CN105936979A - Lead recovery agent for lead-containing wastes and application method thereof - Google Patents
Lead recovery agent for lead-containing wastes and application method thereof Download PDFInfo
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- CN105936979A CN105936979A CN201610526718.3A CN201610526718A CN105936979A CN 105936979 A CN105936979 A CN 105936979A CN 201610526718 A CN201610526718 A CN 201610526718A CN 105936979 A CN105936979 A CN 105936979A
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- lead
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- garbage
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B13/00—Obtaining lead
- C22B13/04—Obtaining lead by wet processes
- C22B13/045—Recovery from waste materials
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
- C22B7/006—Wet processes
- C22B7/007—Wet processes by acid leaching
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/54—Reclaiming serviceable parts of waste accumulators
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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
-
- 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
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/84—Recycling of batteries or fuel cells
Abstract
The invention discloses a lead recovery agent for lead-containing wastes and an application method thereof. According to the application method, an extracting agent (A), an extracting agent (B), and an extracting agent (C) are used to extract the lead element in lead paste or lead-containing wastes in different sections, at the same time, the recovered lead is in a form of lead citrate hydrate; and after burning, the recovered lead is converted into a mixture of lead oxide and lead. The lead recovery rate is high, compared with the lead recovery mode (direct extraction) in a critic acid-lead paste wet process, the cost can be saved, and the recovery rate is increased. Compared with the lead recovery mode of a conventional fire method, the sulfide gas and energy consumption are both reduced, and the environment is protected.
Description
Technical field
The present invention relates to reclaim lead from leaded garbage.Specifically, but not exclusively, the present invention relates to from scrap lead acid
The method reclaiming lead in accumulator, particularly uses wet-leaching and low-temperature bake technique from scrap lead the scrap lead cream polluting environment
Accumulator reclaims and directly prepares Hydrocerussitum (Ceruse), and the end product of the method.
Background technology
At present, the lead bullion of 75% is applied to lead-acid accumulator in the world, it is believed that in lead battery, the lead close to 90% is recovered,
And the lead yield that the whole world is more than 50% is derived from the lead of recovery.Along with electric automobile, electric motor car, the swift and violent of communications industry are sent out
Exhibition, the demand of lead-acid accumulator is continuously increased, and substitutes learies and necessarily also increases.And reclaiming lead can make lead metal
Enter the benign cycle of productive consumption regeneration, make full use of regenerated resources (scrap lead), reduce Resources (lead ore)
Yield, extend its mining term, meet country the strategy of sustainable development, market potential is huge.
In lead-acid accumulator, the process of scrap lead cream is maximum difficult point, and lead plaster is mainly the active substance on pole plate
By forming slurry like material after discharge and recharge, mainly include PbSO4、PbO2, PbO and a small amount of Pb and other impurity composition.State at present
The inside and outside major way processing scrap lead cream includes following several: hydrometallurgical, pyrometallurgical method, wet method-pyrogenic process combination method.
From waste lead accumulator, reclaim lead at present mostly use pyrometallurgical smelting, mainly include three kinds: directly pyrometallurgical smelting, elder generation
Sub-elect lead plaster material, then carry out smelting, lead plaster elder generation desulfurization conversion carries out pyrometallurgical smelting operation again, simple to operate, but these pass
System high temperature pyrometallurgical smelting has the disadvantage in that to be needed by reverberatory furnace, turn round the specialty smelting furnaces such as short stove, blast furnace, and equipment becomes
This height；PbSO in lead plaster4Content typically more than 50%, PbSO4Fusing point is high, reach the temperature decomposed completely will 1000 DEG C with
On, energy consumption is high；In fusion process, vulcanized lead decomposes generation sulfur dioxide, causes sulfurous gas to pollute；Cause a large amount of under high temperature
Lead volatility lose and formed the lead dust of contaminative, reduce lead recovery.
