CN103526016A - Method for recovering lead-containing raw material by using wet process - Google Patents
Method for recovering lead-containing raw material by using wet process Download PDFInfo
- Publication number
- CN103526016A CN103526016A CN201310250004.0A CN201310250004A CN103526016A CN 103526016 A CN103526016 A CN 103526016A CN 201310250004 A CN201310250004 A CN 201310250004A CN 103526016 A CN103526016 A CN 103526016A
- Authority
- CN
- China
- Prior art keywords
- lead
- sulfate
- acid
- solution
- raw material
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
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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
- 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
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 239000007853 buffer solution Substances 0.000 description 1
- 238000001311 chemical methods and process Methods 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
- 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
- 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
- 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
- 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
Images
Classifications
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
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- Manufacture And Refinement Of Metals (AREA)
Abstract
The invention discloses a method for recovering a lead-containing raw material by using a wet process. The method comprises the steps: (1) leaching the lead-containing raw material by using a solution, adding a reducing agent to reduce lead dioxide or lead orthoplumbate in the lead-containing raw material into a soluble lead salt, after a lead compound is completely dissolved, filtering the solution, and separating to obtain a filtrate A and an insoluble substance, wherein the solution contains sulfate, a complexing agent and a catalyst; (2) adjusting the pH value of the filtrate A, separating to obtain lead sulfate and a filtrate B, and returning the filtrate B to the step (1) after sulfate radicals are replenished and the pH value is adjusted; (3) directly using lead sulfate as battery materials or commodities, subjecting a sulfate-containing alkaline solution and lead sulfate to reaction, and separating to obtain basic lead sulfates and a filtrate C, wherein the basic lead sulfates include tribasic lead sulfate and tetrabasic lead sulfate. The method can be used for purifying the lead-containing raw material to form lead sulfate and basic lead sulfates directly used for producing lead-acid batteries, thereby being an environment-friendly wet-process recovery method.
Description
Technical field
The invention belongs to waste lead acid battery and reclaim and regeneration techniques field, 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 since being born, with its cheap price and stability reliably in secondary cell market, particularly automobile battery in occupation of important position.According to relevant industries association statistics, show, within 2011, Chinese lead bullion consumption surpasses 4,000,000 tons, and wherein lead-acid cell consumption accounts for 70%.In lead-acid cell, contain a large amount of poisonous lead and compounds thereof, having realized at present industrialized pyrogenic process reclaims plumbous technology and in plumbous smelting reducing process, produces lead steam and environment is caused to severe contamination, the plumbous technology of hydrometallurgic recovery, because of the too high laboratory stage that rests on of its processing cost, fails to realize industrialization.Therefore, find a kind of efficiently, the waste lead acid battery reclaiming technology of economy and 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, can adopt the methods such as melting to reclaim.Lead plaster accounts for 50% of lead-acid cell weight, and composition is lead powder, plumbous oxide, and lead sulfate and plumbic oxide, and comprise barium sulfate, and sodium lignosulfonate, the positive and negative electrode additive of staple fibre etc., complicated component, separation difficulty, is the difficult point of secondary lead research.
General waste lead acid battery treatment process is pyrogenic process secondary lead technology at present, and representational is oxygen bottom-blowing method (Chinese publication CN200610048548.9).Pyrogenic process secondary lead technology can produce a large amount of lead steams 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 receives the concern of secondary lead industry because of it always to close friend to environmental facies, representational is that acid lead salt electrolysis tech, alkaline lead salt electrolysis tech, Solid phase electrolysis technology and chemical process are converted into some plumbous industrial goods.
The acid lead salt electrolysis tech that the Ginatta technique of take is representative, lead plaster is adopted to volatile salt or sodium carbonate desulfurization Formed lead plumbate, add reductive agent to 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 has been eliminated the pollution to environment of the lead steam that produces in pyrogenic process secondary lead reduction process, but the volatile toxic gas contaminate environment of fluoroboric acid, at electrolytic process Anodic, can produce plumbic oxide by product, need to process again the industrialization that reduced production efficiency and its too high power consumption limitations.
