CN103526016B - A kind of method of raw material containing lead hydrometallurgic recovery - Google Patents
A kind of method of raw material containing lead hydrometallurgic recovery Download PDFInfo
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- CN103526016B CN103526016B CN201310250004.0A CN201310250004A CN103526016B CN 103526016 B CN103526016 B CN 103526016B CN 201310250004 A CN201310250004 A CN 201310250004A CN 103526016 B CN103526016 B CN 103526016B
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- lead
- sulfate
- raw material
- material containing
- solution
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- 239000002994 raw material Substances 0.000 title claims abstract description 40
- 238000011084 recovery Methods 0.000 title claims abstract description 26
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- RILZRCJGXSFXNE-UHFFFAOYSA-N 2-[4-(trifluoromethoxy)phenyl]ethanol Chemical compound OCCC1=CC=C(OC(F)(F)F)C=C1 RILZRCJGXSFXNE-UHFFFAOYSA-N 0.000 description 1
- QDGAVODICPCDMU-UHFFFAOYSA-N 2-amino-3-[3-[bis(2-chloroethyl)amino]phenyl]propanoic acid Chemical compound OC(=O)C(N)CC1=CC=CC(N(CCCl)CCCl)=C1 QDGAVODICPCDMU-UHFFFAOYSA-N 0.000 description 1
- LVBRDPUFMRDJCB-UHFFFAOYSA-N 2-hydroxy-5-sulfobenzoic acid iron Chemical compound [Fe].OC(=O)C=1C(O)=CC=C(S(=O)(=O)O)C1 LVBRDPUFMRDJCB-UHFFFAOYSA-N 0.000 description 1
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 description 1
- 208000035126 Facies Diseases 0.000 description 1
- 239000004606 Fillers/Extenders Substances 0.000 description 1
- 229910000003 Lead carbonate Inorganic materials 0.000 description 1
- 229910000978 Pb alloy Inorganic materials 0.000 description 1
- 238000003723 Smelting Methods 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000001311 chemical methods and process Methods 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000000280 densification Methods 0.000 description 1
- 238000006477 desulfuration reaction Methods 0.000 description 1
- 230000023556 desulfurization Effects 0.000 description 1
- UZUODNWWWUQRIR-UHFFFAOYSA-L disodium;3-aminonaphthalene-1,5-disulfonate Chemical compound [Na+].[Na+].C1=CC=C(S([O-])(=O)=O)C2=CC(N)=CC(S([O-])(=O)=O)=C21 UZUODNWWWUQRIR-UHFFFAOYSA-L 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- XCAUINMIESBTBL-UHFFFAOYSA-N lead(ii) sulfide Chemical compound [Pb]=S XCAUINMIESBTBL-UHFFFAOYSA-N 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000010422 painting Methods 0.000 description 1
- 239000013502 plastic waste Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 230000007096 poisonous effect Effects 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 230000003252 repetitive effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 229920005552 sodium lignosulfonate Polymers 0.000 description 1
- 238000000207 volumetry Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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
Landscapes
- Manufacture And Refinement Of Metals (AREA)
Abstract
The invention discloses a kind of method of raw material containing lead hydrometallurgic recovery, comprise: 1) use the solution containing vitriol, complexing agent, catalyzer to leach raw material containing lead, and add reductive agent and make the plumbic oxide in raw material containing lead or tri-lead tetroxide be reduced to the lead salt of solubility, after lead compound all dissolves, solution filters, and is separated to obtain filtrate A and insoluble substance; 2) regulate the pH value of filtrate A, be separated to obtain lead sulfate and liquor B, wherein, liquor B adds sulfate radical, returns step 1) after adjust ph; 3) lead sulfate is directly as battery material or commodity; React with the basic solution containing vitriol and lead sulfate, be separated and obtain comprising tribasic lead sulfate, the sublimed lead of four sublimed leads and liquor C; It is lead sulfate and the sublimed lead that can be directly used in lead-acid cell production that raw material containing lead can be purified by the method, is a kind of hydrometallurgic recovery method of environmental protection.
Description
Technical field
The invention belongs to waste lead acid battery to reclaim and technical field of regeneration, relate to and a kind ofly utilize chemical method to prepare the method for high purity sulphur lead plumbate or sublimed lead lead plaster in waste lead acid battery or raw material containing lead.
Background technology
Lead-acid cell from birth since, the price cheap with it and reliable stability in secondary cell market, particularly automobile battery in occupation of important position.Show according to relevant industries association statistics, within 2011, Chinese lead bullion consumption is more than 4,000,000 tons, and wherein lead-acid cell consumption accounts for 70%.Containing lead poisonous in a large number and compound thereof in lead-acid cell, realize at present industrialized pyrogenic process to reclaim plumbous technology and in plumbous smelting reducing process, produce lead steam and cause severe contamination to environment, the plumbous technology of hydrometallurgic recovery rests on laboratory stage because its processing cost is too high, fails to realize industrialization.Therefore, find a kind of efficient, economical and the waste lead acid battery reclaiming technology of environmental protection becomes problem demanding prompt solution.