The feature of hydrometallurgy scrap lead battery is first desulfurization, is electrolysed to obtain lead again, does not has sulfur dioxide problem of environmental pollution, with
And avoid pyrogenic process problem, the problem includes: high energy consumption problem.Typical method includes RSR method, CX-EW method；Its principle converts-leaching by lead plaster
Go out-mode of electrodeposition obtains lead and lead oxide, response speed is more slow, inefficient；At present, correlational study person also proposed
The new recovery process of citric acid wet method, but still there is techniques below difficult point: reaction conversion rate is slow, general more than 24-48 h
The desulfuration efficiency of more than 95% could be obtained；Generate crystal and other magazins' layout difficulties of lead citrate；Citric acid solution and lead
The liquid-solid reaction system of cream brings condensation reaction, forms the core-shell structure of product-reactant, and transformation efficiency is on the low side；Citric acid becomes
This height, relatively low reaction efficiency considerably increases the cost of actual recovered and process operation.
Being used mostly wet method-pyrogenic process multiple techniques in developed countries such as the U.S., Germany and Italy, this technology is by lead plaster
First carry out wet desulphurization process, it is to avoid the pollution of the sulfiding gas such as sulfur dioxide；After the lead plaster after desulfurization is melted through pyrogenic process
The technological process of refining, can be reduced to about 300 DEG C by decomposition temperature by 1000 DEG C before converting, and reduces at recycling waste lead batteries
Energy consumption in reason.This technology reduces the pollution section in lead regenerative process and reduces energy consumption, is the method being more worth advocating,
Also it is the developing direction of WeiLai Technology.
Summary of the invention
It is an object of the invention to provide a kind of lead recovery catalyst for leaded garbage, and application process, by wet
Method reclaims the lead in leaded garbage with the form of lead citrate, and provides pyrogenic process method for refining on this basis, by citric acid
Lead converts, and carries out lead recovery with lead oxide or lead simple substance form.
As a example by waste gas lead battery lead plaster, in lead plaster raw material, dominant phase composition comprises lead sulfate, Lead oxide brown, oxygen
Change lead and lead simple substance, the most also there is remaining metal ion compound being scattered in lead plaster, and the separable impurity of physics.
For the leaded garbage of similar lead plaster thing phase composition, the lead recovery catalyst that the present invention can be used to provide carries out lead and returns
Receive, can effectively the metal ion compound in this type of leaded garbage be separated, and all kinds of by leaded garbage
Leaded material is converted into high-purity citric acid lead and reclaims, and lead citrate can be converted into high-purity by high-temperature roasting
Lead oxide and a small amount of lead simple substance, effectively leaded garbage is recycled.
For achieving the above object, the present invention provides a kind of lead recovery catalyst for leaded garbage, is made up of following material:
A kind of lead recovery catalyst for leaded garbage, it is characterised in that be made up of following material:
Digestion agent A: concentration is not less than the sodium chloride solution of 15%, can be dissolved in described sodium chloride solution with concentration not less than 5%
Hydrochloric acid；And the calcium chloride of described sodium chloride solution can be dissolved in not less than 5% with concentration；
Digestion agent B: concentration is the dilute sulfuric acid of 5% ~ 20%；
Digestion agent C: concentration is not less than the citric acid solution of 20%, can be not less than 3% with concentration and be dissolved in described citric acid solution
In hydrogen peroxide, 25% ammonia being dissolved in described citric acid solution can be not less than with concentration；
In mass ratio, described digestion agent A: digestion agent B: digestion agent C=50 ~ 75:1:20 ~ 45.
