CN105567978A - Method for recycling copper, zinc, cobalt and nickel from various kinds of nonferrous metal containing waste - Google Patents
Method for recycling copper, zinc, cobalt and nickel from various kinds of nonferrous metal containing waste Download PDFInfo
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- CN105567978A CN105567978A CN201610057010.8A CN201610057010A CN105567978A CN 105567978 A CN105567978 A CN 105567978A CN 201610057010 A CN201610057010 A CN 201610057010A CN 105567978 A CN105567978 A CN 105567978A
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B7/00—Working 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
- C22B7/006—Wet processes
- C22B7/007—Wet processes by acid leaching
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B19/00—Obtaining zinc or zinc oxide
- C22B19/30—Obtaining zinc or zinc oxide from metallic residues or scraps
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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
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- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
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Abstract
The invention discloses a method for recycling copper, zinc, cobalt and nickel from various kinds of nonferrous metal containing waste. The method comprises the steps that nonferrous metal containing dead catalysts, waste battery materials and other waste raw materials are subjected to leaching dissolution by adding acid and an oxidizing agent, a solution containing nickel, cobalt, copper and zinc is subjected to copper extraction after filter pressing, and reverse extraction is carried out on the copper solution for electro deposited copper production; and P204 extraction is carried out after the raffinate is subjected to deironing treatment, reverse extraction galvanizing zinc is obtained, a zinc carbonate product is obtained through settlement and roughening, P507 nickel and cobalt separation is carried out on the raffinate, and a cobalt salt solution and a nickel salt solution are obtained and used for producing cobalt sulphate, nickel carbonate, electrolytic nickel and other products. Leaching residues and deironining slag obtained after filter pressing are dissolved and enter a waste slag removal treatment workshop for sintering treatment.
Description
Technical field
The present invention relates to the cyclic regeneration field of resource, particularly from the various technology containing reclaiming copper zinc cobalt nickel the waste material of non-ferrous metal.
Background technology
Metallurgy industry all produces a large amount of solid waste every year, and these solid wastes all contain the valuable elements such as copper, cobalt, nickel, zinc.General copper, nickel fibers slag cupric can be even higher to 10 from some thousandths of, and containing cobalt, nickel can from some thousandths of to percentum, and the cobalt in concentrate even more than 90% all enters in smelting slag or blowing slag.Zinc hydrometallurgy factory calcine neutral leached mud and electric arc furnace dirt are containing zinc 10 to two ten.These metallurgical wastes both because have economic worth containing valuable metal, were also put into hazardous waste because of the existence of these elements simultaneously.Due to enormous amount, in addition year by year also in increase, wherein the existing huge economic worth of the cyclic regeneration of resource, has again urgent environment protection significance.
Also have and produce a large amount of recovery refuse batteries and spent catalyst every year, the waste residue after manufacturer just slightly reclaims etc., still containing precious metals such as copper cobalt nickel zinc, if can not extract totally, not only lose economic worth also contaminate environment.
In the prior art, also a lot of from the method for the various waste material of process:
(1), class is disposed in harmless treatment: carry out cement solidification, the innoxious thermal treatment of high temperature, landfill.This process method of disposal is not carried out valuable metal resource utilization in various waste material and is reclaimed, and does not meet resources conservation and circular economy policy.
(2), simple material utilizes class: as cement raw material, modified plastics, ceramic pigment.This process method of disposal is not carried out valuable metal resource utilization in various waste material and is reclaimed.
(3), class is disposed in pyrogenic attack: corronel or low nickel matte are reclaimed in high temperature reduction roasting.This process method of disposal only reclaims copper nickel, and copper nickel product specification is low, added value is little, also must carry out deep processing; Technique highly energy-consuming, produces smoke secondary and pollutes, do not meet energy-saving and emission-reduction policy.
(4), acidleach wet processing: reclaim the valuable metal such as nickel, copper.The maturation process of recycling, but general process method of disposal removal of impurities, separating technology are complicated, copper, nickel total recovery is on the low side, and cost recovery is higher, and product specification is lower, and economic benefit is not very good.
(5), ammonia leaching wet processing: reclaim nickel, copper etc.Although the technology that ammonia leaching process extracts metal has certain history, compared with pickling process, adopt the research report of ammonia leaching process process electroplating sludge relatively less, and in the majority with studies in China report.
Along with the development of technology, the process of electroplating sludge is disposed gradually to the future development recycling valuable resource.Pickling process is as technique the most ripe at present, investigation and application both domestic and external is many, ZL201010117128.8 as special in China discloses a kind of method reclaiming valuable metal from metallurgical waste (mainly wherein having the metallurgical slag of the valuable metal such as ferrosilicate and wustite cupric, cobalt, nickel, zinc, leached mud and flue dust), comprise the steps: 1) acidolysis: metallurgical waste is mixed with water, sulfuric acid, makes its reaction decomposes to discharge the valuable metal wherein combined; 2) roasting: the material after acidolysis and sulphur material are mixed to get compound, then pass into air roasting; Wherein said sulphur material is the material containing non-oxide state sulphur component, and maturing temperature controls at 450 DEG C ~ 800 DEG C; 3) leach: after roasting, calcining adds water leaching; 4) reclaim: after the solid-liquid separation on ore pulp after leaching, obtain supplying to reclaim wherein valuable metal containing the solution of valuable metal.This recovery method leaching efficiency is high, and economical, easy.But the sulfide roasting used can produce a large amount of sulphide staining environment, and valuable metal is separated not thorough.