Solid phase electrolysis technology is coated on lead plaster water furnishing paste on negative electrode, under alkaline condition, 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, does not produce secondary pollution in the removal process of lead-acid cell, but the easily oxidation by air in the process of founding lead pig of its product lead powder, electrolytic process is not thorough simultaneously, is mingled with the lead sulfate more than 2% fully not reducing.
The alkaline lead salt electrolysis tech that a kind of method (Chinese publication ZL201010297522.4) of recycling secondary lead by electrolyzing alkaline leaded solution of take is representative, lead plaster is converted in acidic medium to lead sulfate, be dissolved in afterwards in the NaOH electrolyte of dense heat, in the electrolyzer separating with cationic membrane, electrolysis is that oxygen is with plumbous, anode does not produce plumbic oxide, the lower groove that has obtained 1.5V is pressed and fine and close smooth electrolytic lead, and electrolytic solution is realized recycle, and produces sodium sulfate byproduct.But electrolysis easily produces alkali mist Working environment is impacted at higher temperature, cationic membrane fancy price significantly increases running cost simultaneously.
Comprehensive above-mentioned wet processing both domestic and external and the ripe thermal process analyzed, wet processing can improve lead recovery and the pollution of reduction to environment, has 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 need to consume a large amount of sweetening agents (sodium carbonate, carbonic acid ammonia, sodium hydroxide) and causes cost to increase.
Summary of the invention
Technical problem to be solved by this invention is to provide a kind of method that economy, waste lead acid battery efficient and environmental protection reclaim.
The method of a kind of raw material containing lead hydrometallurgic recovery of the present invention, comprises the following steps:
1) use and to contain vitriol, complexing agent, catalyzer, pH value and at the solution between 6.0-13.0, between temperature 25-110 ℃, raw material containing lead is leached, and the lead salt that adds reductive agent to make plumbic oxide in raw material containing lead or tri-lead tetroxide be reduced to solubility, after lead compound all dissolves, solution filter, separated filtrate A and the insoluble substance of obtaining;
2) regulate the pH value of filtrate A to separate out lead sulfate between 4.0-8.0, separated lead sulfate and the liquor B of obtaining, wherein, liquor B adds sulfate radical supplement to make sulfate concentration in solution to 0.5-4.5mol/L, regulate pH value to return to step 1) after between 6.0-13.0;
3) lead sulfate is directly as battery material or commodity; With containing vitriol, pH value, at the basic solution between 8.5-13.5, between temperature 0-90 ℃, react with lead sulfate, separation obtains comprising sublimed lead and the liquor C of tribasic lead sulfate, four sublimed leads;
Wherein, liquor C recycle to sulfate concentration be as step 2 after 1.5-5.5mol/L) 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, in described raw material containing lead, contain at least one in lead, plumbous oxide, plumbic oxide, tri-lead tetroxide, lead sulfate, sublimed lead.
Further, preferred method is, in step 1), described vitriol is chosen a kind of in ammonium sulfate that concentration is 0.5-4.5mol/L, vitriolate of tartar, sodium sulfate;
Described reductive agent comprises one or both of lead, iron, hydrogen peroxide, sulfurous gas and sulphite;
Described catalyzer is a kind of in the vitriol that comprises 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 is greater than 7.78 with the logarithmic value of lead ion formation soluble complexes and complex compound conditional stability constant, one or both in the complexone that the logarithmic value that complexing agent forms the conditional stability constant of complex compound with lead ion in solution in pH value between 4.0-4.5 is less than 7.78 a-amino acid, organic amine compound, contain amino oxalic acid group 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), further to comprise: in leaching process, while adding buffered soln to maintain reaction, pH value of solution is between 6.0-13.0;
Wherein, buffered soln is to contain 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-sodium bicarbonate, Sodium phosphate dibasic-sodium hydroxide at the solution of 1-50%.
Further, preferably method is, in step 1), temperature of reaction is 45-100 ℃, and the add-on of raw material containing lead is 35-350g/L.