As improvement, this lead recovery catalyst is made up of following material:
Digestion agent A: saturated nacl aqueous solution, the hydrochloric acid that described saturated nacl aqueous solution can be dissolved in concentration not less than 20%；
And the calcium chloride of described saturated nacl aqueous solution can be dissolved in not less than 15% with concentration；
Digestion agent B: concentration is the dilute sulfuric acid of 15% ~ 20%；
Digestion agent C: saturated citric acid solution, 10% mistake being dissolved in described saturated citric acid solution can be not less than with concentration
Hydrogen oxide, the excessive ammonia of relatively described saturated citric acid solution；
In mass ratio, described digestion agent A: digestion agent B: digestion agent C=55 ~ 65:1:20 ~ 30.
Use the lead recovery catalyst that the present invention provides, and use following methods to extract:
(1) by waste gas lead battery lead plaster remove impurity, it is allowed to after pulverizing in even suspension sodium chloride solution in digestion agent A, heating
And add the hydrochloric acid in digestion agent A and be sufficiently mixed, keep heating-up temperature and be sufficiently mixed uniformly, adding the chlorine in digestion agent A
Changing calcium, fully filter pressing repeatedly after reaction, room temperature is down to by the clear liquor after filtering off insoluble matter, and filter pressing obtains the crystalline deposit separated out
Thing；
(2) the crystalline deposit thing addition digestion agent B in step (1) will fully react, and remove impurity, obtain reactant liquor；
(3) reactant liquor in step (2) is added in the citric acid solution in digestion agent C, add the peroxidating in digestion agent C
After hydrogen solution fully reacts, excess adds the ammonia in digestion agent C and to control Leaching Systems be pH 5 ~ 6, makes lead citrate crystallize
Hydrate deposition fully separates out, and obtains lead citrate crystal of hydrate precipitation through filter pressing.
By step (1), hydrochloric acid-sodium chloride-calcium chloride system that digestion agent A is formed, process discarded lead battery lead plaster, energy
Make the metal ion in lead plaster be dissolved in the middle of digestion agent A, and lead sulfate in lead plaster, lead oxide, lead simple substance occur following anti-
Should, generate the lead chloride crystal settling insoluble in digestion agent A；
PbSO4+2NaCl→PbCl2+Na2SO4
PbO+2NaCl+H2O→PbCl2+2NaOH
Pb+2HCl→PbCl2+H2↑
PbO+2HCl→PbCl2+H2O
PbO2+4HCl→PbCl2+2H2O+Cl2↑
Pb+PbO2+4HCl→2PbCl2+2H2O
In above-mentioned reaction, in a heated condition, can be with the sodium chloride following reversible reaction of generation due to lead chloride:
PbCl2+2NaCl⇌Na2PbCl4
For improving lead recovery as far as possible, Na can be made by the way of cooling2PbCl4To PbCl2Convert, and lead chloride is at low temperature
Time, the dissolubility in water is relatively low, is 3.22%, is 1.07% at 25 DEG C under 100 DEG C of states, by the addition of calcium chloride, generates
CaSO insoluble in leaching agent A4, Na can be avoided2SO4Accumulation, as much as possible improve obtain PbCl2Acquisition rate；
Na2SO4+CaCl2→CaSO4↓+2NaCl
Simultaneously as in alkali metal, alkaline earth metal chloride hot solution, the chloride of lead is at acid NaCl, CaCl2Mixed
Close in solution, with PbCl+、PbCl2 0、PbCl3 -、PbCl4 2-Presented in, dissolubility is greatly promoted, the chloride of lead when 65 DEG C
Leaching rate reaches 80%, and when 95 DEG C, the chloride leaching rate of lead reaches 95%, and when temperature promotes, reaction rate improves
The most notable.
To filter off of obtaining be after the clear liquor after insoluble matter is down to room temperature, the PbCl in solution+、PbCl2 0、PbCl3 -、
PbCl4 2-With PbCl2The state of fine crystals separates out, through filter pressing by the PbCl of fine crystals state2, and a small amount of calcium sulfate sinks
Form sediment and jointly leach, and the chloride of remaining trace metal ion such as iron chloride, copper chloride, zinc chloride, antimony chloride are due to dissolubility
Height, is dissolved in solution and being sufficiently separated.
