90 DEG C is warming up to, stirs 1 hour, control terminal PH is 4~4.5, filters to obtain leachate and leached mud;4) leachate is warming up to 80~90 DEG C or more, it is de- is added with stirring purification Lead agent adjusts pH value, and pH to 7 is adjusted within half an hour, after stablizing 30 minutes, a small amount of deleading reagent is added according to pH value and adjusts pH It is 12, reaction is filtered after 30 minutes, obtains liquid and lead skim after de- lead;Liquid and calcium chloride saturated solution enter together after the de- lead adjusts Adding a small amount of HCl behind sour pond and adjusting pH is 2~3, and liquid after the tune acid is made, and liquid, which returns step 3) extracting stage, after the tune acid makes With;5) liquid and a small amount of water after decalcification magnesium is added in the lead skim obtained in the step 4) with liquid-solid ratio 5:1, stirs 30 minutes, filtering It obtains high lead slag and washes liquid after calcium chlorine, use H2SO4Liquid pH is 3~4 after calcium chlorine is washed in adjusting, and liquid returns use in step 1) after washing calcium chlorine;It should Invention is difficult using original technique and domestic most zinc hydrometallurgy factory present in low-grade lead skim or sulfuric acid lead skim as raw material, use Cheap industrial chlorinations sodium, calcium chloride and lime carries out desulfurization and enrichment to lead skim by simple process, and entire technique is realized molten The closed cycle of liquid, three-waste free discharge.In large-scale production, temperature loss is few, and leachate lead concentration is efficiently saved up to 40g/L Can, environmental protection and economy, product is leaded up to 65%~75%, and impurity is few, and post-processing can use pyrogenic process or wet process.Aftertreatment technology letter It is single, it is at low cost.This technique also may extend to the recycling industry of waste lead accumulator.
Detailed description of the invention
Fig. 1 is process flow chart of the invention.
Specific embodiment
Case study on implementation 1
Sulfuric acid lead skim contains Pb17.5%, Zn8%, Fe3.7%, Mn0.2%, Mg0.38%, S10%.
1, sulfuric acid lead skim is added to liquid after washing calcium chlorine with liquid-solid ratio 5:1,40~50 DEG C is heated up to, stirs 30 minutes, filtering Washing lotion and washery slag, washing lotion containing Pb < 50mg/L, Zn3.9g/L, Fe0.78g/L, Mn1.36g/L, Mg0.51g/L, Cl3.8g/L, SO4 2~10g/L, washery slag contain Pb20%.
2, washing lotion is warming up to 70 DEG C, lime is added and adjusts pH > 12, reaction filters to obtain zinc calcium and magnesium slag and dezincification calcium in 30 minutes Liquid after magnesium.Zinc calcium and magnesium slag contains Pb < 0.1%, Zn 12%, Fe2.4%, Mn2.6%, Mg2.6%, after dezincification calcium and magnesium liquid containing Pb < 150mg/L、Zn<200mg/L、Fe<50mg/L、Mn<50mg/L、Mg200mg/L、Cl17g/L。
3, washery slag is added to liquid (Pb140mg/L, Zn140mg/L, Ca 10g/L, Cl 200g/ after adjusting acid with liquid-solid ratio 5:1 L), 70~80 DEG C are warming up to, is stirred 1 hour, terminal pH about 4.5 is controlled, filters to obtain leachate and leached mud.Leachate contains Pb 30.4g/L, Zn 0.8g/L, Ca 4.1g/L, Cl 198g/L, leached mud contain Pb2.74%, Zn6.8%, and leached mud is again into fuming Furnace processing.
4, leachate is warming up to 80 DEG C or more, is added with stirring refined lime cream and adjusts pH value, is adjusted within half an hour PH to 7 is saved, after stablizing 30 minutes, it is 12 that a small amount of milk of lime, which is added, to adjust pH according to pH value, and reaction is filtered after 30 minutes, obtains de- lead Liquid and lead skim afterwards.Liquid contains Pb144mg/L, Zn147mg/L, Ca7.8g/L, Cl190g/L after de- lead, lead skim containing Pb61.8%, Zn0.84%, Cl17.6%.Liquid and calcium chloride saturated solution add a small amount of HCl adjusting pH into after adjusting sour pond together after de- lead It is 2~3, returns extracting stage use.
5, liquid and a small amount of water after decalcification magnesium is added into lead skim with liquid-solid ratio 5:1, stirs 30 minutes, filter high lead slag and Liquid after calcium chlorine is washed, liquid uses H containing Pb100mg/L, Zn200mg/L, Cl19g/L after washing calcium chlorine2SO4Adjusting pH is 3~4, returns first Step uses.High lead slag contains Pb72%, Zn1.2%, Cl8%.