In lead-acid cell, scrap lead mainly comprises electrode plate grid, lug and positive and negative pole lead paste.Wherein grid and lug are metallic lead or lead alloy, and the methods such as melting can be adopted to reclaim.Lead plaster accounts for 50% of lead-acid cell weight, and composition is lead powder, plumbous oxide, lead sulfate and plumbic oxide, and comprises barium sulfate, sodium lignosulfonate, the positive and negative electrode additive of staple fibre etc., complicated component, separation difficulty, is the difficult point of secondary lead research.
Waste lead acid battery treatment process general is at present pyrogenic process secondary lead technology, and representational is oxygen bottom-blowing method (Chinese publication CN200610048548.9).Pyrogenic process secondary lead technology can produce a large amount of lead steam and plumbous waste residue in plumbous reduction process, causes lead recovery to reduce, and also can cause serious environmental pollution simultaneously.
The plumbous technology of wet reclamation to receive the concern of secondary lead industry because of it always to close friend to environmental facies, representational is acid lead salt electrolysis tech, alkaline lead salt electrolysis tech, Solid phase electrolysis technology and chemical process be converted into some plumbous industrial goods.
With the acid lead salt electrolysis tech that Ginatta technique is representative, lead plaster is adopted volatile salt or sodium carbonate desulfurization Formed lead plumbate, add reductive agent and make plumbic oxide be converted into plumbous oxide, plumbous oxide and lead carbonate are dissolved in electrolysis in fluoborate solution subsequently, anode produces oxygen, and negative electrode produces plumbous.Under the condition of bath voltage 2.7V, plumbous electrolysis energy consumption per ton is 700kWh(US.Palent4451340).Acid lead salt electrolysis tech eliminates the lead steam that produces in pyrogenic process secondary lead reduction process to the pollution of environment, but the volatile toxic gas contaminate environment of fluoroboric acid, plumbic oxide by product can be produced at electrolytic process Anodic, need reprocessing, reduce production efficiency and its too high energy consumption limits industrialization.
Lead plaster water furnishing paste is coated on negative electrode by Solid phase electrolysis technology, in the basic conditions lead plaster Direct Electrolysis is reduced into lead powder, and bath voltage is 1.8-2.6V.(nonferrous metal and utilization, 2005, (12): 16-17).The method is comparatively friendly to environment, in the removal process of lead-acid cell, do not produce secondary pollution, but the easy oxidation by air in the process of founding lead pig of its product lead powder, electrolytic process is not thorough simultaneously, is mingled with more than 2% lead sulfate fully do not reduced.
With the alkaline lead salt electrolysis tech that a kind of method of recycling secondary lead by electrolyzing alkaline leaded solution (Chinese publication ZL201010297522.4) is representative, lead plaster is converted into lead sulfate in acidic medium, be dissolved in the NaOH electrolyte of dense heat afterwards, be oxygen with plumbous at the electrolyzer Inner electrolysis separated with cationic membrane, anode does not produce plumbic oxide, obtain the electrolytic lead that the lower groove pressure of 1.5V is smooth with densification, electrolytic solution realizes recycle, and produces sodium sulfate byproduct.But electrolysis easily produces alkali mist and impacts Working environment at a higher temperature, cationic membrane fancy price makes running cost significantly increase simultaneously.
The above-mentioned wet processing both domestic and external of comprehensive analysis and ripe thermal process, wet processing can improve lead recovery and reduce the pollution to environment, there is following problem simultaneously:
1) acidic electrolysis produces toxic gas contaminate environment
2) reduction of Solid phase electrolysis lead plaster is not thorough, is mingled with a large amount of impurity, is not suitable for industrialization
3) alkaline electrolysis operation cost is higher, and electrolytic process produces alkali mist
4) acid, alkaline electrolysis needs to consume a large amount of sweetening agent (sodium carbonate, carbonic acid ammonia, sodium hydroxide) and causes cost to increase.
Summary of the invention
A kind of method that technical problem to be solved by this invention is to provide economy, the efficient and waste lead acid battery of environmental protection reclaims.
The method of a kind of raw material containing lead hydrometallurgic recovery of the present invention, comprises the following steps:
1) solution containing vitriol, complexing agent, catalyzer, pH value between 6.0-13.0, between temperature 25-110 DEG C is used to leach raw material containing lead, and add reductive agent and make the plumbic oxide in raw material containing lead or tri-lead tetroxide be reduced to the lead salt of solubility, after lead compound all dissolves, solution filters, and is separated to obtain filtrate A and insoluble substance;
2) regulate the pH value of filtrate A to separate out lead sulfate between 4.0-8.0, be separated to obtain lead sulfate and liquor B, wherein, liquor B adds sulfate radical supplement to make in solution sulfate concentration to 0.5-4.5mol/L, adjust ph between 6.0-13.0 after return step 1);
3) lead sulfate is directly as battery material or commodity; React with the basic solution containing vitriol, pH value between 8.5-13.5, between temperature 0-90 DEG C and lead sulfate, be separated and obtain comprising tribasic lead sulfate, the sublimed lead of four sublimed leads and liquor C;
Wherein, liquor C recycle and be 1.5-5.5mol/L to sulfate concentration after as step 2) in vitriol replenishment cycles utilize.