Summary of the invention
The object of this invention is to provide a kind of can cost-effectively from various waste material as reclaimed the method for the valuable metal such as copper and cobalt, nickel, zinc the tank liquor containing nickel, cobalt, copper, zinc etc., mud, waste liquid, refuse battery material, waste residue, abandoned mine, spent catalyst and flue dust etc.
From the various method containing reclaiming copper zinc cobalt nickel the waste material of non-ferrous metal, comprise the steps:
(1), leaching is dissolved:
The various waste material containing non-ferrous metal is mixed, with ball milling, waste material is levigate, fineness requirement 200 order-400 order, then join in the sulfuric acid of 30%, add sodium chlorate simultaneously, stirring intensity 40 ~ 100rpm, first time is warmed up to more than 50 DEG C, reaction leaching 1 ~ 3 hour, then, start to drip the washing water of water or step (2), (4), can produce a large amount of heats, temperature controls at 60 ~ 90 DEG C, the cooling water temperature when temperature is too high, heat up water coolant can be used for first time heat up, can two complete equipment coproduction so that save energy; Drip 1 ~ 2 hour time of washing water, add washing water complete, stir 2 ~ 3 hours, so that soluble non-ferrous metal fully dissolves leaching; The mass ratio of waste material, sulfuric acid, water is 1:0.5 ~ 2:0.5 ~ 5;
(2), press filtration:
Dissolving leach liquor is cooled to less than 50 DEG C, press filtration, filter residue goes to Solid state fermentation workshop to carry out sintering processes after washing, filter residue needs repeatedly to wash, until metal content is lower than 0.1% in filter residue, washing water return step (1) and dissolve leaching operation, and press filtration mother liquor enters next process;
(3), copper extraction:
Leach press filtration mother liquor and be sent to copper extraction process, the copper compound in mother liquor is extracted through extraction, extraction liquid is made up of extraction agent and thinner, extraction agent is the composite extractant of LIX984 and M5640, thinner is 260# solvent oil, at room temperature multi-stage solvent extraction, and by multi-grade oil liquid/gas separator, extraction liquid and organic phase are collected together, aqueous phase enters down extraction together, until copper compound content is less than 1% in aqueous phase, last aqueous phase enters deironing press filtration operation, and 10% dilute sulphuric acid segmentation back extraction of organic phase preparation obtains copper-bath; Copper-bath adopts electrodeposition to reclaim copper; Extraction liquid can repeatedly use; The mass ratio of press filtration mother liquor, extraction liquid is 1:0.1 ~ 1; Mass ratio 1:8 ~ 10 of extractant in extract, thinner; Mass ratio 1:0.5 ~ 1.5 of LIX984, M5640 in extraction agent;
(4), deironing press filtration:
Aqueous phase after copper extraction is first 2.5 ~ 3.0 with alkali adjust ph, and add oxygenant, temperature controls at 20 ~ 50 DEG C, reacts 0.5 ~ 1 hour, then adds alkali and pH is adjusted to 3.5 ~ 3.8, press filtration, and the mother liquor after press filtration enters next process, press filtration mother liquor requirement Fe
2+< 0.05g/L; Filtering medium and scum warm water wash, and to improve nickel yield, slag washing water returns step (1) and dissolves leaching operation; Scum goes to Solid state fermentation workshop to carry out sintering processes;
(5), crude zinc extraction:
Deironing press filtration filtrate and aqueous phase are sent to crude zinc extraction process, by 10% sulfuric acid fine setting pH value, pH value controls 1 ~ 3, zn cpds in extraction extraction mother liquor and a small amount of Cu, Mn, Ca, the impurity elements such as Mg, extraction liquid is made up of extraction agent and thinner, extraction agent is P204, thinner is 260# solvent oil, at room temperature multi-stage solvent extraction, until metal ion content is less than 1% in aqueous phase, aqueous phase enters down extraction together, last aqueous phase enters cobalt nickel separation circuit, 10% dilute sulphuric acid segmentation back extraction of organic phase preparation obtains zinc-containing solution, after oil-liquid separator, add sodium carbonate neutralization precipitation and obtain rough zinc carbonate, extraction liquid and organic phase can repeatedly recycle, the mass ratio of deironing press filtration filtrate, extraction liquid is 1:0.1 ~ 1, mass ratio 1:8 ~ 10 of extractant in extract, thinner, pH value controls 1 ~ 3,
(6), Separation of nickel and cobalt:
Crude zinc aqueous phase extracted is sent to Separation of nickel and cobalt operation, finely tune pH value with sodium carbonate, pH value controls 4 ~ 7, extracts the cobalt compound in aqueous phase through extraction, extraction liquid is made up of extraction agent and thinner, extraction agent is P507, and thinner is 260# solvent oil, at room temperature multi-stage solvent extraction, until metal ion content is less than 1% in aqueous phase, aqueous phase enters down together extraction, and last aqueous phase enters nickel precipitation operation, add sodium carbonate neutralization precipitation obtain nickelous carbonate or aqueous phase concentrated after for electrolysis production electro deposited nickel; 10% dilute sulphuric acid segmentation back extraction of organic phase preparation obtains cobalt-carrying solution.Extraction liquid and organic phase can repeatedly recycle; The mass ratio of crude zinc aqueous phase extracted, extraction liquid is 1:0.1 ~ 1; Mass ratio 1:8 ~ 10 of extractant in extract, thinner; PH value controls 4 ~ 7;
(7), electro deposited copper, electro deposited nickel.
