CN103374657A - Ultrafine lead oxide prepared by using waste lead plaster and preparation method thereof - Google Patents
Ultrafine lead oxide prepared by using waste lead plaster and preparation method thereof Download PDFInfo
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- CN103374657A CN103374657A CN2012101216362A CN201210121636A CN103374657A CN 103374657 A CN103374657 A CN 103374657A CN 2012101216362 A CN2012101216362 A CN 2012101216362A CN 201210121636 A CN201210121636 A CN 201210121636A CN 103374657 A CN103374657 A CN 103374657A
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- 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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- 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
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Abstract
The invention discloses an ultrafine lead oxide prepared by using a waste lead plaster and a preparation method thereof. The preparation method comprises the following steps of: carrying out desulphurization process by mixing the waste lead plaster with an aqueous solution containing a composite desulfurizer for reaction; carrying out filtration to remove the desulphurization filtering solution to obtain the desulfurated lead plaster (filter residue); carrying out a leaching and crystal transformation process by adding a citric acid solution and a reducing agent into the desulfurated lead plaster obtained in the process, and carrying out filtration, washing, and drying to obtain the lead citrate after the desulfurated lead plaster reacts with the citric acid solution; carrying out a roasting process by roasting the lead citrate to obtain the ultrafine lead oxide. According to the preparation method disclosed by the invention, the ultrafine lead oxide is prepared from the waste lead storage lead plaster; a two-step leaching process is adopted; the filtering solution is simple in ingredient and can be recycled; a side product is recycled from the desulphurization solution. The preparation method disclosed by the invention is low in energy consumption, simple in equipment, high in lead recycling rate, and high in ultrafine lead product quality, and has the characteristics of good resource recycling effect, environmentally-friendly and pollution-free production process, and capability of clean production.
Description
Technical field
The present invention relates to the recycling field of lead-acid accumulator, particularly the scrap lead cream with contaminate environment adopts wet-leaching and low-temperature bake technique to reclaim the directly ultra-fine lead powder of preparation from waste lead accumulator, belongs to the Production of Secondary Lead technical field.
Background technology
Plumbous purposes is very extensive, and its annual production occupies the 4th and is only second to aluminium, copper, zinc in non-ferrous metal.Along with the increase of automobile quantity, Lead Acid Battery Industry is developed rapidly, and the annual waste lead accumulator quantity that produces is in continuous increase.Lead acid cell is a kind of battery that output is maximum in all kinds of batteries in the world, purposes is the widest, it consume plumbous amount account for the total consumption in the whole world plumbous measure 82%.In order to save limited mineral wealth, avoid the scrap lead material to the pollution of environment, all attach great importance to the recycling of scrap lead material both at home and abroad.National governments all support to reclaim plumbous Production of Secondary Lead and the research of Production of Secondary Lead new technology energetically from waste lead accumulator.
Lead-containing material comprises grid and cream mud two portions in the waste lead accumulator.The composition of grid is lead alloy, and is leaded up to 90%-95%; The lead plaster complicated component is mainly by PbSO
4, PbO
2, PbO, Pb and a small amount of impurity forms leaded 60%-80%.The type of furnace of scrap lead lights method melting mainly contains the professional type of furnaces such as reverberatory furnace, the short stove of revolution, blast furnace.PbSO in the lead plaster
4Content is generally more than 50%, PbSO
4Fusing point is high, and reaching the temperature of decomposing fully will more than 1000 ℃, be to produce SO in the fusion process
2Major cause.Simultaneously cause a large amount of plumbous volatilization loss under the high temperature and form the lead dust of contaminative.The operator's lead poisoning that causes owing to the volatilization of lead and compound thereof is very serious, and the fume amount that causes increases the reduction that also must cause refining vertical yield and leaded flue dust to the pollution of environment.The energy consumption of pyrometallurgical smelting is also higher in addition, and domestic little secondary lead factory produces the plumbous general energy consumption 500-600kg mark coal of 1t, and the energy consumption of domestic professional secondary lead enterprise is at 130-310kg/t, and the common level of at present external energy consumption reaches below the 200kg/t.