Further, preferred method is, in step 1), described raw material containing lead choose lead plaster in waste lead acid battery, arbitrary in lead plaster thermal decomposition product, plumbous oxide ore, lead glance oxidation products, lead-acid cell drip washing waste material, leaded flue dust in waste lead acid battery;
Wherein, at least one in lead, plumbous oxide, plumbic oxide, tri-lead tetroxide, lead sulfate, sublimed lead is contained in described raw material containing lead.
Further, preferred method is, in step 1), described vitriol chooses the one in ammonium sulfate that concentration is 0.5-4.5mol/L, potassium sulfate, sodium sulfate;
Described reductive agent comprises one or both of lead, iron, hydrogen peroxide, sulfurous gas and sulphite;
Described catalyzer is the one comprised in the vitriol of iron or cobalt or manganese, muriate, nitrate, perchlorate, edetate, sulfosalicylate, salicylate, and catalyst concn is not higher than 0.1mol/L;
Described complexing agent is characterized as in the solution between pH value 8.5-9.5 and forms soluble complexes with lead ion and the logarithmic value of complex compound conditional stability constant is greater than 7.78, complexing agent pH value forms the conditional stability constant of complex compound between 4.0-4.5 with lead ion logarithmic value in solution be less than 7.78 a-amino acid, organic amine compound, containing one or both in the complexone of aminoacetaldehyde diethyl acid groups or Padil group, complexing agent concentration is 0.5-5.0mol/L.
Wherein, described complexing agent is methylamine, ethamine, quadrol, propylene diamine, thanomin, trolamine, imidazoles, Diethylenetriamine, three second tetramines, ethylenediamine-N,N'-diacetic acid(EDDA), propylene diamine oxalic acid, nitrilotriacetic acid(NTA), iminodiethanoic acid, aspartic acid L-Ala, α-amino-isovaleric acid, L-glutamic acid, proline(Pro), sarkosine, phenylalanine, leucine, Histidine, l-asparagine, glycine, Threonine, Serine, glutamine, citrulline, Methionin, arginine, halfcystine, methionine(Met), one or both in ornithine, complexing agent concentration is 0.5-5.0mol/L.
Further, preferred method is, in step 1), comprises further: in leaching process, add buffered soln maintain reaction time pH value of solution between 6.0-13.0;
Wherein, buffered soln is containing the solution of a kind of mass concentration in methylamine, ethamine, quadrol, propylene diamine, ammonia, sodium hydroxide, potassium hydroxide, potassium primary phosphate-sodium hydroxide, boric acid-borax, hydrochloric acid-thanomin, sodium carbonate-bicarbonate, Sodium phosphate dibasic-sodium hydroxide at 1-50%.
Further, preferred method is, in step 1), temperature of reaction is 45-100 DEG C, and the add-on of raw material containing lead is 35-350g/L.
Further, preferred method is, step 2) in, specifically comprise: in solution, add acid or strong acid weak base salt, pass into that sour gas makes solution absorb sour gas, the pH value of one or both adjustment filtrate A in the method that the alkaline matter in solution volatilize by the mode reduced pressure or pass into gas separates out lead sulfate between 4.0-8.0;
Wherein, described acid comprises mass concentration at the hydrochloric acid of 1%-37%, the sulfuric acid of 2%-98%, the perchloric acid of 2%-70% in interior one; Described sour gas comprises the one of hydrogenchloride, sulfurous gas, carbonic acid gas; Described strong acid weak base salt comprise Tai-Ace S 150, ferric sulfate, ferrous sulfate mass concentration at the solution of 1-50% or solid in interior one; Described alkaline matter comprises the one of methylamine, ethamine, quadrol, propylene diamine, ammonia; Described sulfate radical supplement comprise ammonium sulfate containing 1.5-7.0mol/L or sodium sulfate or potassium sulfate solution, the sulfuric acid of 10-98%, sulfate concentration are one in 1.5-5.5mol/L solution.
Further, preferred method is, in step 3), and the one in the ammonium sulfate of described vitriol to be concentration be 0.25-5.5mol/L, potassium sulfate, sodium sulfate;
The solution that it is 1%-50% that described basic solution uses containing a kind of mass concentration in methylamine, ethamine, quadrol, propylene diamine, thanomin, triethanolamine, ammonia, sodium hydroxide, potassium hydroxide, carbonate, supercarbonate maintain in reaction process reaction soln in reaction process pH value between 8.5-13.5.
Further, preferred method comprises: step 2) in, the temperature of reaction of described solution is 45-100 DEG C.
Further, preferred method is, in step 3), comprises further:
Maintain temperature of reaction 0-90 DEG C in reaction process, reaction times 0.15-24 hour, lead sulfate add-on is 50-500g/L.