The waste material containing non-ferrous metal described in described step (1) refers to tank liquor, mud, waste liquid, refuse battery material, waste residue, abandoned mine, spent catalyst and flue dust containing nickel, cobalt, copper, zinc etc.
The heat that adding water described in described step (1) produces is for intensification during acid adding, and recycle heat utilizes.
Washing water described in described step (2) can repeatedly repeated washing, and washing water return step (1) and dissolve and leach operation.
Extraction liquid described in described step (3) is made up of extraction agent and thinner, and extraction agent is the composite extractant of LIX984 and M5640, and thinner is 260# solvent oil; The multistage of described multi-stage solvent extraction, multistage fluid separation is more than 3 grades.
Alkali described in described step (4) is the one in sodium carbonate, sodium bicarbonate; Described oxygenant is the one in hydrogen peroxide, sodium chlorate, sodium perchlorate.
Filtering medium described in described step (4) and scum warm water wash, and slag washing water returns step (1) and dissolves leaching operation; Described scum goes to Solid state fermentation workshop to carry out sintering processes.
Extraction liquid described in described step (5) is made up of extraction agent and thinner, and extraction agent is P204, and thinner is 260# solvent oil; The multistage of described multi-stage solvent extraction, multistage fluid separation is more than 3 grades.
Extraction liquid described in described step (6) is made up of extraction agent and thinner, and extraction agent is P507, and thinner is 260# solvent oil; Described pH value controls 4 ~ 7; The multistage of described multi-stage solvent extraction, multistage fluid separation is more than 3 grades.
The reaction equation of each step:
Step (1):
MeO＋H
2SO
4=MeSO
4＋H
2O
Me＋H
2SO
4=MeSO
4＋H
2 ↑
3Cu＋3H
2SO
4＋NaClO
3=3CuSO
4＋3H
2O＋NaCl
Wherein: Me is metal (being mainly Ni, Cu, Fe, Mn, Ca, Mg, Al, Zn etc.).
Step (3):
H
2O
2+Fe
2++2H
+=Fe
3++2H
2O
3Fe
2(SO
4)
3+6H
2O=6Fe(OH)SO
4+3H
2SO
4
2Fe(OH)SO
4+2H
2O=Fe
2(OH)
4SO
4+H
2SO
4
2Fe(OH)SO
4+2Fe
2(OH)
4SO
4+Na
2SO
4+2H
2O=Na
2Fe
6(OH)
12(SO
4)
4+H
2SO
4
3Fe
2(SO
4)
3+12H
2O+Na
2SO
4=Na
2Fe
6(OH)
12(SO
4)
4+6H
2SO
4
Step (5):
ZnSO
4+Na
2CO
3=ZnCO
3↓+Na
2SO
4
Step (6):
NiSO
4+Na
2CO
3=NiCO
3↓+Na
2SO
4
Step (7):
Anode: 2HO
--2e
-=O
2↑+2H
+(oxidizing reaction)
Negative electrode: Ni
2++ 2e
-=Ni(reduction reaction) (electro deposited nickel)
Negative electrode: Cu
2++ 2e
-=Cu(reduction reaction) (electro deposited copper)
Compared with prior art, beneficial effect of the present invention is embodied in:
(1), that the present invention reclaims copper cobalt nickel zinc yield is higher, and copper cobalt nickel zinc purity is high, impurity is few, has good economic worth.
(2), dissolve in leaching, first levigate intensification acid adding adds the method that sodium chlorate adds water again, and fully can leach the metal in waste material and metallic compound, leaching yield is higher, and can not need outside resources, accomplishes heat recovery.Save energy and cost.
(3), in copper extraction process, the method for composite extractant is adopted, high to copper extraction selectivity, good separating effect.
(4), the method for taking strict control ph and multi-stage solvent extraction to be separated with fluid in zinc, cobalt, nickel extraction process, make various metal separation effective, the rate of recovery is high.
Accompanying drawing explanation
Fig. 1 is production technique figure;
Embodiment:
Please refer to Fig. 1:
Embodiment 1
(1), leaching is dissolved:
Various for the 500kg waste material containing non-ferrous metal is mixed, surveys the mass content of each metal, copper 2.10%, cobalt 0.56%, zinc 3.12%, iron 16.33%, nickel 1.88%.With ball milling, waste material is levigate, below fineness requirement 200 order, then join in the sulfuric acid of 250kg30%, add 5kg sodium chlorate, stirring intensity 40rpm, first time is warmed up to 50 DEG C, reaction leaching 1 ~ 3 hour, then, start the washing water dripping 250kg step (2), (4), can produce a large amount of heats, temperature controls at 60 DEG C, the cooling water temperature when temperature is too high.Drip 1 ~ 2 hour time of washing water, add washing water complete, stir 2 ~ 3 hours, so that soluble non-ferrous metal fully dissolves leaching.
(2), press filtration:
Dissolving leach liquor is cooled to less than 50 DEG C, press filtration, filter residue goes to Solid state fermentation workshop to carry out sintering processes after washing, washing water can repeated multiple timesly be used for washing, until non-ferrous metal content is less than 0.1% in filter residue, press filtration mother liquor weight 650kg, enters next process.Washing water return step (1).