Further, preferred method is, step 2) in, specifically comprise: to adding acid or strong acid weak base salt in solution, pass into sour gas and make solution absorb sour gas, make one or both in the method for the alkaline matter volatilization in solution regulate the pH value of filtrate A to separate out lead sulfate between 4.0-8.0 by the mode reducing pressure or pass into gas;
Wherein, described acid comprise mass concentration at the hydrochloric acid of 1%-37%, the perchloric acid of the sulfuric acid of 2%-98%, 2%-70% interior a kind of; Described sour gas comprises a kind of of hydrogenchloride, sulfurous gas, carbonic acid gas; The mass concentration that described strong acid weak base salt comprises Tai-Ace S 150, ferric sulfate, ferrous sulfate at the solution of 1-50% or solid interior a kind of; Described alkaline matter comprises a kind of of methylamine, ethamine, quadrol, propylene diamine, ammonia; Described sulfate radical supplement comprise that the ammonium sulfate that contains 1.5-7.0mol/L or sodium sulfate or potassium sulfate solution, the sulfuric acid of 10-98%, sulfate concentration are a kind of in 1.5-5.5mol/L solution.
Further, preferred method is, in step 3), described vitriol is that concentration is a kind of in the ammonium sulfate, vitriolate of tartar, sodium sulfate of 0.25-5.5mol/L;
Described basic solution use contain solution that a kind of mass concentration in methylamine, ethamine, quadrol, propylene diamine, thanomin, triethanolamine, ammonia, sodium hydroxide, potassium hydroxide, carbonate, supercarbonate is 1%-50% in reaction process, maintain reaction soln in reaction process pH value between 8.5-13.5.
Further, preferred method comprises: step 2), the temperature of reaction of described solution is 45-100 ℃.
Further, preferred method is, in step 3), further to comprise:
In reaction process, maintain temperature of reaction 0-90 ℃, reaction times 0.15-24 hour, lead sulfate add-on is 50-500g/L.
Further, preferred method is, in step 3), further to comprise:
Temperature of reaction is between 0-40 ℃, and the control reaction times is 0.15-4 hour.After the present invention has taked such scheme, utilize complexing agent (for example quadrol) to there is stronger complexing action to lead salt, regulator solution pH value is 6.0-13.0, in solution, exist and under the condition of a large amount of sulfate radicals, make lead sulfate dissolve (complexing agent is greater than 7.78 with the logarithmic value that lead ion forms the conditional stability constant of soluble complexes and complex compound in this solution), adopt and filter the impurity getting final product in separated lead plaster, regulate afterwards the pH value of lead complex solution, pH is reduced, increase the sour effect of complexing agent, reduce the complex ability of complexing agent to lead salt, make lead salt in solution produce precipitation (complexing agent is less than 7.78 with the logarithmic value that lead ion forms the conditional stability constant of complex compound in this solution) with lead sulfate form, and then separated, realize insolubles lead sulfate and in traditional method, be difficult to the purification realizing, directly obtain highly purified lead sulfate, and by processing and obtain lead-acid cell raw material sublimed lead again, farthest followed the angle of atom economy, lead plaster is directly purified as can be used as the lead sulfate that the purity of lead-acid cell raw material is 99.995%, 3BS(tribasic lead sulfate) or 4BS(tetra-sublimed leads), reacted filtrate can be used as vitriol and participates in circulating reaction, realize the recycling of sulfate radical.
Compare the wet reclamation splicer skill of having 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, do not need the lead powder manufacturing processed in lead-acid cell production simultaneously, having eliminated the environmental pollution of preparing lead powder process at secondary lead industry and lead-acid cell completely, realized the combination of secondary lead industry with 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, so that above-mentioned advantage of the present invention is clearer and more definite.
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 by lead plaster be reduced to lead bullion again refining be electrolytic lead, lead-acid cell industry is oxidized to plumbous oxide by electrolytic lead, then makes lead-acid cell.Lead plaster obtains electrolytic lead through reduction, and electrolytic lead oxidation obtains lead-acid cell raw material plumbous oxide, and warp and cream process obtain tribasic lead sulfate (3BS) or four sublimed leads (4BS) are coated with 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 is more than 99.995%) to the chemical reduction of lead plaster and purification, lead sulfate is processed and obtained high-purity sublimed lead that comprises 3BS and 4BS, sublimed lead can directly 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 do 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 contains vitriol, complexing agent, catalyzer, the pH solution between 6.0-13.0 leaded material is leached, the lead salt that adds reductive agent to make the plumbic oxide that may exist in leaded material or tri-lead tetroxide be reduced to solubility, after the plumbic oxide in leaded material or the whole dissolvings of other lead compounds, solution filter, separated filtrate A and the insoluble substance (residuals) of obtaining.