Conclusion: technique lead recovery 95%, filter plant uses vertical type blotter press in leaching section, and supplementary product onsumption is few.
Case study on implementation 2
Sulfuric acid lead skim contains Pb27%, Zn10.9%, Fe2.8%, Mn0.3%, Mg0.38%, S11%.
1, sulfuric acid lead skim is added to liquid after washing calcium chlorine with liquid-solid ratio 5:1,50~60 DEG C is heated up to, stirs 30 minutes, filtering Washing lotion and washery slag are obtained, washing lotion contains Pb179mg/L, Zn3.9g/L, Fe 0.8g/L, Mn1.56g/L, Mg 0.62g/L, Cl 3.8g/ L、SO4 2~11g/L, washery slag contain Pb 34%.
2, washing lotion is warming up to 65 DEG C, lime is added and adjusts pH13~14, zinc calcium and magnesium slag and de- is filtered to obtain in reaction for 30 minutes Liquid after zinc calcium and magnesium.Zinc calcium and magnesium slag contains Pb < 0.1%, Zn 16.5%, Fe2.4%, Mn2.6%, Mg2.6%, liquid after dezincification calcium and magnesium Containing Pb < 50mg/L, Zn < 50mg/L, Fe < 50mg/L, Mn < 50mg/L, Mg200mg/L, Cl 25g/L.
3, washery slag is added to liquid (Pb 500mg/L, Zn 300mg/L, Ca 13.5g/L, Cl after adjusting acid with liquid-solid ratio 5:1 210g/L), 80~90 DEG C are warming up to, is stirred 1 hour, terminal pH about 4.0 is controlled, filters to obtain leachate and leached mud.Leachate 40.2g/L containing Pb, Zn0.8g/L, Ca 5.1g/L, Cl 205g/L, leached mud contain Pb1.5%, Zn 5.5%, leached mud again into Fuming furnace processing.
4, leachate temperature is maintained at 85~90 DEG C, be added with stirring refined lime cream adjust pH value, half an hour it Interior adjusting pH to 7, after stablizing 30 minutes, it is 12 that a small amount of milk of lime, which is added, to adjust pH according to pH value, and reaction is filtered after 30 minutes, is obtained Liquid and lead skim after de- lead.Liquid 200mg/L containing Pb, Zn500mg/L, Ca 12.0g/L, Cl 200g/L after de- lead, lead skim contain Pb 65%, Zn 0.65%, Cl 15.6%.Liquid and calcium chloride saturated solution add on a small quantity into after adjusting sour pond together after de- lead It is 2~3 that HCl, which adjusts pH, returns extracting stage use.
5, liquid and a small amount of water after decalcification magnesium is added into lead skim with liquid-solid ratio 5:1, stirs 30 minutes, filter high lead slag and Liquid after calcium chlorine is washed, liquid 50mg/L containing Pb, Zn 100mg/L, Cl19g/L after calcium chlorine is washed, uses H2SO4Adjusting pH is 3~4, returns first Step uses.High lead slag contains Pb75%, Zn1.5%, Cl 6.5%.
Conclusion: when raw material lead content is high, lead concentration is also high in leachate, lead recovery 95%.
Case study on implementation 3
Lead skim contains Pb10%, Zn13%, Fe5%, Mn0.8%, Mg0.4%, S12%.
1, low-grade lead skim is added to liquid after washing calcium chlorine with liquid-solid ratio 5:1,60 DEG C is heated up to, stirs 30 minutes, filter Washing lotion and washery slag, washing lotion 200mg/L containing Pb, Zn 20g/L, Fe 5g/L, Mn1.3g/L, Mg 0.62g/L, Cl 3.8g/L, SO4 2~13g/L, washery slag contain Pb 34%.
2, washing lotion is warming up to 65 DEG C, lime is added and adjusts pH13~14, zinc calcium and magnesium slag and de- is filtered to obtain in reaction for 30 minutes Liquid after zinc calcium and magnesium.Zinc calcium and magnesium slag contains Pb < 0.1%, Zn 16.5%, Fe2.4%, Mn2.6%, Mg2.6%, liquid after dezincification calcium and magnesium Containing Pb < 50mg/L, Zn < 50mg/L, Fe < 50mg/L, Mn < 50mg/L, Mg200mg/L, Cl 25g/L.
3, washery slag is added to liquid (Pb100mg/L, Zn 100mg/L, Ca 8.1g/L, Cl after adjusting acid with liquid-solid ratio 6:1 180g/L), 80~90 DEG C are warming up to, is stirred 1 hour, terminal pH about 4.0 is controlled, filters to obtain leachate and leached mud.Leachate Containing Pb15.5g/L, Zn0.3g/L, Ca 5.1g/L, Cl 178g/L, leached mud contains Pb0.75%, Zn 7.5%, leached mud again into Fuming furnace processing.