Further, preferred method is, in step 3), comprises further:
Temperature of reaction is between 0-40 DEG C, and the control reaction times is 0.15-4 hour.After this invention takes such scheme, complexing agent (such as quadrol) is utilized to have stronger complexing action to lead salt, regulator solution pH value is 6.0-13.0, lead sulfate is made to dissolve (complexing agent forms soluble complexes with lead ion in this solution and the logarithmic value of the conditional stability constant of complex compound is greater than 7.78) under there is the condition of a large amount of sulfate radical in solution, adopt the impurity filtering and can be separated in lead plaster, regulate the pH value of lead complex solution afterwards, solution ph is reduced, increase the Radiation grafting of complexing agent, reduce complexing agent to the complex ability of lead salt, the lead salt in solution is made to produce precipitation (logarithmic value that complexing agent forms the conditional stability constant of complex compound with lead ion is in this solution less than 7.78) with lead sulfate form, and then be separated, achieve the purification that insolubles lead sulfate is difficult to realize in conventional methods where, the highly purified lead sulfate of direct acquisition, and obtain lead-acid cell raw material sublimed lead by reprocessing, farthest have followed the angle of atom economy, lead plaster is directly purified for the purity that can be used as lead-acid cell raw material is the lead sulfate of 99.995%, 3BS(tribasic lead sulfate) or 4BS(tetra-sublimed lead), reacted filtrate can be used as vitriol and participates in circulating reaction, realize the recycling of sulfate radical.
Compare the wet reclamation splicer skill reported, the present invention directly obtains lead-acid cell raw material by the method for chemical purification from waste lead acid battery, do not consume sweetening agent, do not consume electric energy electrolysis and refining, lead powder manufacturing processed in simultaneously not needing lead-acid cell to produce, completely eliminate the environmental pollution preparing lead powder process at secondary lead industry and lead-acid cell, achieving the combination of secondary lead industry and lead-acid cell industry, is a kind of environmental protection, energy-conservation, efficient lead-acid cell recovery method.
Accompanying drawing explanation
Below in conjunction with the drawings and specific embodiments, the present invention will be described in detail, to make above-mentioned advantage of the present invention definitely.
Fig. 1 is the schematic flow sheet of the method for a kind of raw material containing lead hydrometallurgic recovery of the present invention.
Embodiment
The waste lead acid battery treatment process of traditional secondary lead industry be lead plaster is reduced to lead bullion again refining be electrolytic lead, electrolytic lead is oxidized to plumbous oxide by lead-acid cell industry, then makes lead-acid cell.Lead plaster obtains electrolytic lead through reduction, and it is plumbous that electrolytic lead oxidation obtains lead-acid cell material oxidation, and warp and cream process obtain tribasic lead sulfate (3BS) or four sublimed leads (4BS) carry out painting cream, and this process is not only loaded down with trivial details but also energy consumption is higher.
For this reason, the present invention is by obtaining lead sulfate (purity more than 99.995%) to the chemical reduction of lead plaster and purification, reprocessing is carried out to lead sulfate and obtains high-purity sublimed lead comprising 3BS and 4BS, sublimed lead directly can carry out lead-acid cell and be coated with cream, and lead sulfate also can be used as lead-acid cell raw material and uses or make commodity selling.
Wherein, Fig. 1 is the schematic flow sheet of the method for a kind of raw material containing lead hydrometallurgic recovery of the present invention.
As shown in Figure 1, described method comprises the following steps:
Step 1): use and containing vitriol, complexing agent, catalyzer, the solution of pH between 6.0-13.0, leaded material is leached, add the lead salt that plumbic oxide that reductive agent makes may exist in leaded material or tri-lead tetroxide are reduced to solubility, after the plumbic oxide in leaded material or other lead compounds all dissolve, solution filters, and is separated to obtain filtrate A and insoluble substance (residuals).
In this step 1), vitriol is the one in ammonium sulfate, potassium sulfate, sodium sulfate, and concentration is 0.5-4.5mol/L.
Described reductive agent comprises one or both of lead, iron, hydrogen peroxide, sulfurous gas and sulphite.
Described catalyzer is the one comprised in the vitriol of iron or cobalt or manganese, muriate, nitrate, perchlorate, edetate, sulfosalicylate, salicylate, and catalyst concn is not higher than 0.1mol/L;
Described complexing agent is characterized as in the solution between pH value 8.5-9.5 and forms soluble complexes with lead ion and the logarithmic value of complex compound conditional stability constant is greater than 7.78, complexing agent pH value forms the conditional stability constant of complex compound between 4.0-4.5 with lead ion logarithmic value in solution be less than 7.78 a-amino acid, organic amine compound, containing one or both in the complexone of aminoacetaldehyde diethyl acid groups or Padil group, complexing agent concentration is 0.5-5.0mol/L.
Further, described complexing agent is methylamine, ethamine, quadrol, propylene diamine, thanomin, trolamine, imidazoles, Diethylenetriamine, three second tetramines, ethylenediamine-N,N'-diacetic acid(EDDA), propylene diamine oxalic acid, nitrilotriacetic acid(NTA), iminodiethanoic acid, aspartic acid, L-Ala, α-amino-isovaleric acid, L-glutamic acid, proline(Pro), sarkosine, phenylalanine, leucine, Histidine, l-asparagine, glycine, Threonine, Serine, glutamine, citrulline, Methionin, arginine, halfcystine, methionine(Met), one or both in ornithine, concentration is 0.5-5.0mol/L.