In this step 1), vitriol is a kind of in ammonium sulfate, vitriolate of tartar, 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 a kind of in the vitriol that comprises 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 is greater than 7.78 with the logarithmic value of lead ion formation soluble complexes and complex compound conditional stability constant, one or both in the complexone that the logarithmic value that complexing agent forms the conditional stability constant of complex compound with lead ion in solution in pH value between 4.0-4.5 is less than 7.78 a-amino acid, organic amine compound, contain amino oxalic acid group 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.
And in order to guarantee the efficiency in leaching process, in leaching process, while adding buffered soln to maintain reaction, pH value of solution is between 6.0-13.0; Wherein, buffered soln can be chosen a kind of mass concentration of containing in methylamine, ethamine, quadrol, propylene diamine, ammonia, sodium hydroxide, potassium hydroxide, potassium primary phosphate-sodium hydroxide, boric acid-borax, hydrochloric acid-thanomin, sodium carbonate-sodium bicarbonate, Sodium phosphate dibasic-sodium hydroxide at the solution of 1-50%.
In above process, preferred temperature of reaction is 45-100 ℃.
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, in described raw material containing lead, contain at least one in lead, plumbous oxide, plumbic oxide, tri-lead tetroxide, lead sulfate, sublimed lead, in an embodiment, choose lead plaster, and lead plaster add-on is 35-350g/L.
Wherein, described complexing agent feature describes in the above-described embodiments, be that it is that the logarithmic value that forms the conditional stability constant of soluble complexes and complex compound with lead ion in the solution of complexing agent between pH value 8.5-9.5 is greater than 7.78, it is that lead sulfate is containing 1.0-2.0mol/L sulfate radical that the logarithmic value that complexing agent forms the conditional stability constant of complex compound with lead ion in pH value in the solution between 4.0-4.5 is less than 7.78(, 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 is separated out with lead sulfate form for lead complex in the solution between 4.0-4.5) a-amino acid, organic amine compound, one or both in the complexone that contains amino oxalic acid group or Padil group, complexing agent concentration is 0.5-5.0mol/L.。
Therefore, utilize complexing agent (for example quadrol) to have stronger complexing action to lead salt, regulator solution pH value is 6.0-13.0, exists under the condition of a large amount of sulfate radicals lead sulfate is dissolved in solution, adopts that to filter be the impurity in separable raw material containing lead.
Step 2): regulate the pH value of filtrate A to separate out lead sulfate between 4.0-8.0, separated lead sulfate and liquor B, comprising: adopt to comprise to adding acid or strong acid weak base salt in solution, pass into sour gas and make solution absorb sour gas, by the mode reducing pressure or pass into gas, make one or both in the method for the alkaline matter volatilization in solution regulate the pH value of filtrate A to separate 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, regulates pH value to return to step 1) after between 6.0-13.0,
Wherein, described sulfate radical supplement comprise that the ammonium sulfate that contains 1.5-7.0mol/L or sodium sulfate or potassium sulfate solution, the sulfuric acid of 10-98%, sulfate concentration are a kind of in 1.5-5.0mol/L solution.Described acid comprise mass concentration at the hydrochloric acid of 1%-37%, the perchloric acid of the sulfuric acid of 2%-98%, 2%-70% interior a kind of, described sour gas comprises a kind of of hydrogenchloride, sulfurous gas, carbonic acid gas, the mass concentration that described strong acid weak base salt comprises Tai-Ace S 150, ferric sulfate, ferrous sulfate is at the solution of 1-50% or solid interior a kind of, and described alkaline matter comprises a kind of of methylamine, ethamine, quadrol, propylene diamine, ammonia.
And lead sulfate can be directly as battery material or commodity; Or, in preferred embodiment, also comprise:
Step 3): react with lead sulfate at the basic solution between 8.5-13.5, between temperature 0-90 ℃ with containing vitriol, pH value, separation obtains comprising sublimed lead and the liquor C of tribasic lead sulfate, four sublimed leads, wherein, sublimed lead can be through sintering or directly as battery material, is used.
