CN105936979B - A kind of lead recovery catalyst and its application method for leaded waste - Google Patents
A kind of lead recovery catalyst and its application method for leaded waste Download PDFInfo
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- CN105936979B CN105936979B CN201610526718.3A CN201610526718A CN105936979B CN 105936979 B CN105936979 B CN 105936979B CN 201610526718 A CN201610526718 A CN 201610526718A CN 105936979 B CN105936979 B CN 105936979B
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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
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
- C22B7/006—Wet processes
- C22B7/007—Wet processes by acid leaching
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- 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
A kind of lead recovery catalyst and its application method for leaded waste, pass through the lead element in digestion agent A, digestion agent B, digestion agent C segmentation extraction lead plaster or leaded waste, and obtain the lead regenerant in the form of lead citrate hydrate, pass through roasting, moreover it is possible to convert lead oxide/lead mixture for lead regenerant.Lead recovery of the present invention is high, cost-saved relative to citric acid-lead plaster wet process derect seething lead way of recycling, promotes the rate of recovery；And the mode of recycling lead is refined relative to traditional pyrogenic process, reduce pollution and huge energy consumption of the sulfiding gas to environment.
Description
Technical field
The present invention relates to recycle lead from leaded waste.Specifically, but not exclusively, the present invention relates to sour from scrap lead
The scrap lead cream for polluting environment is especially used wet-leaching and low-temperature bake technique from scrap lead by the method that lead is recycled in battery
Recycling directly prepares the final product of lead powder and this method in battery.
Background technique
Currently, 75% lead bullion is applied to lead-acid accumulator in the world, it is believed that the lead in lead battery close to 90% is recovered,
And the whole world is more than that 50% lead yield is derived from the lead of recycling.With electric car, electric vehicle, communications industry swift and violent hair
Exhibition, the demand of lead-acid accumulator are continuously increased, and are substituted learies and are necessarily also increased.And reclaiming lead can make lead metal
It into the regenerated benign cycle of production-consumption-, makes full use of regenerated resources (scrap lead), reduces Resources (lead ore)
Yield, extend its mining term, meet the strategy of sustainable development of country, market potential is huge.
In lead-acid accumulator, the processing of scrap lead cream is the largest difficult point, and lead plaster is mainly the active material on pole plate
It mainly include PbSO by forming slurry like material after charge and discharge4、PbO2, PbO and a small amount of Pb and other impurities composition.State at present
The major way of inside and outside processing scrap lead cream includes following several: hydrometallurgical, pyrometallurgical method, wet process-pyrogenic process are combined method.
Lead is recycled from waste lead accumulator at present and mostly uses pyrometallurgical smelting, main includes three kinds: direct pyrometallurgical smelting, elder generation
Sub-elect lead plaster material, then smelted, lead plaster elder generation desulfurization conversion carries out pyrometallurgical smelting operation again, easy to operate, but these are passed
System high temperature pyrometallurgical smelting, which has the disadvantage in that, to be needed through professional smelting furnaces such as reverberatory furnace, the short furnace of revolution, blast furnaces, equipment at
This height；PbSO in lead plaster4Content is generally in 50% or more, PbSO4Fusing point is high, reach the temperature decomposed completely will 1000 DEG C with
On, energy consumption is high；Vulcanized lead, which decomposes, in fusion process generates sulfur dioxide, and sulfurous gas is caused to pollute；It is caused under high temperature a large amount of
Lead volatility lose and formed the lead dust of pollution, reduce lead recovery.
The characteristics of hydrometallurgy scrap lead battery, is first desulfurization, is electrolysed to obtain lead again, does not have sulfur dioxide problem of environmental pollution, with
And avoid high energy consumption issues existing for pyrogenic process.Typical method includes RSR method, CX-EW method；Its principle passes through lead plaster conversion-leaching
Out-electrodeposition mode obtains lead and lead oxide, and reaction speed is more slow, and efficiency is lower；Currently, correlative study person also proposed
The new recovery process of citric acid wet process, but still there are following technological difficulties: and reaction conversion rate is slow, general 24-48 h or more
95% or more desulfuration efficiency could be obtained；The crystal for generating lead citrate separates difficulty with other impurities；Citric acid solution and lead
The liquid-solid reaction system of cream brings condensation reaction, forms product-reactant core-shell structure, and transformation efficiency is relatively low；Citric acid at
This height, lower reaction efficiency considerably increase the cost of actual recovered and process operation.