Further, in order to ensure the efficiency in leaching process, in leaching process, add buffered soln maintain reaction time pH value of solution between 6.0-13.0; Wherein, buffered soln can be chosen containing the solution of a kind of mass concentration in methylamine, ethamine, quadrol, propylene diamine, ammonia, sodium hydroxide, potassium hydroxide, potassium primary phosphate-sodium hydroxide, boric acid-borax, hydrochloric acid-thanomin, sodium carbonate-bicarbonate, Sodium phosphate dibasic-sodium hydroxide at 1-50%.
In above process, preferred temperature of reaction is 45-100 DEG C.
Described raw material containing lead is chosen in lead plaster in waste lead acid battery, waste lead acid battery arbitrary in lead plaster thermal decomposition product, plumbous oxide ore, lead glance oxidation products, lead-acid cell drip washing waste material, leaded flue dust; Wherein, containing at least one in lead, plumbous oxide, plumbic oxide, tri-lead tetroxide, lead sulfate, sublimed lead in described raw material containing lead, in an embodiment, choose lead plaster, and lead plaster add-on is 35-350g/L.
Wherein, described complexing agent feature is described in the above-described embodiments, namely it is form soluble complexes with lead ion in the solution of complexing agent between pH value 8.5-9.5 and the logarithmic value of the conditional stability constant of complex compound is greater than 7.78, complexing agent forms the conditional stability constant of complex compound in the solution of pH value between 4.0-4.5 logarithmic value with lead ion is less than 7.78(and lead sulfate containing 1.0-2.0mol/L sulfate radical, 1.0-2.0mol/L complexing agent, pH value is that in the solution between 8.5-9.5, lead sulfate dissolves with lead complex form, lead complex solution is containing 1.0-2.0mol/L sulfate radical, 1.0-2.0mol/L complexing agent, pH value be in the solution between 4.0-4.5 lead complex with lead sulfate form separate out) a-amino acid, organic amine compound, containing one or both in the complexone of aminoacetaldehyde diethyl acid groups or Padil group, complexing agent concentration is 0.5-5.0mol/L.。
Therefore, utilize complexing agent (such as quadrol) to have stronger complexing action to lead salt, regulator solution pH value is 6.0-13.0, under there is the condition of a large amount of sulfate radical, lead sulfate is dissolved in solution, adopts the impurity in filtration and separable raw material containing lead.
Step 2): regulate the pH value of filtrate A to separate out lead sulfate between 4.0-8.0, be separated to obtain lead sulfate and liquor B, comprise: adopt comprise in solution, to add acid or strong acid weak base salt, pass into that sour gas makes solution absorb sour gas, the pH value of one or both adjustment filtrate A in the method that the alkaline matter in solution volatilize by the mode reduced pressure or pass into gas separates out lead sulfate between 4.0-8.0.
Wherein, it is 0.5-4.5mol/L that liquor B adds sulfate radical supplement concentration to solution sulfate concentration, adjust ph between 6.0-13.0 after return step 1),
Wherein, described sulfate radical supplement comprise ammonium sulfate containing 1.5-7.0mol/L or sodium sulfate or potassium sulfate solution, the sulfuric acid of 10-98%, sulfate concentration are one in 1.5-5.0mol/L solution.Described acid comprises mass concentration at the hydrochloric acid of 1%-37%, the sulfuric acid of 2%-98%, the perchloric acid of 2%-70% in interior one, described sour gas comprises the one of hydrogenchloride, sulfurous gas, carbonic acid gas, described strong acid weak base salt comprise Tai-Ace S 150, ferric sulfate, ferrous sulfate mass concentration at the solution of 1-50% or solid in interior one, described alkaline matter comprises the one of methylamine, ethamine, quadrol, propylene diamine, ammonia.
And lead sulfate can directly as battery material or commodity; Or, in preferred embodiment, also comprise:
Step 3): react with the basic solution containing vitriol, pH value between 8.5-13.5, between temperature 0-90 DEG C and lead sulfate, be separated and obtain comprising tribasic lead sulfate, the sublimed lead of four sublimed leads and liquor C, wherein, sublimed lead through sintering or directly can use as battery material.
In this step, described vitriol is the one comprising ammonium sulfate, potassium sulfate, sodium sulfate, and concentration is 0.25-5.5mol/L.
The solution that it is 1%-50% that described basic solution adopts containing a kind of mass concentration comprised in methylamine, ethamine, quadrol, propylene diamine, thanomin, triethanolamine, ammonia, sodium hydroxide, potassium hydroxide, carbonate, supercarbonate maintain reaction soln in reaction process pH value between 8.5-13.0.
Wherein, keep temperature of reaction 0-90 DEG C, the reaction times is 0.15-24 hour, and preferred temperature of reaction is between 0-40 DEG C, and reaction times 0.15-4 hour, lead sulfate add-on is 50-500g/L.
In addition, liquor C can as step 2 after can be recycled and being 1.5-5.5mol/L to sulfate concentration) in sulfate extender recycle.