In this step, described vitriol is comprise ammonium sulfate, vitriolate of tartar, sodium sulfate a kind of, and concentration is 0.25-5.5mol/L.
Described basic solution adopt contain comprise solution that a kind of mass concentration in methylamine, ethamine, quadrol, propylene diamine, thanomin, triethanolamine, ammonia, sodium hydroxide, potassium hydroxide, carbonate, supercarbonate is 1%-50% maintain reaction soln in reaction process pH value between 8.5-13.0.
Wherein, keep temperature of reaction 0-90 ℃, the reaction times is 0.15-24 hour, preferred temperature of reaction between 0-40 ℃, reaction times 0.15-4 hour, lead sulfate add-on is 50-500g/L.
In addition, liquor C can be recycled and can be used as step 2 after sulfate concentration is 1.5-5.5mol/L) in the recycle of vitriol supplement.
After the present invention has taked such scheme, utilize complexing agent (for example quadrol) to there is stronger complexing action to lead salt, regulator solution pH value is 6.0-13.0, in solution, existing under the condition of a large amount of sulfate radicals dissolves lead sulfate, adopt and filter the impurity getting final product in separated lead plaster, regulate afterwards the pH value of lead complex solution, pH is reduced, increase the sour effect of complexing agent, reduce the complex ability of complexing agent to lead salt, make the lead salt in solution produce precipitation with lead sulfate form, and then separated, realize insolubles lead sulfate and in traditional method, be difficult to the purification realizing, directly obtain highly purified lead sulfate, and by processing and obtain lead-acid cell raw material sublimed lead again, farthest followed the angle of atom economy, lead plaster is directly purified as can be used as the lead sulfate that the purity of lead-acid cell raw material is 99.995%, 3BS(tribasic lead sulfate) or 4BS(tetra-sublimed leads), reacted filtrate can be used as vitriol and participates in circulating reaction, realize the recycling of sulfate radical.
Below in conjunction with several specific embodiments, the method is elaborated, so that above-mentioned advantage of the present invention is clearer and more definite.
embodiment 1
Getting commercially available specification is that 12V, 7Ah weight are the waste and old valve controlled sealed lead-acid accumulator of 2 kilograms, and treating processes is as follows:
1), by its fragmentation, isolate lead plaster, grid, Waste Sulfuric Acid and plastic waste.
2) lead plaster of 1 kilogram is wherein 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-sodium bicarbonate buffer solution maintain solution in reaction process pH value between 10.0 ± 0.2.Under the condition that constant temperature is 50 ℃, stir 1 hour, react completely to the plumbic oxide of reddish-brown.
3) by 2) solution filter of process separated filtrate A and filter residue.
4) filtrate A is proceeded in the reactor 2 of 10L, under the condition of 75 ℃ of constant temperature, stir, add sulfuric acid regulation solution pH to 5.0 that the lead salt in solution is separated out with lead sulfate form.
5) filter 4) Process liquor, separated liquor B and the lead sulfate of obtaining.Lead sulfate washing is clean.Dry lead sulfate quality is 1.55 kilograms.
6) get in the reactor 3 that 500g lead sulfate proceeds to 2L, the sodium sulfate that this reactor contains 4mol/L, constantly adding sodium hydroxide solution to maintain solution pH value in reaction process is 13.0 ± 0.2, under 15 ℃ of constant temperatures, stirs 15 hours.
7) by 6) solution filter of process separated liquor C and the 4BS that contains a small amount of 3BS.Sublimed lead is dried to obtain 401g product after being washed to neutrality.
Through ICP quantitative analysis, in lead sulfate product, plumbous metals content impurity is as following table 1:
Table 1
In sublimed lead product, plumbous metals content impurity is as following table 2:
Table 2
As calculated, plumbous comprehensive recovery is 99.4%.
embodiment 2
The waste and old standby power supply lead acid cell of getting 12V, 100Ah, weight is 30 kilograms, concrete treating processes is as follows:
1) by its fragmentation, sub-elect lead plaster standby.