By the PbCl of fine crystals2It is dissolved in digestion agent B, after a small amount of calcium sulfate precipitation mixed can be removed and molten
Lead chloride solution in dilute sulfuric acid is with H+、Pb2+、Cl4 -、SO4 2-Ionic condition exist.
In citric acid solution during it is passed through digestion agent C by reactant liquor, then add the hydroperoxidation in digestion agent C
After, adding ammonia and to control Leaching Systems be pH 5 ~ 6, the citrate ionized out in Leaching Systems directly can enter with lead ion
Row complexing, directly produces lead citrate hydrate, reacts relative to the lead sulfate of citric acid with solid-state, both avoided
Condensation reaction forms the core-shell structure of product-reactant, and the lead of ionic state and citrate directly carry out complex reaction simultaneously, make
Response speed is greatly promoted.
After adding ammonia, the pH controlling Leaching Systems is pH 5 ~ 6, now acid-base reaction, lead sulfate and citric acid
Reaction makes the temperature of Leaching Systems be greatly improved, and further increases the reaction rate of Leaching Systems.
PbSO4+C6H8O7+2NH4OH→Pb(C6H6O7)·H2O+(NH4)2SO4+H2O
3PbSO4+3C6H8O7+8NH4OH→Pb3(C6H6O7)2·3H2O+(NH4)2C6H8O7+3(NH4)2SO4+3H2O
Pb3(C6H6O7)2·3H2O+C6H8O7→3[Pb(C6H6O7)·H2O]
H2SO4+2NH4OH→(NH4)2SO4+2H2O
HCl+NH4OH→NH4Cl+H2O
Lead in Leaching Systems fully separates out with lead citrate crystalline hydrate precipitation, after filter pressing, obtains citric acid lead water
Compound crystalline deposit, completes the recovery of lead.
In the middle of this process, digestion agent A uses lower-cost mineral acid, inorganic salt, produces the lead of ionic condition and becomes
This higher citric acid reactions, can be greatly promoted reaction rate, and add ammonia generation exothermic effect, improve leaching further
The generating rate of system lead citrate hydrate, relative to traditional pyrogenic process, hydrometallurgic recovery, is improving the same of production efficiency
Time, cost is substantially reduced.
In order to carry out the recovery of lead with the form of lead oxide, on the basis of above-mentioned steps, also include step (4), described
Step (4) be by the lead citrate crystalline hydrate in step (3), at nitrogen or noble gas or the ring of oxygen rich gas protection
High-temperature roasting is carried out, it is thus achieved that superfine lead powder under border.
In described step (4), the temperature of high-temperature roasting is 300 DEG C-500 DEG C, can be fully by lead citrate hydrate roasting
For the fine powder of lead oxide Yu lead, and can effectively control energy consumption.
Further, the content of the described each component of digestion agent A at least can make lead chloride crystalline deposit thing precipitate completely.
In order to improve the reaction rate of step (1), it is characterised in that the heating-up temperature of described step (1) is 50 DEG C ~
100℃。
In order to avoid producing too much calcium sulfate precipitation in Leaching Systems, the content of described step (2) digestion agent B does not surpasses
Cross the amount of lead chloride crystalline deposit thing in step (1) that is completely dissolved, it is simple to the remove impurity of subsequent step.
The time that in described step (3), addition hydrogen peroxide fully reacts is 30min ~ 120min, through adding peroxide
Change after hydrogen, can the leaching rate of effective catalyzing infusion system.
Accompanying drawing explanation
Fig. 1 is the core-shell structure schematic diagram that condensation reaction forms product-reactant；
Fig. 2 is the flow chart of each step of the present invention.
Detailed description of the invention
In order to make the purpose of the present invention, technical scheme and advantage be more easily understood, below in conjunction with drawings and Examples, right
The present invention is further elaborated.Should be appreciated that specific embodiment described herein only in order to explain the present invention, and
It is not used in the restriction present invention.