(3), copper extraction:
Leach press filtration mother liquor 650kg and be sent to copper extraction process, the copper compound in mother liquor is extracted through extraction, extraction liquid is made up of 6.5kg extraction agent and 58.5kg thinner, extraction agent is the composite extractant of 2.17kgLIX984 and 4.33kgM5640, thinner is 58.5kg260# solvent oil, at room temperature three grades of extractions, and by three grades of oil-liquid separators, extraction liquid and organic phase are collected together, aqueous phase enters down extraction together, until copper compound content is less than 1% in aqueous phase, last aqueous phase enters deironing press filtration operation, 10% dilute sulphuric acid segmentation back extraction of organic phase 100kg preparation obtains the copper-bath of sulfur acid copper 25.33kg.Yield about 96.5%.Copper-bath adopts electrodeposition to reclaim copper.Extraction liquid can repeatedly use.
(4), deironing press filtration:
Aqueous phase 620kg after copper extraction is first 2.5 ~ 3.0 by soda ash adjust ph, and add 50kg hydrogen peroxide, temperature controls at 20 DEG C, react 0.5 ~ 1 hour, then add soda ash and pH is adjusted to 3.5 ~ 3.8, press filtration, mother liquor 800kg after press filtration enters next process, press filtration mother liquor Fe
2+content 0.02g/L.Filtering medium and scum warm water wash, and to improve nickel yield, slag washing water returns step (1) and dissolves leaching operation.230kg scum goes to Solid state fermentation workshop to carry out sintering processes.
(5), crude zinc extraction:
Deironing press filtration filtrate 800kg is sent to crude zinc extraction process, by 10% sulfuric acid fine setting pH value, pH value controls 1, zn cpds in extraction extraction mother liquor and a small amount of Cu, Mn, Ca, the impurity elements such as Mg, 80kg extraction liquid is made up of 8kg extraction agent P204 and 72kg thinner 260# solvent oil, at room temperature three grades of extractions, and by three grades of oil-liquid separators, extraction liquid and organic phase are collected together, aqueous phase enters down extraction together, until other impurity compound content are less than 1% in aqueous phase, last aqueous phase 750kg enters cobalt nickel separation circuit, 10% dilute sulphuric acid segmentation back extraction of organic phase 100kg preparation obtains the solution of zinc sulfate of sulfur acid zinc 35kg.Then add 34kg sodium carbonate neutralization precipitation and obtain the rough zinc carbonate of 27kg.Yield about 90.5%.Extraction liquid can repeatedly use rear employing sodium hydroxide solution and carry out saponification regeneration.
(6), Separation of nickel and cobalt:
Crude zinc aqueous phase extracted 750kg is sent to Separation of nickel and cobalt operation, pH value is finely tuned with sodium carbonate, pH value controls 4, the cobalt compound in aqueous phase is extracted through extraction, 75kg extraction liquid is made up of 7.5kg extraction agent P507 and 67.5kg thinner 260# solvent oil, at room temperature three grades of extractions, and by three grades of oil-liquid separators, extraction liquid and organic phase are collected together, aqueous phase enters next process, until cobalt compound content is less than 1% in aqueous phase, last aqueous phase 740kg enters nickel precipitation operation, add 20kg sodium carbonate neutralization precipitation and obtain 18kg nickelous carbonate, yield 94.9%, or aqueous phase concentrated after for electrolysis production electro deposited nickel.10% dilute sulphuric acid segmentation back extraction of organic phase 50kg preparation must containing the cobalt sulfate solution of 7kg rose vitriol.Yield 92.5%.Extraction liquid can repeatedly use rear employing sodium hydroxide solution and carry out saponification regeneration.
(7), electro deposited copper, electro deposited nickel:
Electrodeposition method adopts universal method, is not described herein.
Embodiment 2
(1), leaching is dissolved:
Various for the 500kg waste material containing non-ferrous metal is mixed, surveys the mass content of each metal, copper 2.10%, cobalt 0.56%, zinc 3.12%, iron 16.33%, nickel 1.88%.With ball milling, waste material is levigate, below fineness requirement 200 order, then join in the sulfuric acid of 1000kg30%, add 5kg sodium chlorate, stirring intensity 100rpm, first time is warmed up to 50 DEG C, reaction leaching 1 ~ 3 hour, then, start the water dripping 2500kg step (2), (4), can produce a large amount of heats, temperature controls at 90 DEG C, the cooling water temperature when temperature is too high.Drip 1 ~ 2 hour time of washing water, add washing water complete, stir 2 ~ 3 hours, so that soluble non-ferrous metal fully dissolves leaching.
(2), press filtration:
Dissolving leach liquor is cooled to less than 50 DEG C, press filtration, filter residue goes to Solid state fermentation workshop to carry out sintering processes after washing, washing water can repeated multiple timesly be used for washing, until non-ferrous metal content is less than 0.1% in filter residue, press filtration mother liquor weight 3800kg, enters next process.Washing water return step (1).