2) configuration 50L solution, wherein contain 0.5mol/L sodium sulfate, 0.001mol/L cobalt chloride, 1.5mol/L phenylalanine, adopt sodium hydroxide solution to maintain in solution reaction process pH value between 7.0 ± 0.2, with adding 1 in backward solution) 10 kilograms of lead plasters obtaining in process add excessive lead powder, under 65 ℃ of conditions of constant temperature, stir 1.5 hours, react completely to reddish-brown plumbic oxide.
3) filter 2) solution that process obtains, isolate 50L filtrate A and filter residue.
4) by 50L filtrate A under the condition of 80 ℃ of constant temperature, add perchloric acid to regulate pH value to reach below 4.5 lead salt all separated out with lead sulfate form.
5) filter 4) reaction soln of process, separated liquor B and lead sulfate.Lead sulfate is cleaned.
6) by 5) lead sulfate of process adds the solution 15L that contains 5% sodium hydroxide, adds anhydrous sodium sulphate solid 1kg, and use 10% sodium hydroxide solution to maintain solution pH value in reaction process and, between 9.0-10.0, under 0 ℃ of agitation condition of temperature, react 2 hours.
7) filter 6) product of process, isolate liquor C and sublimed lead.Sublimed lead is dry after cleaning, and obtains 9.5 kilograms of products, and through EDTA volumetry, analyzing sublimed lead is 4BS and 3BS mixture.
Through ICP quantitative analysis, in sublimed lead product, plumbous metals content impurity is as following table 3:
Table 3
As calculated, plumbous comprehensive recovery is 99.6%.
embodiment 3
1) heavy 60 kilograms by one, the lead-acid cell of 12V, 200Ah is broken, isolates lead plaster.
2) solution that adds 40L to contain 0.7mol/L ammonium sulfate, 0.05mol/L manganous nitrate, 0.8mol/L Histidine in reactor 1, adopt 10% potassium hydroxide solution maintain solution in reaction process pH value between 8.5-9.5, adition process 1) 2 kilograms of lead plasters of gained.Under the condition of 70 ℃ of constant temperature, stir 0.75 hour, pass into appropriate sulfur dioxide gas, make plumbic oxide be reduced completely and dissolve by the lead powder in lead plaster and sulfurous gas.
3) by process 2) reacted solution filter, obtain filtrate A and filter residue.
4) filtrate A constant temperature under 60 ℃ of conditions, and pass into hydrogen chloride gas and regulate the pH value of filtrate A to reduce lead sulfate is precipitated completely gradually.
5) filtration procedure 4) reacted solution, obtain liquor B and lead sulfate.Lead sulfate is cleaned.
6) by process 5) product lead sulfate add in the reaction solution that 5L contains 0.7mol/L sodium sulfate, at room temperature stir 5 hours, in reaction process, adopt 30% ammoniacal liquor to maintain pH between 10.2-11.0.
7) filtration procedure 6) product, obtain liquor C and sublimed lead.After being cleaned, sublimed lead is dried to obtain product.
8) use liquor C and sulfuric acid to regulate the sulfate radical content in liquor B, make sulfate concentration in liquor B more than 0.7mol/L, and by potassium hydroxide buffered soln adjusting pH value 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.
Product sublimed lead is tested to wherein plumbous purity, and 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 adds 100L to contain 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 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 90 ℃ of temperature of reaction, 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 and makes ethamine volatilization under the condition of 90 ℃ of constant temperature, and the pH value of filtrate A is reduced to below 7.0 and 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 in the reaction solution that 200L contains 4mol/L sodium sulfate, at 40 ℃, stir 0.5 hour, in reaction process, adopt 20% ethylamine solution to maintain pH between 9.5-10.9.
6) filtration procedure 5) product, obtain liquor C and sublimed lead.After being cleaned, sublimed lead is dried to obtain product.
7) use sulfuric acid to regulate the sulfate radical content in liquor B, make sulfate concentration in liquor B more than 1.5mol/L, and by 20% ethylamine solution adjusting pH value between 8.0 ± 0.2.As process 1) reaction solution reuse.
Product sublimed lead and lead sulfate are tested to wherein plumbous purity, and 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 of having 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, do not need the lead powder manufacturing processed in lead-acid cell production simultaneously, having eliminated the environmental pollution of preparing lead powder process in secondary lead industry and lead-acid cell industry completely, realized the combination of secondary lead industry with 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 instruction 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 improvement or distortion drop in protection scope of the present invention.