By old and useless battery lead plaster is carried out remove impurity, dry, after crushing, cross 200 mesh sieves, determine it by chemical titration
The content (representing with lead element equivalent) of middle lead, between the 75 ± 1% of the most former old and useless battery lead plaster quality.
Embodiment 1
Step (1): take above-mentioned old and useless battery lead plaster 10g, pulverizes after being cleaned removing impurity；In flask, add 1000g's
The sodium chloride solution of concentration 20%, is heated to 60 DEG C ~ 70 DEG C, is put into by lead plaster in sodium chloride solution and stir, make lead plaster fully divide
Dissipate；Add 100g hydrochloric acid and be sufficiently mixed, keeping heated condition, be allowed to fully react；Then add 100g calcium chloride, then will
Leachate carries out filter pressing repeatedly 5 times, after fully removing insoluble matter, is cooled to room temperature no longer separates out to crystalline deposit thing；Step
Suddenly (1) total time-consuming about 5 hours；
Step (2): the crystalline deposit thing of precipitation is transferred to 20g concentration is in 10% dilute sulfuric acid, after fully dissolving, removes precipitation
Insoluble matter, it is thus achieved that reactant liquor；Total time-consuming about 0.5 hour of step (2)；
Step (3): reactant liquor is injected in the citric acid that 60g concentration is 22%, and add the hydrogen peroxide that 8g concentration is 30%,
After Leaching Systems gradually heats up, keep reaction 50min, persistently inject saturated ammonia, and the pH controlling Leaching Systems is 5-6, leaching
Going out system to be rapidly heated, lead citrate hydrate is Precipitation, keeps the acid-base value of Leaching Systems and persistently injects saturated ammonia
Water is to excess, and after 2 hours, lead citrate hydrate no longer separates out.Lead citrate hydrate filter pressing is leached, completes recovery process；
Total time-consuming about 3 hours of step (3).
On the basis of step (3), the lead citrate hydrate that will reclaim, proceed step (4) and protect at oxygen rich gas
In the environment of, carry out high-temperature roasting with 300 ± 5 DEG C, repeat to test three groups of these tests, result such as following table:
Table 1
| Group | Step (3) lead citrate hydrate reclaims quality/g | Step (4) solid product reclaims quality/g | Weight-loss ratio % | Preferable lead element equivalent/g | The response rate (calculating for waste diachylon 75% with lead element equivalent quality) % |
| 1 | 14.396 | 7.745 | 46.202% | 7.457 | 99.427% |
| 2 | 14.468 | 7.781 | 46.221% | 7.492 | 99.893% |
| 3 | 14.439 | 7.767 | 46.208% | 7.478 | 99.707% |
With ideally, in lead oxide, lead element equivalent accounts for the 96.282% of its quality, to infer that in step (4), solid produces
Lead element equivalent quality in thing, thus judge the response rate, lead recovery of the present invention all reaches more than 99%, has the higher response rate.
Due under excess oxygen, it is assumed that lead citrate hydrate can burn at perfect condition complete oxidation, generates oxygen completely
Changing lead, its equation is as follows:
Pb(C6H6O7)·H2O+4.5O2→PbO+6CO2+4H2O
Solid product is lead oxide, and relative to citric acid hydrate, total weightlessness is 46.2%；
Under the conditions of oxygen-deficient, it is assumed that lead citrate hydrate burns in the ideal situation, generate lead completely, its equation
As follows:
Pb(C6H6O7)·H2O+4O2→Pb+6CO2+4H2O
Solid product is lead, and relative to citric acid hydrate, total weightlessness is 50%；
In the present embodiment, step (4) calcined solids product reclaims quality and is about the 46.2% of step (3) lead citrate hydrate,
The lead citrate hydrate that deducibility is reclaimed is converted into lead oxide, with very low lead simple substance under roasting.