(3), copper extraction:
Leach press filtration mother liquor 3800kg and be sent to copper extraction process, the copper compound in mother liquor is extracted through extraction, 3800kg extraction liquid is made up of 345.45kg extraction agent and 3454.55kg thinner, extraction agent is the composite extractant of 138.18kgLIX984 and 207.27kgM5640, thinner is 3454.55kg260# solvent oil, at room temperature ten grades of extractions, and by ten grades of oil-liquid separators, extraction liquid and organic phase are collected together, aqueous phase enters down extraction together, until copper compound content is less than 1% in aqueous phase, last aqueous phase enters deironing press filtration operation, 10% dilute sulphuric acid segmentation back extraction of organic phase 100kg preparation obtains the copper-bath of sulfur acid copper 25.80kg.Yield about 97.5%.Copper-bath adopts electrodeposition to reclaim copper.Extraction liquid can repeatedly use.
(4), deironing press filtration:
Aqueous phase 3750kg after copper extraction is first 2.5 ~ 3.0 by soda ash adjust ph, and add 40kg sodium perchlorate, temperature controls at 50 DEG C, react 0.5 ~ 1 hour, then add soda ash and pH is adjusted to 3.5 ~ 3.8, press filtration, mother liquor 4500kg after press filtration enters next process, press filtration mother liquor Fe
2+content 0.01g/L.Filtering medium and scum warm water wash, and to improve nickel yield, slag washing water returns step (1) and dissolves leaching operation.231kg scum goes to Solid state fermentation workshop to carry out sintering processes.
(5), crude zinc extraction:
Deironing press filtration filtrate 4500kg is sent to crude zinc extraction process, by 10% sulfuric acid fine setting pH value, pH value controls 3, zn cpds in extraction extraction mother liquor and a small amount of Cu, Mn, Ca, the impurity elements such as Mg, 4500kg extraction liquid is made up of 409.09kg extraction agent P204 and 4090.91kg thinner 260# solvent oil, at room temperature ten grades of extractions, and by ten grades of oil-liquid separators, extraction liquid and organic phase are collected together, aqueous phase enters down extraction together, until other impurity compound content are less than 1% in aqueous phase, last aqueous phase 4450kg enters cobalt nickel separation circuit, 10% dilute sulphuric acid segmentation back extraction of organic phase 100kg preparation obtains the solution of zinc sulfate of sulfur acid zinc 35.5kg.Then add 34.5kg sodium carbonate neutralization precipitation and obtain the rough zinc carbonate of 27.2kg.Yield about 90.8%.Extraction liquid can repeatedly use rear employing sodium hydroxide solution and carry out saponification regeneration.
(6), Separation of nickel and cobalt:
Crude zinc aqueous phase extracted 4450kg is sent to Separation of nickel and cobalt operation, pH value is finely tuned with sodium carbonate, pH value controls 7, the cobalt compound in aqueous phase is extracted through extraction, 4450kg extraction liquid is made up of 404.55kg extraction agent P507 and 4045.45kg thinner 260# solvent oil, at room temperature ten grades of extractions, and by ten grades of oil-liquid separators, extraction liquid and organic phase are collected together, aqueous phase enters next process, until cobalt compound content is less than 1% in aqueous phase, last aqueous phase 4440kg enters nickel precipitation operation, add 20kg sodium carbonate neutralization precipitation and obtain 18.1kg nickelous carbonate, yield 95.2%, or aqueous phase concentrated after for electrolysis production electro deposited nickel.10% dilute sulphuric acid segmentation back extraction of organic phase 50kg preparation must containing the cobalt sulfate solution of 7.1kg rose vitriol.Yield 92.7%.Extraction liquid can repeatedly use rear employing sodium hydroxide solution and carry out saponification regeneration.
(7), electro deposited copper, electro deposited nickel:
Electrodeposition method adopts universal method, is not described herein.
Embodiment 3
(1), leaching is dissolved:
Various for the 500kg waste material containing non-ferrous metal is mixed, surveys the mass content of each metal, copper 2.10%, cobalt 0.56%, zinc 3.12%, iron 16.33%, nickel 1.88%.With ball milling, waste material is levigate, below fineness requirement 200 order, then join in the sulfuric acid of 500kg30%, add 5kg sodium chlorate, stirring intensity 60rpm, first time is warmed up to 50 DEG C, reaction leaching 1 ~ 3 hour, then, start the washing water dripping 1000kg step (2), (4), can produce a large amount of heats, temperature controls at 80 DEG C, the cooling water temperature when temperature is too high.Drip 1 ~ 2 hour time of washing water, add washing water complete, stir 2 ~ 3 hours, so that soluble non-ferrous metal fully dissolves leaching.
(2), press filtration:
Dissolving leach liquor is cooled to less than 50 DEG C, press filtration, filter residue goes to Solid state fermentation workshop to carry out sintering processes after washing, washing water can repeated multiple timesly be used for washing, until non-ferrous metal content is less than 0.1% in filter residue, press filtration mother liquor weight 1700kg, enters next process.Washing water return step (1).
(3), copper extraction:
Leach press filtration mother liquor 1700kg and be sent to copper extraction process, the copper compound in mother liquor is extracted through extraction, 850kg extraction liquid is made up of 94.44kg extraction agent and 755.56kg thinner, extraction agent is the composite extractant of 47.22kgLIX984 and 47.22kgM5640, thinner is 755.56kg260# solvent oil, at room temperature six grades of extractions, and by six grades of oil-liquid separators, extraction liquid and organic phase are collected together, aqueous phase enters down extraction together, until copper compound content is less than 1% in aqueous phase, last aqueous phase enters deironing press filtration operation, 10% dilute sulphuric acid segmentation back extraction of organic phase 100kg preparation obtains the copper-bath of sulfur acid copper 25.40kg.Yield about 96.6%.Copper-bath adopts electrodeposition to reclaim copper.Extraction liquid can repeatedly use.