After this invention takes such scheme, complexing agent (such as quadrol) is utilized to have stronger complexing action to lead salt, regulator solution pH value is 6.0-13.0, under there is the condition of a large amount of sulfate radical in solution, lead sulfate is dissolved, adopt the impurity filtering and can be separated in lead plaster, regulate the pH value of lead complex solution afterwards, solution ph is reduced, increase the Radiation grafting of complexing agent, reduce complexing agent to the complex ability of lead salt, the lead salt in solution is made to produce precipitation with lead sulfate form, and then be separated, achieve the purification that insolubles lead sulfate is difficult to realize in conventional methods where, the highly purified lead sulfate of direct acquisition, and obtain lead-acid cell raw material sublimed lead by reprocessing, farthest have followed the angle of atom economy, lead plaster is directly purified for the purity that can be used as lead-acid cell raw material is the lead sulfate of 99.995%, 3BS(tribasic lead sulfate) or 4BS(tetra-sublimed lead), reacted filtrate can be used as vitriol and participates in circulating reaction, realize the recycling of sulfate radical.
Below in conjunction with several specific embodiment, the method is described in detail, to make above-mentioned advantage of the present invention definitely.
embodiment 1
To get commercially available specification be 12V, 7Ah weight is the waste and old valve controlled sealed lead-acid accumulator of 2 kilograms, and treating processes is as follows:
1) it is broken, isolate lead plaster, grid, Waste Sulfuric Acid and plastic waste.
2) the wherein lead plaster of 1 kilogram is put into the reactor 1 of 10L, this reactor contains excessive iron powder, 0.01mol/L ferric sulfate, the sodium sulfate of 1mol/L, the Diethylenetriamine of 0.9mol/L, add sodium carbonate-bicarbonate buffered soln maintain solution in reaction process pH value between 10.0 ± 0.2.Stir 1 hour under the condition that constant temperature is 50 DEG C, the plumbic oxide to reddish-brown reacts completely.
3) by 2) the solution filtering separation of process obtains filtrate A and filter residue.
4) filtrate A is proceeded in the reactor 2 of 10L, stir under the condition of constant temperature 75 DEG C, add sulfuric acid regulation solution pH to 5.0 and the lead salt in solution is separated out with lead sulfate form.
5) 4 are filtered) Process liquor, be separated to obtain liquor B and lead sulfate.Lead sulfate washing is clean.Dry lead sulfate quality is 1.55 kilograms.
6) getting 500g lead sulfate proceeds in the reactor 3 of 2L, and this reactor contains the sodium sulfate of 4mol/L, and constantly adding sodium hydroxide solution maintenance solution pH value in reaction process is 13.0 ± 0.2, stirs 15 hours under 15 DEG C of constant temperatures.
7) by 6) the solution filtering separation of process obtains liquor C and the 4BS containing a small amount of 3BS.Sublimed lead is dry after being washed to neutrality obtains 401g product.
Through ICP quantitative analysis, metals content impurity plumbous in lead sulfate product is as following table 1:
Table 1
Metals content impurity plumbous in sublimed lead product is as following table 2:
Table 2
As calculated, plumbous comprehensive recovery is 99.4%.
embodiment 2
Get the waste and old standby power supply lead acid cell of 12V, 100Ah, weight is 30 kilograms, and concrete treating processes is as follows:
1) it is broken, sub-elect lead plaster for subsequent use.
2) 50L solution is configured, wherein containing 0.5mol/L sodium sulfate, 0.001mol/L cobalt chloride, 1.5mol/L phenylalanine, in employing sodium hydroxide solution maintenance solution reaction process, pH value is between 7.0 ± 0.2,1 is added subsequently in solution) 10 kilograms of lead plasters obtaining in process add excessive lead powder, stir 1.5 hours under constant temperature 65 DEG C of conditions, react completely to reddish-brown plumbic oxide.
3) 2 are filtered) solution that process obtains, isolate 50L filtrate A and filter residue.
4) by 50L filtrate A under the condition of constant temperature 80 DEG C, add perchloric acid adjust ph and reach less than 4.5 lead salt is all separated out with lead sulfate form.
5) 4 are filtered) reaction soln of process, be separated to obtain liquor B and lead sulfate.Lead sulfate is cleaned.
6) by 5) lead sulfate of process adds solution 15L containing 5% sodium hydroxide, and add anhydrous sodium sulphate solid 1kg, use 10% sodium hydroxide solution to maintain solution pH value in reaction process and, between 9.0-10.0, react 2 hours under temperature 0 DEG C of agitation condition.
7) 6 are filtered) product of process, isolate liquor C and sublimed lead.Sublimed lead is dry after cleaning, and obtains product 9.5 kilograms, and analyzing sublimed lead through EDTA volumetry is 4BS and 3BS mixture.
Through ICP quantitative analysis, metals content impurity plumbous in sublimed lead product is as following table 3:
Table 3
As calculated, plumbous comprehensive recovery is 99.6%.
embodiment 3
1) by one piece heavy 60 kilograms, the lead-acid cell of 12V, 200Ah is broken, isolates lead plaster.