Embodiment 2
Step (1): take old and useless battery lead plaster 10g, pulverizes after cleaning removes impurity；The saturated of 1000g is added in flask
Sodium chloride solution, is heated to 60 DEG C ~ 70 DEG C, is put into by lead plaster in saturated nacl aqueous solution and stir, make lead plaster fully dispersed；Add
Enter 250g hydrochloric acid and be sufficiently mixed, keeping heated condition, be allowed to fully react；Then add 180g calcium chloride, then will leach
Liquid carries out filter pressing repeatedly, after fully removing insoluble matter, is cooled to room temperature no longer separates out to crystalline deposit thing；Step (1) is total
Time-consuming about 4 hours；
Step (2): the crystalline deposit thing of precipitation is transferred to 20g concentration is in 18% dilute sulfuric acid, after fully dissolving, removes precipitation
Insoluble matter, it is thus achieved that reactant liquor；Total time-consuming about 0.5 hour of step (2)；
Step (3): reactant liquor is injected in the citric acid that 50g concentration is 22%, and add the hydrogen peroxide that 6g concentration is 30%,
After Leaching Systems gradually heats up, keep reaction 80min, persistently inject saturated ammonia, and the pH controlling Leaching Systems is 5-6, leaching
Going out system to be rapidly heated, lead citrate hydrate is Precipitation, keeps the acid-base value of Leaching Systems and persistently injects saturated ammonia
Water to excess, 1 as a child lead citrate hydrate no longer separate out.Lead citrate hydrate filter pressing is leached, completes recovery process；
Total time-consuming about 3 hours of step (3).
The conventional direct Wet Method Reaction of citric acid-lead plaster, it usually needs keep the response time of more than 12 hours, and due to contracting
Close the existence of reaction so that reaction not exclusively, needs to expend the raw materials such as more citric acid；This method substantially reduces required
Response time, and avoid the existence of condensation reaction in step (3), improve the utilization rate of reaction efficiency and raw material.
On the basis of step (3), the lead citrate hydrate that will reclaim, proceed step (4), at nitrogen/indifferent gas
In the environment of body protection, carrying out high-temperature roasting with 300 ± 5 DEG C, the lead citrate hydrate of recovery converts under roasting, repeats examination
Test three groups of these tests, result such as following table:
Table 2
| Group | Step (3) lead citrate hydrate reclaims quality/g | Step (4) solid product reclaims quality/g | Weight-loss ratio % |
| 1 | 14.972 | 7.752 | 48.225% |
| 2 | 14.997 | 7.771 | 48.184% |
| 3 | 15.034 | 7.787 | 48.206% |
In the present embodiment, step (4) calcined solids product reclaims quality and is about the 48.2% of step (3) lead citrate hydrate,
The lead citrate hydrate that deducibility is reclaimed is converted into the mixture of lead oxide and lead simple substance under roasting.
The above, the only present invention preferably detailed description of the invention, but protection scope of the present invention is not limited thereto,
Any those familiar with the art in the technical scope that the invention discloses, the change that can readily occur in or replacement,
All should contain within protection scope of the present invention.Therefore, protection scope of the present invention should be with scope of the claims
It is as the criterion.
Claims (9)
1. the lead recovery catalyst for leaded garbage, it is characterised in that be made up of following material:
Digestion agent A: concentration is not less than the sodium chloride solution of 15%, can be dissolved in described sodium chloride solution with concentration not less than 5%
Hydrochloric acid；And the calcium chloride of described sodium chloride solution can be dissolved in not less than 5% with concentration；
Digestion agent B: concentration is the dilute sulfuric acid of 5% ~ 20%；
Digestion agent C: concentration is not less than the citric acid solution of 20%, can be not less than 3% with concentration and be dissolved in described citric acid solution
In hydrogen peroxide, 25% ammonia being dissolved in described citric acid solution can be not less than with concentration；
In mass ratio, described digestion agent A: digestion agent B: digestion agent C=50 ~ 75:1:20 ~ 45.