(4), deironing press filtration:
Aqueous phase 1650kg after copper extraction is first 2.5 ~ 3.0 by sodium bicarbonate adjust ph, and add 45kg sodium chlorate, temperature controls at 30 DEG C, react 0.5 ~ 1 hour, then add sodium bicarbonate and pH is adjusted to 3.5 ~ 3.8, press filtration, mother liquor 1800kg after press filtration enters next process, press filtration mother liquor Fe
2+content 0.02g/L.Filtering medium and scum warm water wash, and to improve nickel yield, slag washing water returns step (1) and dissolves leaching operation.231kg scum goes to Solid state fermentation workshop to carry out sintering processes.
(5), crude zinc extraction:
Deironing press filtration filtrate 1800kg is sent to crude zinc extraction process, by 10% sulfuric acid fine setting pH value, pH value controls 2, zn cpds in extraction extraction mother liquor and a small amount of Cu, Mn, Ca, the impurity elements such as Mg, 900kg extraction liquid is made up of 100kg extraction agent P204 and 800kg thinner 260# solvent oil, at room temperature six grades of extractions, and by six grades of oil-liquid separators, extraction liquid and organic phase are collected together, aqueous phase enters down extraction together, until other impurity compound content are less than 1% in aqueous phase, last aqueous phase 1750kg enters cobalt nickel separation circuit, 10% dilute sulphuric acid segmentation back extraction of organic phase 100kg preparation obtains the solution of zinc sulfate of sulfur acid zinc 35.1kg.Then add 34kg sodium carbonate neutralization precipitation and obtain the rough zinc carbonate of 27.1kg.Yield about 90.6%.Extraction liquid can repeatedly use rear employing sodium hydroxide solution and carry out saponification regeneration.
(6), Separation of nickel and cobalt:
Crude zinc aqueous phase extracted 1750kg is sent to Separation of nickel and cobalt operation, pH value is finely tuned with sodium carbonate, pH value controls 6, the cobalt compound in aqueous phase is extracted through extraction, 875kg extraction liquid is made up of 97.22kg extraction agent P507 and 777.78kg thinner 260# solvent oil, at room temperature six grades of extractions, and by six grades of oil-liquid separators, extraction liquid and organic phase are collected together, aqueous phase enters next process, until cobalt compound content is less than 1% in aqueous phase, last aqueous phase 1740kg enters nickel precipitation operation, add 20kg sodium carbonate neutralization precipitation and obtain 18.1kg nickelous carbonate, yield 95.1%, or aqueous phase concentrated after for electrolysis production electro deposited nickel.10% dilute sulphuric acid segmentation back extraction of organic phase 50kg preparation must containing the cobalt sulfate solution of 7.1kg rose vitriol.Yield 92.6%.Extraction liquid can repeatedly use rear employing sodium hydroxide solution and carry out saponification regeneration.
(7), electro deposited copper, electro deposited nickel:
Electrodeposition method adopts universal method, is not described herein.
Embodiment 4
(1), leaching is dissolved:
Various for the 500kg waste material containing non-ferrous metal is mixed, surveys the mass content of each metal, copper 2.10%, cobalt 0.56%, zinc 3.12%, iron 16.33%, nickel 1.88%.With ball milling, waste material is levigate, below fineness requirement 200 order, then join in the sulfuric acid of 300kg30%, add 5kg sodium chlorate, stirring intensity 80rpm, first time is warmed up to 50 DEG C, reaction leaching 1 ~ 3 hour, then, start the washing water dripping 500kg step (2), (4), can produce a large amount of heats, temperature controls at 70 DEG C, the cooling water temperature when temperature is too high.Drip 1 ~ 2 hour time of washing water, add washing water complete, stir 2 ~ 3 hours, so that soluble non-ferrous metal fully dissolves leaching.
(2), press filtration:
Dissolving leach liquor is cooled to less than 50 DEG C, press filtration, filter residue goes to Solid state fermentation workshop to carry out sintering processes after washing, washing water can repeated multiple timesly be used for washing, until non-ferrous metal content is less than 0.1% in filter residue, press filtration mother liquor weight 1000kg, enters next process.Washing water return step (1).
(3), copper extraction:
Leach press filtration mother liquor 1000kg and be sent to copper extraction process, the copper compound in mother liquor is extracted through extraction, 200kg extraction liquid is made up of 20kg extraction agent and 180kg thinner, extraction agent is the composite extractant of 12.5kgLIX984 and 7.5kgM5640, thinner is 180kg260# solvent oil, at room temperature eight grades of extractions, and by eight grades of oil-liquid separators, extraction liquid and organic phase are collected together, aqueous phase enters down extraction together, until copper compound content is less than 1% in aqueous phase, last aqueous phase enters deironing press filtration operation, 10% dilute sulphuric acid segmentation back extraction of organic phase 100kg preparation obtains the copper-bath of sulfur acid copper 25.35kg.Yield about 96.35%.Copper-bath adopts electrodeposition to reclaim copper.Extraction liquid can repeatedly use.