4, leachate temperature is maintained at 85~90 DEG C, be added with stirring refined lime cream adjust pH value, half an hour it Interior adjusting pH to 7, after stablizing 30 minutes, it is 12 that a small amount of milk of lime, which is added, to adjust pH according to pH value, and reaction is filtered after 30 minutes, is obtained Liquid and lead skim after de- lead.Liquid 200mg/L containing Pb, Zn 200mg/L, Ca 7.1g/L, Cl 175g/L after de- lead, lead skim contain Pb 60.2%, Zn 0.65%, Cl 15.6%.Liquid and calcium chloride saturated solution add on a small quantity into after adjusting sour pond together after de- lead It is 2~3 that HCl, which adjusts pH, returns extracting stage use.
5, liquid and a small amount of water after decalcification magnesium is added into lead skim with liquid-solid ratio 5:1, stirs 30 minutes, filter high lead slag and Liquid after calcium chlorine is washed, liquid 20mg/L containing Pb, Zn 500mg/L, Cl 14g/L after calcium chlorine is washed, uses H2SO4Adjusting pH is 3~4, returns the One step uses.High lead slag contains Pb 65%, Zn 2.5%, Cl 9.5%.
Conclusion: this technique lead recovery is 94.8%, selects washup according to the soluble impurity content of used lead skim Liquid-solid ratio increases washup number, can promote product quality, improve Pb-Zn separation effect.
The above shows and describes the basic principle, main features and advantages of the invention.The technology of the industry Personnel are it should be appreciated that the present invention is not limited to the above embodiments, and the above embodiments and description only describe this The principle of invention, without departing from the spirit and scope of the present invention, various changes and improvements may be made to the invention, these changes Change and improvement all fall within the protetion scope of the claimed invention.The claimed scope of the invention by appended claims and its Equivalent circle.

Claims (3)

1. a kind of method of the enriched lead from low-grade lead skim, characterized in that it comprises the following steps:
1) low-grade lead skim is added to liquid after washing calcium chlorine with liquid-solid ratio 5:1,40~60 DEG C is heated up to, stirs 30 minutes, filter Washing lotion and washery slag;
2) washing lotion is warming up to 65~70 DEG C, lime is added and adjusts pH > 12, reaction filters to obtain zinc calcium and magnesium slag and dezincification in 30 minutes Liquid after calcium and magnesium;
3) washery slag is added to liquid after adjusting acid with 6~5:1 of liquid-solid ratio, 70~90 DEG C is warming up to, stirs 1 hour, control terminal pH is 4~4.5, filter to obtain leachate and leached mud;
4) leachate is warming up to 80~90 DEG C or more, is added with stirring purification deleading reagent and adjusts pH value, is adjusted within half an hour PH to 7 is saved, after stablizing 30 minutes, it is 12 that a small amount of deleading reagent, which is added, to adjust pH according to pH value, and reaction is filtered after 30 minutes, is obtained Liquid and lead skim after de- lead;Liquid and calcium chloride saturated solution add a small amount of HCl adjusting into after adjusting sour pond together after the de- lead PH is 2~3, liquid after the tune acid is made, liquid returns the use of step 3) extracting stage after the tune acid;
5) liquid and a small amount of water after decalcification magnesium is added in the lead skim obtained in the step 4) with liquid-solid ratio 5:1, stirs 30 minutes, filtering It obtains high lead slag and washes liquid after calcium chlorine, use H2SO4Liquid pH is 3~4 after calcium chlorine is washed in adjusting, and liquid returns use in step 1) after washing calcium chlorine.
2. a kind of method of the enriched lead from low-grade lead skim as described in claim 1, it is characterised in that: in the step 4) De- lead temperature is 80~90 DEG C, and deleading reagent is various alkaline reagents.
3. a kind of method of the enriched lead from low-grade lead skim as described in claim 1, it is characterised in that: in the step 4) Deleading reagent is milk of lime.
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CN106939377A (en) * 2017-04-27 2017-07-11 中南大学 A kind of chlorination of sulfur acid lead materials takes off the method that lead liquid is recycled

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CN101555550A (en) * 2009-05-22 2009-10-14 北京科技大学 Method for recycling lead-tin in silver separating residue of copper anode slime of circuit board
CN103194615A (en) * 2013-03-27 2013-07-10 云南祥云飞龙有色金属股份有限公司 Lead hydrometallurgical technology through utilizing lead sulfate
CN104532014A (en) * 2014-12-23 2015-04-22 东莞市粤威环保科技有限公司 Innocent treatment of low-grade lead slag
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CN105907986A (en) * 2016-06-29 2016-08-31 江西铜业集团公司 Extracting method for lead in silver separating residues
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