Wet process-pyrogenic process joint technology is used mostly in developed countries such as the U.S., Germany and Italy, and the technology is by lead plaster
Wet desulphurization processing is first carried out, the pollution of the sulfiding gas such as sulfur dioxide is avoided；The lead plaster after desulfurization is melted by pyrogenic process afterwards
Decomposition temperature can be reduced to 300 DEG C or so by 1000 DEG C before converting, reduced at recycling waste lead batteries by the process flow of refining
Energy consumption in reason.The technology reduces the pollution section in lead regenerative process and reduces energy consumption, is the method for more worth promotion,
It is also the developing direction of WeiLai Technology.
Summary of the invention
The purpose of the present invention is to provide a kind of lead recovery catalysts and its application method for leaded waste, by wet
Method recycles the lead in leaded waste in the form of lead citrate, and provides pyrogenic process method for refining on this basis, by citric acid
Lead is converted, and carries out lead recycling with lead oxide or lead simple substance form.
By taking exhaust gas lead battery lead plaster as an example, in lead plaster raw material, main object phase composition includes lead sulfate, brown lead oxide, oxygen
Change lead and lead simple substance, in addition also there is remaining to be scattered in metal ion compound and the separable impurity of physics in lead plaster.
For the leaded waste of similar lead plaster object phase composition, it lead recovery catalyst provided by the invention can be used to carry out lead and return
It receives, can effectively separate the metal ion compound in such leaded waste, and will be all kinds of in leaded waste
Leaded substance is converted into high-purity citric acid lead and is recycled, and can also convert high-purity for lead citrate by high-temperature roasting
Lead oxide and a small amount of lead simple substance, effectively leaded waste is recycled.
To achieve the above object, the present invention provides a kind of lead recovery catalyst for leaded waste, by following material composition:
A kind of lead recovery catalyst for leaded waste, which is characterized in that by following material composition:
Digestion agent A: sodium chloride solution of the concentration not less than 15% can be dissolved in the sodium chloride not less than 5% with concentration
The hydrochloric acid of solution；And the calcium chloride of the sodium chloride solution can be dissolved in not less than 5% with concentration；
Digestion agent B: the dilute sulfuric acid that concentration is 5% ~ 20%；
Digestion agent C: citric acid solution of the concentration not less than 20% can be dissolved in the citric acid not less than 3% with concentration
Hydrogen peroxide in solution, the ammonium hydroxide that can be dissolved in concentration not less than 25% in the citric acid solution；
In mass ratio, the digestion agent A: digestion agent B: digestion agent C=50 ~ 75:1:20 ~ 45.
As an improvement, the lead recovery catalyst is by following material composition:
Digestion agent A: saturated sodium chloride solution can be dissolved in the saturated sodium chloride solution not less than 20% with concentration
Hydrochloric acid；And the calcium chloride of the saturated sodium chloride solution can be dissolved in not less than 15% with concentration；
Digestion agent B: the dilute sulfuric acid that concentration is 15% ~ 20%；
Digestion agent C: saturated citric acid solution can be dissolved in the saturated citric acid solution with concentration not less than 10%
Hydrogen peroxide, the relatively described saturated citric acid solution excessive ammonia；
In mass ratio, the digestion agent A: digestion agent B: digestion agent C=55 ~ 65:1:20 ~ 30.