2) solution that 40L contains 0.7mol/L ammonium sulfate, 0.05mol/L manganous nitrate, 0.8mol/L Histidine is added in reactor 1, adopting 10% potassium hydroxide solution to maintain solution pH value in reaction process is between 8.5-9.5, adition process 1) 2 kilograms of lead plasters of gained.Stir 0.75 hour under the condition of constant temperature 70 DEG C, pass into appropriate sulfur dioxide gas, make plumbic oxide be reduced completely by the lead powder in lead plaster and sulfurous gas and dissolve.
3) by process 2) reacted solution filtration, obtain filtrate A and filter residue.
4) filtrate A constant temperature under 60 DEG C of conditions, and pass into hydrogen chloride gas and regulate the pH value of filtrate A to reduce gradually lead sulfate is precipitated completely.
5) filtration procedure 4) reacted solution, obtain liquor B and lead sulfate.Lead sulfate is cleaned.
6) by process 5) product lead sulfate add 5L and contain in the reaction solution of 0.7mol/L sodium sulfate, at room temperature stir 5 hours, in reaction process, adopt 30% ammoniacal liquor to maintain solution ph between 10.2-11.0.
7) filtration procedure 6) product, obtain liquor C and sublimed lead.Dry product after sublimed lead is cleaned.
8) use liquor C and sulfuric acid to regulate sulfate radical content in liquor B, make sulfate concentration in liquor B at more than 0.7mol/L, and by potassium hydroxide buffered soln adjust ph between 8.5-9.5.As process 1) reaction solution recycle.
9) repetitive process 1) ~ process 8) reaction 5 times, obtain sublimed lead product and amount to 7.5 kilograms.
The purity wherein plumbous to the test of product sublimed lead, through ICP quantitative analysis, the plumbous purity in sublimed lead is 99.9991%.
As calculated, plumbous comprehensive recovery is 99.8%.
embodiment 4
1) solution that 100L contains 0.5mol/L nitrilotriacetic acid(NTA), 0.6mol/L ethylenediamine-N,N'-diacetic acid(EDDA), 0.05mol/L sulphosalicylic acid iron, 1.5mol/L sodium sulfate is added in reactor 1, and with 50% ethamine buffered soln maintain solution during reaction pH value be 8.0 ± 0.2, add 30Kg lead plaster, excessive hydrogen peroxide, control temperature of reaction 90 DEG C, stopped reaction after the plumbic oxide in solution reacts completely.
2) by process 1) reaction soln filter, obtain filtrate A and filter residue.
3) filtrate A proceeds in reactor 2, is decompressed to below 20kPa ethamine is volatilized under the condition of constant temperature 90 DEG C, and the pH value of filtrate A is reduced to less than 7.0 makes the lead complex in solution be precipitated as lead sulfate completely.
4) filtered while hot step 3) solution, obtains liquor B and lead sulfate, and lead sulfate is cleaned.
5) by process 4) product lead sulfate add 200L and contain in the reaction solution of 4mol/L sodium sulfate, stir 0.5 hour at 40 DEG C, in reaction process, adopt 20% ethylamine solution to maintain solution ph between 9.5-10.9.
6) filtration procedure 5) product, obtain liquor C and sublimed lead.Dry product after sublimed lead is cleaned.
7) use sulfuric acid to regulate sulfate radical content in liquor B, make sulfate concentration in liquor B at more than 1.5mol/L, and by 20% ethylamine solution adjust ph between 8.0 ± 0.2.As process 1) reaction solution reuse.
Test wherein plumbous purity to product sublimed lead and lead sulfate, through ICP quantitative analysis, the plumbous purity in sublimed lead and lead sulfate is all not less than 99.999%.
As calculated, plumbous comprehensive recovery is 99.7%.
Compare the wet reclamation splicer skill reported, the present invention directly obtains lead-acid cell raw material by the method for chemical purification from waste lead acid battery, do not consume sweetening agent, do not consume electric energy electrolysis and refining, lead powder manufacturing processed in simultaneously not needing lead-acid cell to produce, completely eliminate and prepare the environmental pollution of lead powder process in secondary lead industry and lead-acid cell industry, achieving the combination of secondary lead industry and lead-acid cell industry, is a kind of environmental protection, energy-conservation, efficient lead-acid cell recovery method.
It should be noted that above-mentioned specific embodiment is only exemplary, under the teachings of the present invention, those skilled in the art can carry out various improvement and distortion on the basis of above-described embodiment, and these improve or distortion drops in protection scope of the present invention.
It will be understood by those skilled in the art that specific descriptions are above to explain object of the present invention, not for limiting the present invention.Protection scope of the present invention is by claim and equivalents thereof.