It will be understood by those skilled in the art that specific descriptions are above in order to explain object of the present invention, not for limiting the present invention.Protection scope of the present invention is limited by claim and equivalent thereof.
Claims (11)
1. a method for raw material containing lead hydrometallurgic recovery, is characterized in that, comprising:
1) use and to contain vitriol, complexing agent, catalyzer, pH value and at the solution between 6.0-13.0, between temperature 25-110 ℃, raw material containing lead is leached, and the lead salt that adds reductive agent to make the plumbic oxide that exists in raw material containing lead or tri-lead tetroxide be reduced to solubility, after lead compound all dissolves, solution filter, separated filtrate A and the insoluble substance of obtaining;
2) regulate the pH value of filtrate A to separate out lead sulfate between 4.0-8.0, separated lead sulfate and the liquor B of obtaining, wherein, liquor B adds sulfate radical supplement to regulate sulfate concentration to 0.5-4.5mol/L, regulates pH value to return to step 1) after between 6.0-13.0;
3) lead sulfate is directly as battery material or commodity; With containing vitriol, pH value, at the basic solution between 8.5-13.5, between temperature 0-90 ℃, react with lead sulfate, separation obtains comprising sublimed lead and the liquor C of tribasic lead sulfate, four sublimed leads;
Wherein, liquor C recycle to sulfate concentration be as step 2 after 1.5-5.5mol/L) 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, in step 1), 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, in described raw material containing lead, contain at least one in lead, plumbous oxide, plumbic oxide, tri-lead tetroxide, lead sulfate, sublimed lead.
3. the method for raw material containing lead hydrometallurgic recovery according to claim 1, is characterized in that, in step 1), described vitriol is chosen a kind of in vitriolate of tartar that concentration is 0.5-4.5mol/L, ammonium sulfate, sodium sulfate;
Described reductive agent comprises one or both of lead, iron, hydrogen peroxide, sulfurous gas and sulphite;
Described catalyzer is a kind of in the vitriol that comprises 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 is greater than 7.78 with the logarithmic value of lead ion formation soluble complexes and complex compound conditional stability constant, one or both in the complexone that the logarithmic value that complexing agent forms the conditional stability constant of complex compound with lead ion in solution in pH value between 4.0-4.5 is less than 7.78 a-amino acid, organic amine compound, contain amino oxalic acid group or Padil group, complexing agent concentration is 0.5-5.0mol/L.
4. according to the method for the raw material containing lead hydrometallurgic recovery described in claim 2 or 3, it is characterized in that, 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.
5. according to the method for the raw material containing lead hydrometallurgic recovery described in claim 1 or 3, it is characterized in that, in step 1), further comprise: in leaching process, while adding buffered soln to maintain reaction, pH value of solution is between 6.0-13.0;
Wherein, buffered soln is to contain 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-sodium bicarbonate, Sodium phosphate dibasic-sodium hydroxide at the solution of 1-50%.
6. the method for raw material containing lead hydrometallurgic recovery according to claim 5, is characterized in that, in step 1), preferable reaction temperature is 45-100 ℃, and the add-on of raw material containing lead is 35-350g/L.
7. the method for raw material containing lead hydrometallurgic recovery according to claim 1, it is characterized in that, step 2) in, specifically comprise: to adding acid or strong acid weak base salt in solution, pass into sour gas and make solution absorb sour gas, make one or both in the method for the alkaline matter volatilization in solution regulate the pH value of filtrate A to separate out lead sulfate between 4.0-8.0 by the mode reducing pressure or pass into gas;
Wherein, described acid comprise mass concentration at the hydrochloric acid of 1%-37%, the perchloric acid of the sulfuric acid of 2%-98%, 2%-70% interior a kind of; Described sour gas comprises a kind of of hydrogenchloride, sulfurous gas, carbonic acid gas; The mass concentration that described strong acid weak base salt comprises Tai-Ace S 150, ferric sulfate, ferrous sulfate at the solution of 1-50% or solid interior a kind of; Described alkaline matter comprises a kind of of methylamine, ethamine, quadrol, propylene diamine, ammonia; Described sulfate radical supplement comprise that the ammonium sulfate that contains 1.5-7.0mol/L or sodium sulfate or potassium sulfate solution, the sulfuric acid of 10-98%, sulfate concentration are a kind of in 1.5-5.5mol/L solution.