It is extracted using lead recovery catalyst provided by the invention, and using following methods:
(1) exhaust gas lead battery lead plaster is cleaned, even suspension is allowed to after crushing in the sodium chloride solution in digestion agent A,
It heats and the hydrochloric acid that is added in digestion agent A and is sufficiently mixed, keep heating temperature to be simultaneously sufficiently mixed uniformly, be added in digestion agent A
Calcium chloride, sufficiently reaction after filters pressing repeatedly, by filter off insoluble matter after clarified solution be down to room temperature, the crystallization that filters pressing is precipitated
Sediment；
(2) the crystalline deposit object in step (1) is added in digestion agent B and is sufficiently reacted, and remove impurity, reacted
Liquid；
(3) reaction solution in step (2) is added in the citric acid solution in digestion agent C, adds the mistake in digestion agent C
After hydrogen peroxide solution is sufficiently reacted, the excessive ammonium hydroxide being added in digestion agent C simultaneously controls Leaching Systems as pH 5 ~ 6, makes lead citrate
Crystalline hydrate precipitating is sufficiently precipitated, and obtains lead citrate crystal of hydrate precipitating by filters pressing.
Hydrochloric acid-sodium chloride-calcium chloride the system formed by step (1), digestion agent A handles discarded lead battery lead plaster, energy
It is dissolved in the metal ion in lead plaster in digestion agent A, and the lead sulfate, lead oxide, the generation of lead simple substance in lead plaster are following anti-
It answers, generates 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, since with sodium chloride following reversible reaction can occur for lead chloride:
PbCl2+2NaCl⇌Na2PbCl4
To improve lead recovery as far as possible, Na can be made by way of cooling2PbCl4To PbCl2Conversion, and lead chloride exists
When low temperature, solubility in water is lower, is 3.22% under 100 DEG C of states, is 1.07% at 25 DEG C, by the addition of calcium chloride,
Generate the CaSO insoluble in leaching agent A4, can avoid Na2SO4Accumulation, as much as possible improve obtain PbCl2Acquisition rate；
Na2SO4+CaCl2→CaSO4↓+2NaCl
Simultaneously as the chloride of lead is in acid NaCl, CaCl in alkali metal, alkaline earth metal chloride hot solution2
Mixed solution in, with PbCl+、PbCl2 0、PbCl3 -、PbCl4 2-Form exist, solubility greatly promotes, the chlorine of lead at 65 DEG C
Compound leaching rate reaches 80%, and the chloride leaching rate of lead reaches 95% at 95 DEG C, and in the state that temperature is promoted, reaction rate
It improves more significant.
After what is obtained is down to room temperature for the clarified solution after elimination insoluble matter, the PbCl in solution+、PbCl2 0、PbCl3 -、
PbCl4 2-With PbCl2The states of fine crystals is precipitated, through filters pressing by the PbCl of fine crystals state2And a small amount of calcium sulfate is heavy
Shallow lake filters out jointly, and the chloride of remaining trace metal ion such as iron chloride, copper chloride, zinc chloride, antimony chloride are due to solubility
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 it is molten
Chlorination lead solution in dilute sulfuric acid is with H+、Pb2+、Cl4 -、SO4 2-Ionic condition exist.
By reaction solution, it is passed through in the citric acid solution in digestion agent C, and the hydroperoxidation in digestion agent C is then added
Afterwards, it is pH 5 ~ 6 that ammonium hydroxide, which is added, and controls Leaching Systems, the citrate ionized out in Leaching Systems can with lead ion directly into
Row complexing, directly generation lead citrate hydrate, react relative to citric acid and solid lead sulfate, both avoided
Condensation reaction forms product-reactant core-shell structure, while the lead of ionic state and citrate directly carry out complex reaction, make
Reaction speed greatly promotes.
After ammonium hydroxide is added, the pH for controlling Leaching Systems is pH 5 ~ 6, at this time acid-base reaction, lead sulfate and citric acid
The temperature of Leaching Systems is greatly improved in reaction, 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 is precipitated with lead citrate crystalline hydrate to be sufficiently precipitated, and after filters pressing, obtains citric acid
Lead hydrate crystalline deposit, completes the recycling of lead.
In this process, digestion agent A uses lower-cost inorganic acid, inorganic salts, generate the lead of ionic condition at
This higher citric acid reactions can greatly promote reaction rate, and ammonium hydroxide is added and generates exothermic effect, further improve leaching
The generating rate of system lead citrate hydrate is improving the same of production efficiency relative to traditional pyrogenic process, hydrometallurgic recovery
When, cost substantially reduces.