(4) deironing press filtration:
Aqueous phase 950kg after copper extraction is first 2.5 ~ 3.0 by sodium carbonate adjust ph, and add 50kg hydrogen peroxide, temperature controls at 40 DEG C, react 0.5 ~ 1 hour, then add sodium carbonate and pH is adjusted to 3.5 ~ 3.8, press filtration, mother liquor 850kg after press filtration enters next process, press filtration mother liquor Fe
2+content 0.03g/L.Filtering medium and scum warm water wash, and to improve nickel yield, slag washing water returns step (1) and dissolves leaching operation.231kg scum goes to Solid state fermentation workshop to carry out sintering processes.
(5) crude zinc extraction:
Deironing press filtration filtrate 850kg is sent to crude zinc extraction process, by 10% sulfuric acid fine setting pH value, pH value controls 2, zn cpds in extraction extraction mother liquor and a small amount of Cu, Mn, Ca, the impurity elements such as Mg, 170kg extraction liquid is made up of 17kg extraction agent P204 and 163kg thinner 260# solvent oil, at room temperature eight grades of extractions, and by eight grades of oil-liquid separators, extraction liquid and organic phase are collected together, aqueous phase enters down extraction together, until other impurity compound content are less than 1% in aqueous phase, last aqueous phase 800kg enters cobalt nickel separation circuit, 10% dilute sulphuric acid segmentation back extraction of organic phase 100kg preparation obtains the solution of zinc sulfate of sulfur acid zinc 35.0kg.Then add 34kg sodium carbonate neutralization precipitation and obtain the rough zinc carbonate of 27.2kg.Yield about 90.8%.Extraction liquid can repeatedly use rear employing sodium hydroxide solution and carry out saponification regeneration.
(6) Separation of nickel and cobalt:
Crude zinc aqueous phase extracted 800kg is sent to Separation of nickel and cobalt operation, pH value is finely tuned with sodium carbonate, pH value controls 6, the cobalt compound in aqueous phase is extracted through extraction, 160kg extraction liquid is made up of 16kg extraction agent P507 and 144kg thinner 260# solvent oil, at room temperature eight grades of extractions, and by eight grades of oil-liquid separators, extraction liquid and organic phase are collected together, aqueous phase enters next process, until cobalt compound content is less than 1% in aqueous phase, last aqueous phase 790kg enters nickel precipitation operation, add 20kg sodium carbonate neutralization precipitation and obtain 18.1kg nickelous carbonate, yield 95.1%, or aqueous phase concentrated after for electrolysis production electro deposited nickel.10% dilute sulphuric acid segmentation back extraction of organic phase 50kg preparation must containing the cobalt sulfate solution of 7.1kg rose vitriol.Yield 92.6%.Extraction liquid can repeatedly use rear employing sodium hydroxide solution and carry out saponification regeneration.
(7) electro deposited copper, electro deposited nickel:
Electrodeposition method adopts universal method, is not described herein.
Claims (9)
1., from the various method containing reclaiming copper zinc cobalt nickel the waste material of non-ferrous metal, it is characterized in that: comprise the steps:
(1), leaching is dissolved:
The various waste material containing non-ferrous metal is mixed, with ball milling, waste material is levigate, fineness requirement 200 order-400 order, then join in the sulfuric acid of 30%, add sodium chlorate simultaneously, stirring intensity 40 ~ 100rpm, first time is warmed up to more than 50 DEG C, reaction leaching 1 ~ 3 hour, then, start to drip the washing water of water or step (2), (4), can produce a large amount of heats, temperature controls at 60 ~ 90 DEG C, the cooling water temperature when temperature is too high, heat up water coolant can be used for first time heat up, can two complete equipment coproduction so that save energy; Drip 1 ~ 2 hour time of washing water, add washing water complete, stir 2 ~ 3 hours, so that soluble non-ferrous metal fully dissolves leaching; The mass ratio of waste material, sulfuric acid, water is 1:0.5 ~ 2:0.5 ~ 5;
(2), press filtration:
Dissolving leach liquor is cooled to less than 50 DEG C, press filtration, filter residue goes to Solid state fermentation workshop to carry out sintering processes after washing, filter residue needs repeatedly to wash, until metal content is lower than 0.1% in filter residue, washing water return step (1) and dissolve leaching operation, and press filtration mother liquor enters next process;
(3), copper extraction:
Leach press filtration mother liquor and be sent to copper extraction process, the copper compound in mother liquor is extracted through extraction, extraction liquid is made up of extraction agent and thinner, extraction agent is the composite extractant of LIX984 and M5640, thinner is 260# solvent oil, at room temperature multi-stage solvent extraction, and by multi-grade oil liquid/gas separator, extraction liquid and organic phase are collected together, aqueous phase enters down extraction together, until copper compound content is less than 1% in aqueous phase, last aqueous phase enters deironing press filtration operation, and 10% dilute sulphuric acid segmentation back extraction of organic phase preparation obtains copper-bath; Copper-bath adopts electrodeposition to reclaim copper; Extraction liquid can repeatedly use; The mass ratio of press filtration mother liquor, extraction liquid is 1:0.1 ~ 1; Mass ratio 1:8 ~ 10 of extractant in extract, thinner; Mass ratio 1:0.5 ~ 1.5 of LIX984, M5640 in extraction agent;
(4), deironing press filtration:
Aqueous phase after copper extraction is first 2.5 ~ 3.0 with alkali adjust ph, and add oxygenant, temperature controls at 20 ~ 50 DEG C, reacts 0.5 ~ 1 hour, then adds alkali and pH is adjusted to 3.5 ~ 3.8, press filtration, and the mother liquor after press filtration enters next process, press filtration mother liquor requirement Fe