Claims (10)
1. a method for raw material containing lead hydrometallurgic recovery, is characterized in that, comprising:
1) solution containing ammonium sulfate, complexing agent, catalyzer, pH value between 6.0-13.0, between temperature 25-110 DEG C is used to leach raw material containing lead, and add the lead salt that plumbic oxide that reductive agent makes to exist in raw material containing lead or tri-lead tetroxide are reduced to solubility, after lead compound all dissolves, solution filters, and is separated to obtain filtrate A and insoluble substance;
2) regulated between the pH value of filtrate A to 4.0-8.0 by the mode of ammonia of volatilizing and separate out lead sulfate, be separated to obtain lead sulfate and liquor B, wherein, liquor B add sulfate radical supplement regulate sulfate concentration to 0.5-4.5mol/L, adjust ph between 6.0-13.0 after return step 1);
3) lead sulfate is directly as battery material or commodity; React with the ammonia soln containing ammonium sulfate, pH value between 8.5-13.5, between temperature 0-90 DEG C and lead sulfate, be separated and obtain comprising tribasic lead sulfate, the sublimed lead of four sublimed leads and liquor C;
Wherein, complexing agent be aspartic acid, L-Ala, pick in propylhomoserin, L-glutamic acid, proline(Pro), sarkosine, phenylalanine, leucine, Histidine, l-asparagine, glycine, Threonine, Serine, glutamine, citrulline, Methionin, arginine, half sarkosine, methionine(Met), ornithine one or both;
Catalyzer is the one in the vitriol of iron or cobalt or manganese, muriate, nitrate, perchlorate, edetate, sulfosalicylate, salicylate;
As step 2 after liquor C recycles and is 1.5-5.5mol/L to ammonium sulfate concentrations) in sulfate radical supplement realize recycle.
2. the method for raw material containing lead hydrometallurgic recovery according to claim 1, it is characterized in that, step 1) in, described raw material containing lead is chosen in lead plaster in waste lead acid battery, waste lead acid battery arbitrary in lead plaster thermal decomposition product, plumbous oxide ore, lead glance oxidation products, lead-acid cell drip washing waste material, leaded flue dust;
Wherein, at least one in lead, plumbous oxide, plumbic oxide, tri-lead tetroxide, lead sulfate, sublimed lead is contained in described raw material containing lead.
3. the method for raw material containing lead hydrometallurgic recovery according to claim 1, is characterized in that, step 1) in, described ammonium sulfate concentrations is 0.5-4.5mol/L;
Described reductive agent comprises one or both of lead, iron, hydrogen peroxide, sulfurous gas and sulphite;
Described catalyst concn is not higher than 0.1mol/L;
Described complexing agent is aspartic acid, L-Ala, pick in propylhomoserin, L-glutamic acid, proline(Pro), sarkosine, phenylalanine, leucine, Histidine, l-asparagine, glycine, Threonine, Serine, glutamine, citrulline, Methionin, arginine, half sarkosine, methionine(Met), ornithine one or both, complexing agent concentration is 0.5-5.0mol/L.
4. the method for the raw material containing lead hydrometallurgic recovery according to claim 1 or 3, is characterized in that, step 1) in, comprise further: in leaching process, add mass concentration be 1-50% ammoniacal liquor maintain reaction time pH value of solution between 6.0-13.0.
5. the method for raw material containing lead hydrometallurgic recovery according to claim 4, is characterized in that, step 1) in, preferable reaction temperature is 45-100 DEG C, and the add-on of raw material containing lead is 35-350g/L.
6. the method for raw material containing lead hydrometallurgic recovery according to claim 1, it is characterized in that, step 2) in, specifically comprise: one or both in the method alkaline matter in solution being volatilized by the mode reduced pressure or pass into gas regulate the pH value of filtrate A to separate out lead sulfate between 4.0-8.0;
Described sulfate radical supplement comprise the solution containing 1.5-7.0mol/L ammonium sulfate.
7. the method for raw material containing lead hydrometallurgic recovery according to claim 1, is characterized in that, step 3) in, the concentration of described ammonium sulfate is 0.25-5.5mol/L;
Functional quality concentration be the ammonia soln of 1%-50% maintain in reaction process reaction soln in reaction process pH between 8.5-13.5.
8. the method for the raw material containing lead hydrometallurgic recovery according to claim 1 or 7, is characterized in that, step 2) in, the temperature of reaction of described filtrate A is 45-105 DEG C.
9. the method for raw material containing lead hydrometallurgic recovery according to claim 1, is characterized in that, step 3) in, comprise further: maintain temperature of reaction 0-90 DEG C in reaction process, the reaction times is 0.15-24 hour, and lead sulfate add-on is 50-500g/L.
10. the method for raw material containing lead hydrometallurgic recovery according to claim 9, is characterized in that, step 3) in, comprise further: preferable reaction temperature is between 0-40 DEG C, the control reaction times is 0.15-4 hour.
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| PCT/CN2014/079059 WO2014201948A1 (en) | 2013-06-21 | 2014-06-03 | Wet method for recovering lead-containing raw material |
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| WO2014201948A1 (en) * | 2013-06-21 | 2014-12-24 | Zhang Chao | Wet method for recovering lead-containing raw material |
| CN104141045B (en) | 2014-08-20 | 2017-04-12 | 北京化工大学 | Method for recovering lead oxide from waste lead plaster |
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| CN105197988A (en) * | 2015-11-02 | 2015-12-30 | 扬州大学 | Ammonia process separation and refinement method of lead sulfate |
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