It further include step (4) on the basis of above-mentioned steps to carry out the recycling of lead in the form of lead oxide, it is described
The step of (4) be by the lead citrate crystalline hydrate in step (3), in the ring that nitrogen or inert gas or oxygen rich gas are protected
High-temperature roasting is carried out under border, obtains superfine lead powder.
The temperature of step (4) the high temperature roasting is 300 DEG C -500 DEG C, can sufficiently be roasted lead citrate hydrate
For the fine powder of lead oxide and lead, and it can be effectively controlled energy consumption.
Further, the content of the digestion agent A each component can at least be such that lead chloride crystalline deposit object precipitates completely.
In order to improve the reaction rate of step (1), which is characterized in that the heating temperature of the step (1) be 50 DEG C ~
100℃。
In order to avoid generating excessive calcium sulfate precipitation in Leaching Systems, the content of the step (2) digestion agent B does not surpass
The amount for being completely dissolved lead chloride crystalline deposit object in step (1) is crossed, convenient for the removal of impurities of subsequent step.
It is 30min ~ 120min that the time that hydrogen peroxide sufficiently reacts is added in the step (3), by peroxide is added
After changing hydrogen, can effective catalyzing infusion system leaching rate.
Detailed description of the invention
Fig. 1 is that condensation reaction forms product-reactant core-shell structure schematic diagram；
Fig. 2 is the flow chart of each step of the present invention.
Specific embodiment
It is with reference to the accompanying drawings and embodiments, right in order to be more easily understood the objectives, technical solutions, and advantages of the present invention
The present invention is further elaborated.It should be appreciated that the specific embodiments described herein are merely illustrative of the present invention, and
It is not used in the restriction present invention.
By the way that old and useless battery lead plaster cleans, dries, after being crushed, cross 200 meshes, it is determined by chemical titration
The content (being indicated with lead element equivalent) of middle lead, about between the 75 ± 1% of original old and useless battery lead plaster quality.
Embodiment 1
Step (1): taking above-mentioned old and useless battery lead plaster 10g, is cleaned after removing impurity and is crushed；It is added in flask
The sodium chloride solution of the concentration 20% of 1000g is heated to 60 DEG C ~ 70 DEG C, and lead plaster is put into sodium chloride solution and stirred, makes lead
Cream is fully dispersed；100g hydrochloric acid is added and is sufficiently mixed, keeps heated condition, is allowed to sufficiently react；100g chlorination is then added
Leachate is then carried out filters pressing 5 times repeatedly after sufficiently removing insoluble matter and is cooled to room temperature to crystalline deposit object and no longer analyses by calcium
Until out；Step (1) total time-consuming about 5 hours；
Step (2): it is after completely dissolution, to remove in 10% dilute sulfuric acid that the crystalline deposit object of precipitation, which is transferred to 20g concentration,
The insoluble matter of precipitating obtains reaction solution；Step (2) total time-consuming about 0.5 hour；
Step (3): reaction solution being injected into the citric acid that 60g concentration is 22%, and the peroxide that 8g concentration is 30% is added
Change hydrogen, after Leaching Systems are gradually warmed up, keeps reaction 50min, lasting injection saturation ammonium hydroxide, and the pH for controlling Leaching Systems is 5-
6, Leaching Systems are rapidly heated, and lead citrate hydrate is in Precipitation, keep the pH value of Leaching Systems and continue to inject full
With ammonium hydroxide to excess, lead citrate hydrate is no longer precipitated after 2 hours.Lead citrate hydrate filters pressing is filtered out, recycling is completed
Process；Step (3) total time-consuming about 3 hours.
On the basis of step (3), by the lead citrate hydrate of recycling, continues step (4) and protected in oxygen rich gas
In the environment of, with 300 ± 5 DEG C of progress high-temperature roastings, repeat to test three groups of this tests, the result is as follows:
Table 1
| Group | Step (3) lead citrate hydrate recycles quality/g | Step (4) solid product recycles quality/g | Weight-loss ratio % | Ideal lead element equivalent/g | The rate of recovery (calculates) % by waste diachylon 75% of 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% |
It is solid in step (4) to infer with ideally, lead element equivalent accounts for about the 96.282% of its quality in lead oxide
Lead element equivalent quality in body product, to judge the rate of recovery, lead recovery of the present invention is up to 99% or more, with higher time
Yield.