2+< 0.05g/L; Filtering medium and scum warm water wash, and to improve nickel yield, slag washing water returns step (1) and dissolves leaching operation; Scum goes to Solid state fermentation workshop to carry out sintering processes;
(5), crude zinc extraction:
Deironing press filtration filtrate and aqueous phase are sent to crude zinc extraction process, by 10% sulfuric acid fine setting pH value, pH value controls 1 ~ 3, zn cpds in extraction extraction mother liquor and a small amount of Cu, Mn, Ca, the impurity elements such as Mg, extraction liquid is made up of extraction agent and thinner, extraction agent is P204, thinner is 260# solvent oil, at room temperature multi-stage solvent extraction, until metal ion content is less than 1% in aqueous phase, aqueous phase enters down extraction together, last aqueous phase enters cobalt nickel separation circuit, 10% dilute sulphuric acid segmentation back extraction of organic phase preparation obtains zinc-containing solution, after oil-liquid separator, add sodium carbonate neutralization precipitation and obtain rough zinc carbonate, extraction liquid and organic phase can repeatedly recycle, the mass ratio of deironing press filtration filtrate, extraction liquid is 1:0.1 ~ 1, mass ratio 1:8 ~ 10 of extractant in extract, thinner, pH value controls 1 ~ 3,
(6), Separation of nickel and cobalt:
Crude zinc aqueous phase extracted is sent to Separation of nickel and cobalt operation, finely tune pH value with sodium carbonate, pH value controls 4 ~ 7, extracts the cobalt compound in aqueous phase through extraction, extraction liquid is made up of extraction agent and thinner, extraction agent is P507, and thinner is 260# solvent oil, at room temperature multi-stage solvent extraction, until metal ion content is less than 1% in aqueous phase, aqueous phase enters down together extraction, and last aqueous phase enters nickel precipitation operation, add sodium carbonate neutralization precipitation obtain nickelous carbonate or aqueous phase concentrated after for electrolysis production electro deposited nickel; 10% dilute sulphuric acid segmentation back extraction of organic phase preparation obtains cobalt-carrying solution; Extraction liquid and organic phase can repeatedly recycle; The mass ratio of crude zinc aqueous phase extracted, extraction liquid is 1:0.1 ~ 1; Mass ratio 1:8 ~ 10 of extractant in extract, thinner; PH value controls 4 ~ 7;
(7), electro deposited copper, electro deposited nickel.
2. according to claim 1 from the various method containing reclaiming copper zinc cobalt nickel the waste material of non-ferrous metal, it is characterized in that, the waste material containing non-ferrous metal described in described step (1) refers to tank liquor, mud, waste liquid, refuse battery material, waste residue, abandoned mine, spent catalyst and flue dust containing nickel, cobalt, copper, zinc etc.
3. the method reclaiming copper zinc cobalt nickel from the various waste material containing non-ferrous metal according to claim 1, is characterized in that, the heat that adding water described in described step (1) produces is for intensification during acid adding, and recycle heat utilizes.
4. the method reclaiming copper zinc cobalt nickel from the various waste material containing non-ferrous metal according to claim 1, is characterized in that, the washing water described in described step (2) can repeatedly repeated washing, and washing water return step (1) and dissolve and leach operation.
5. according to claim 1 from the various method containing reclaiming copper zinc cobalt nickel the waste material of non-ferrous metal, it is characterized in that, extraction liquid described in described step (3) is made up of extraction agent and thinner, and extraction agent is the composite extractant of LIX984 and M5640, and thinner is 260# solvent oil; The multistage of described multi-stage solvent extraction, multistage fluid separation is more than 3 grades.
6. according to claim 1 from the various method containing reclaiming copper zinc cobalt nickel the waste material of non-ferrous metal, it is characterized in that, the alkali described in described step (4) is the one in sodium carbonate, sodium bicarbonate; Described oxygenant is the one in hydrogen peroxide, sodium chlorate, sodium perchlorate.
7. according to claim 1 from the various method containing reclaiming copper zinc cobalt nickel the waste material of non-ferrous metal, it is characterized in that, the filtering medium described in described step (4) and scum warm water wash, and slag washing water returns step (1) and dissolves leaching operation; Described scum goes to Solid state fermentation workshop to carry out sintering processes.
8. according to claim 1 from the various method containing reclaiming copper zinc cobalt nickel the waste material of non-ferrous metal, it is characterized in that, the extraction liquid described in described step (5) is made up of extraction agent and thinner, and extraction agent is P204, and thinner is 260# solvent oil; The multistage of described multi-stage solvent extraction, multistage fluid separation is more than 3 grades.
9. according to claim 1 from the various method containing reclaiming copper zinc cobalt nickel the waste material of non-ferrous metal, it is characterized in that, the extraction liquid described in described step (6) is made up of extraction agent and thinner, and extraction agent is P507, and thinner is 260# solvent oil; Described pH value controls 4 ~ 7; The multistage of described multi-stage solvent extraction, multistage fluid separation is more than 3 grades.
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