A kind of lead recovery catalyst for leaded garbage, it is characterised in that by following material group
Become:
Digestion agent A: saturated nacl aqueous solution, the hydrochloric acid that described saturated nacl aqueous solution can be dissolved in concentration not less than 20%；
And the calcium chloride of described saturated nacl aqueous solution can be dissolved in not less than 15% with concentration；
Digestion agent B: concentration is the dilute sulfuric acid of 15% ~ 20%；
Digestion agent C: saturated citric acid solution, 10% mistake being dissolved in described saturated citric acid solution can be not less than with concentration
Hydrogen oxide, the excessive ammonia of relatively described saturated citric acid solution；
In mass ratio, described digestion agent A: digestion agent B: digestion agent C=55 ~ 65:1:20 ~ 30.
3. the application process of one kind such as the claim 1 or 2 lead recovery catalyst being used for leaded garbage formula, it is characterised in that comprise
Following steps:
(1) by waste gas lead battery lead plaster remove impurity, it is allowed to after pulverizing in even suspension sodium chloride solution in digestion agent A, heating,
And add the hydrochloric acid in digestion agent A and be sufficiently mixed, keep heating-up temperature and be sufficiently mixed uniformly, adding the chlorine in digestion agent A
Changing calcium, fully filter pressing repeatedly after reaction, room temperature is down to by the clear liquor after filtering off insoluble matter, and filter pressing obtains the crystalline deposit separated out
Thing；
(2) the crystalline deposit thing addition digestion agent B in step (1) will fully react, and remove impurity, obtain reactant liquor；
(3) reactant liquor in step (2) is added in the citric acid solution in digestion agent C, add the peroxidating in digestion agent C
After hydrogen solution fully reacts, excess adds the ammonia in digestion agent C and to control Leaching Systems be pH 5 ~ 6, makes lead citrate crystallize
Hydrate deposition fully separates out, and obtains lead citrate crystal of hydrate precipitation through filter pressing.
The application process of a kind of lead recovery catalyst for leaded garbage, it is characterised in that also wrap
Including step (4), described step (4) is by the lead citrate crystalline hydrate in step (3), in nitrogen or noble gas or richness
High-temperature roasting is carried out, it is thus achieved that superfine lead powder in the environment of carrier of oxygen protection.
5. the application process of a kind of lead recovery catalyst for leaded garbage as described in claim 3 or 4, it is characterised in that
The content of the described each component of digestion agent A at least can make lead chloride crystalline deposit thing precipitate completely.
6. the application process of a kind of lead recovery catalyst for leaded garbage as described in claim 3 or 4, it is characterised in that
The heating-up temperature of described step (1) is 50 DEG C ~ 100 DEG C.
7. the application process of a kind of lead recovery catalyst for leaded garbage as described in claim 3 or 4, it is characterised in that
The content of described step (2) digestion agent B is less than being completely dissolved the amount of lead chloride crystalline deposit thing in step (1).
8. the application process of a kind of lead recovery catalyst for leaded garbage as described in claim 3 or 4, it is characterised in that
The time that in described step (3), addition hydrogen peroxide fully reacts is 30min ~ 120min.
The application process of a kind of lead recovery catalyst for leaded garbage, it is characterised in that described
Step (4) in the temperature of high-temperature roasting be 300 DEG C-500 DEG C.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106435179A (en) * | 2016-10-28 | 2017-02-22 | 广东工业大学 | Leaching method of metals in lead-zinc sulfide mineral tailings and application of leaching method |
| CN108842072A (en) * | 2018-08-24 | 2018-11-20 | 淄博淦达环保科技有限公司 | A kind of leaching liquid and extract technology of zinc |
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| CN115504439B (en) * | 2022-09-07 | 2023-09-29 | 金川集团股份有限公司 | Method for removing lead from high-lead tellurium powder |
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