Due under excess oxygen, it is assumed that lead citrate hydrate can burn in perfect condition complete oxidation, completely generation oxygen
Change lead, equation is as follows:
Pb(C6H6O7)·H2O+4.5O2→PbO+6CO2+4H2O
Solid product is lead oxide, relative to citric acid hydrate, total weight loss 46.2%；
Under the conditions of oxygen-deficient, it is assumed that lead citrate hydrate burns in the ideal situation, completely generation lead, side
Formula is as follows:
Pb(C6H6O7)·H2O+4O2→Pb+6CO2+4H2O
Solid product is lead, relative to citric acid hydrate, total weight loss 50%；
In the present embodiment, it is about step (3) lead citrate hydrate that step (4) calcined solids product, which recycles quality,
46.2%, the lead citrate hydrate of deducibility recycling is converted into lead oxide under roasting, with very low lead simple substance.
Embodiment 2
Step (1): taking old and useless battery lead plaster 10g, crushes after cleaning is removed impurity；The full of 1000g is added in flask
The sodium chloride solution of sum is heated to 60 DEG C ~ 70 DEG C, and lead plaster is put into saturated sodium chloride solution and stirred, divides lead plaster sufficiently
It dissipates；250g hydrochloric acid is added and is sufficiently mixed, keeps heated condition, is allowed to sufficiently react；180g calcium chloride is then added, then will
Leachate carries out filters pressing repeatedly and is cooled to room temperature until crystalline deposit object is no longer precipitated after sufficiently removing insoluble matter；Step
(1) total time-consuming about 4 hours；
Step (2): it is after completely dissolution, to remove in 18% dilute sulfuric acid that the crystalline deposit object of precipitation, which is transferred to 20g concentration,
The insoluble matter of precipitating obtains reaction solution；Step (2) total time-consuming about 0.5 hour；
Step (3): reaction solution being injected into the citric acid that 50g concentration is 22%, and the peroxide that 6g concentration is 30% is added
Change hydrogen, after Leaching Systems are gradually warmed up, keeps reaction 80min, lasting injection saturation ammonium hydroxide, and the pH for controlling Leaching Systems is 5-
6, Leaching Systems are rapidly heated, and lead citrate hydrate is in Precipitation, keep the pH value of Leaching Systems and continue to inject full
With ammonium hydroxide to excess, 1 as a child lead citrate hydrate be no longer precipitated.Lead citrate hydrate filters pressing is filtered out, recycling is completed
Process；Step (3) total time-consuming about 3 hours.
The conventional direct wet process reaction of citric acid-lead plaster, it usually needs holding 12 hours or more reaction time, and due to contracting
The presence of reaction is closed, so that reaction is not exclusively, needs to expend the raw materials such as more citric acids；This method substantially reduces required
Reaction time, and the presence of condensation reaction is avoided in step (3), improve the utilization rate of reaction efficiency and raw material.
On the basis of step (3), by the lead citrate hydrate of recycling, continue step (4), in nitrogen/indifferent gas
In the environment of body protection, with 300 ± 5 DEG C of progress high-temperature roastings, the lead citrate hydrate of recycling converts under roasting, repeats to try
Three groups of this tests are tested, the result is as follows:
Table 2
| Group | Step (3) lead citrate hydrate recycles quality/g | Step (4) solid product recycles 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, it is about step (3) lead citrate hydrate that step (4) calcined solids product, which recycles quality,
48.2%, the lead citrate hydrate of deducibility recycling is converted into the mixture of lead oxide Yu lead simple substance under roasting.
The foregoing is only a preferred embodiment of the present invention, but scope of protection of the present invention is not limited thereto,
In the technical scope disclosed by the present invention, any changes or substitutions that can be easily thought of by anyone skilled in the art,
It should be covered by the protection scope of the present invention.Therefore, protection scope of the present invention should be with scope of protection of the claims
Subject to.