8. the method for raw material containing lead hydrometallurgic recovery according to claim 1, is characterized in that, in step 3), described vitriol is that concentration is a kind of in the ammonium sulfate, vitriolate of tartar, sodium sulfate of 0.25-5.5mol/L;
Described basic solution use contain solution that a kind of mass concentration in methylamine, ethamine, quadrol, propylene diamine, thanomin, trolamine, ammonia, sodium hydroxide, potassium hydroxide, carbonate, supercarbonate is 1%-50% in reaction process, maintain reaction soln in reaction process pH between 8.5-13.5.
9. according to the method for the raw material containing lead hydrometallurgic recovery described in claim 1 or 8, it is characterized in that step 2) in, the preferable reaction temperature of described solution is 45-105 ℃.
10. the method for raw material containing lead hydrometallurgic recovery according to claim 1, is characterized in that, in step 3), further comprises:
In reaction process, maintain temperature of reaction 0-90 ℃, the reaction times is 0.15-24 hour, and lead sulfate add-on is 50-500g/L.
The method of 11. raw material containing lead hydrometallurgic recovery according to claim 10, is characterized in that, in step 3), further comprises:
Preferable reaction temperature is between 0-40 ℃, and the control reaction times is 0.15-4 hour.
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| BG62098B1 (en) * | 1996-05-31 | 1999-02-26 | Химико-технологичен и металургичен Университет | Method for reworking of waste lead battery paste |
| CN1948162A (en) * | 2006-10-30 | 2007-04-18 | 南昌大学 | Technology of preparing tribasic lead sulphate using bismusic acid leaching slag |
| CN101636512A (en) * | 2007-01-17 | 2010-01-27 | 米尔布鲁克铅再生科技有限公司 | From the scrap lead battery that contains electrode paste, reclaim the lead of high purity carbon lead plumbate form |
| CN101831668A (en) * | 2010-05-21 | 2010-09-15 | 北京化工大学 | Clean wet-method solid-liquid two-phase electroreduction lead recovery method |
| CN102206750A (en) * | 2011-05-04 | 2011-10-05 | 中南大学 | Method for recovering lead from lead-containing material by matching leaching-electrowinning method |
| CN102275982A (en) * | 2011-06-07 | 2011-12-14 | 沈阳化工大学 | Mixed solvent for dissolving lead sulfate |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| SU619532A1 (en) * | 1977-02-01 | 1978-08-15 | Сибирский металлургический институт им.С.Орджоникидзе | Method of obtaining lead |
-
2013
- 2013-06-21 CN CN201310250004.0A patent/CN103526016B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| BG62098B1 (en) * | 1996-05-31 | 1999-02-26 | Химико-технологичен и металургичен Университет | Method for reworking of waste lead battery paste |
| CN1948162A (en) * | 2006-10-30 | 2007-04-18 | 南昌大学 | Technology of preparing tribasic lead sulphate using bismusic acid leaching slag |
| CN101636512A (en) * | 2007-01-17 | 2010-01-27 | 米尔布鲁克铅再生科技有限公司 | From the scrap lead battery that contains electrode paste, reclaim the lead of high purity carbon lead plumbate form |
| CN101831668A (en) * | 2010-05-21 | 2010-09-15 | 北京化工大学 | Clean wet-method solid-liquid two-phase electroreduction lead recovery method |
| CN102206750A (en) * | 2011-05-04 | 2011-10-05 | 中南大学 | Method for recovering lead from lead-containing material by matching leaching-electrowinning method |
| CN102275982A (en) * | 2011-06-07 | 2011-12-14 | 沈阳化工大学 | Mixed solvent for dissolving lead sulfate |
Cited By (24)
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|---|---|---|---|---|
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Effective date of registration: 20170323 Address after: 100176 Beijing economic and Technological Development Zone, No. five, sea road, building 58, building 7, floor 1 Patentee after: Beijing Ruifeng Environmental Protection Technology Co., Ltd. Address before: 100052 Shanxi street, Beijing, No. 18, No. Patentee before: Zhang Chao |