Claims (6)
1. a kind of application method of the lead recovery catalyst for leaded waste, which is characterized in that comprise the steps of:
(1) exhaust gas lead battery lead plaster is cleaned, even suspension is allowed to after crushing in the sodium chloride solution in digestion agent A, heated,
And the hydrochloric acid that is added in digestion agent A and be sufficiently mixed, it keeps heating temperature to be simultaneously sufficiently mixed uniformly, the chlorine in digestion agent A is added
Change calcium solution, sufficiently filters pressing repeatedly after reaction, the clarified solution after elimination insoluble matter is down to room temperature, the crystallization that filters pressing is precipitated
Sediment；
(2) the crystalline deposit object in step (1) is added in digestion agent B and is sufficiently reacted, and remove impurity, obtain reaction solution；
(3) reaction solution in step (2) is added in the citric acid solution in digestion agent C, adds the peroxidating in digestion agent C
After hydrogen solution sufficiently reacts, the excessive ammonium hydroxide being added in digestion agent C simultaneously controls Leaching Systems as pH 5 ~ 6, crystallizes lead citrate
Hydrate deposition is sufficiently precipitated, and obtains lead citrate crystal of hydrate precipitating by filters pressing；
In above-mentioned steps (1)-(3), in mass ratio, the digestion agent A: digestion agent B: digestion agent C=50 ~ 75:1:20 ~ 45,
In:
Digestion agent A: the hydrochloric acid of sodium chloride solution, concentration not less than 5% by concentration not less than 15%, concentration are not less than 5% chlorination
Calcium solution composition, the hydrochloric acid, calcium chloride solution can be dissolved in the sodium chloride solution, and each substance in digestion agent A
It is separately contained；
Digestion agent B: the dilute sulfuric acid that concentration is 5% ~ 20%；
Digestion agent C: the hydrogen peroxide of citric acid solution, concentration not less than 3% by concentration not less than 20%, concentration are not less than 25%
Ammonium hydroxide composition, the hydrogen peroxide, ammonia solvent in the citric acid solution, and in digestion agent C each substance separate
It contains.
2. a kind of application method of the lead recovery catalyst for leaded waste as described in claim 1, which is characterized in that described
The step of (1)-(3) in, in mass ratio, the digestion agent A: digestion agent B: digestion agent C=55 ~ 65:1:20 ~ 30；Wherein:
Digestion agent A: hydrochloric acid, concentration by saturated sodium chloride solution, concentration not less than 20% are not less than 15% calcium chloride solution group
At the hydrochloric acid, calcium chloride solution can be dissolved in the saturated sodium chloride solution, and each substance separates in digestion agent A
It contains；
Digestion agent B: the dilute sulfuric acid that concentration is 15% ~ 20%；
Digestion agent C: the peroxidating that is not less than 10% by saturated citric acid solution, concentration and can be dissolved in saturated citric acid solution
The excessive ammonia composition of hydrogen, relative saturation citric acid solution, each substance is separately contained in digestion agent C.
3. a kind of application method of the lead recovery catalyst for leaded waste as claimed in claim 1 or 2, which is characterized in that
It further include step (4), the step (4) is by the lead citrate crystalline hydrate in step (3), in nitrogen or inert gas
Or high-temperature roasting is carried out in the environment of oxygen rich gas protection, obtain superfine lead powder.
4. a kind of application method of the lead recovery catalyst for leaded waste as claimed in claim 1 or 2, which is characterized in that
The heating temperature of the step (1) is 50 DEG C to 100 DEG C.
5. a kind of application method of the lead recovery catalyst for leaded waste as claimed in claim 1 or 2, which is characterized in that
It is 30min ~ 120min that the time that hydrogen peroxide sufficiently reacts is added in the step (3).
6. a kind of application method of the lead recovery catalyst for leaded waste as claimed in claim 3, which is characterized in that described
The step of (4) high temperature roasting temperature be 300 DEG C -500 DEG C.
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| 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 |
| CN108946795B (en) * | 2018-09-25 | 2020-12-18 | 马鞍山钢铁股份有限公司 | Method for preparing high-purity basic lead carbonate by using lead-containing dedusting ash |
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