The environmental problem of bringing in order to solve the pyrogenic process high melt, some scholar introduces the hydrometallurgical processes that strike (abbreviation electrodeposition method) has been studied lead acid cell.Representational is the RSR technique of Prengmann and McDonald invention.RSR technique transforms-the used typical agents of reduction conversion-electrodeposition method dissolving Leaching reaction according to desulfurization, can be summarized as (NH
4)
2CO
3-Na
2SO
3-H
2SiF
4Syllogic wet method electrodeposition process.
Domestic professor Chen Weiping of Hunan University has developed the lead plaster hydrometallurgical processes similar to the RSR technological line.This technique uses strong base solution NaOH as sweetening agent, FeSO
4As reductive agent, use KNaC
4H
4O
6Leach reagent as dissolving before the electrolysis.Can similarly be summarized as NaOH-FeSO
4-KNaC
4H
4O
6Syllogic wet method electrodeposition process.
In addition, also has the research of other similar lead plaster conversion-leaching-electrodeposition hydrometallurgical processes.Introduce the hydrometallurgical recovery technique of electrodeposition method, solved the SO in the lead plaster pyrometallurgical smelting process
2The volatilization problem of lead under discharging and the high temperature.Yet this technology investment is large, is only suitable in building large-scale recovery plant, and energy consumption is larger, even more taller than traditional fire metallurgy process.Therefore, the problem of high energy consumption still has to be solved.
Lead oxide powder is as the core of whole lead acid cell, and exploration and the improvement of its performance caused numerous scientific and technical personnel's interest.Lead element has the many oxide form, and that wherein be used for lead acid cell mainly is PbO, PbO
2And Pb
3O
4Wherein that the most frequently used is PbO.The PbO powder is one of active substance of commonly using in the chemical power source, and according to data, China's plumbous amount nearly 30% of annual lead storage battery consumption is for the preparation of lead storage battery PbO isoreactivity material.In addition, also for the manufacture of the white lead powder, become lead soap with oil; Make paint drier, plastic plasticizer, pigment; Be used for opticglass etc.PbO has two kinds of polymorphisms.Light yellow or khaki color powder is rhombic system α-PbO, and reddish yellow is tetragonal spheroidal β-PbO, and water insoluble and ethanol is dissolved in nitric acid, plumbic acetate, chlorination money, calcium chloride and liquid caustic soda.
Mostly lead acid cell manufacturing concern adopts PbO, and present so-called lead powder just refers to the mixture that the freedom lead by 70%～80% PbO and 20%～30% forms.Pb
3O
4Also being red lead, is that PbO is heated to the product about 540 ℃ in air, has special crystalline structure, just is used for a long time ago lead acid cell, is particularly useful for the manufacturing of tubulose pole plate.
The waste and old lead acid accumulator lead plaster mainly is the product that active substance discharges and recharges rear conversion for a long time on the battery lead plate.Pyrometallurgy or the electrodeposition hydrometallurgical recovery metal Pb of scrap lead cream process high energy consumption, if metal Pb wants again to prepare for the production of lead acid cell as raw material the active substance of pole plate, must be through the complicated production technical process of multiple working procedure.Wherein prepare lead powder by lead pig, pass through again the technique of the high energy consumption of melting-oxidation.
The method for preparing at present lead powder mainly contains ball milled, vapour phase oxidation process etc.The manufacturing process of lead powder is to adopt ball milled (claim not only Shimadzu method) or vapour phase oxidation process (but also claiming Ba Dunfa) by lead pig, makes by the oxidation screening through the specific equipment lead-power machine to contain the lead powder that PbO is main component.Ball milled is because shot or the mutual friction of lead phase and a large amount of heat of bump generation in lead-power machine, so that temperature increases in the cylindrical shell, under the effect of oxygen, oxidation occurs and generates PbO in shot or lead surface in to the air draught of input certain temperature and humidity in the lead-power machine.The plumbous liquid that vapour phase oxidation process (claim again bar a powder process method) mainly refers to melting closes the process of producing lead powder with airborne oxidation after being stirred into the droplet shape in that gaseous oxidation is indoor, and the lead powder that makes thus is commonly referred to a bar powder.PbO content is about 75% (being also referred to as the oxidisability of lead powder) in the general control lead powder.Vapour phase oxidation process has the characteristics such as the power consumption low yield is large, operation is easy to control, environmental pollution is little, and apparent density and the particle size of the lead powder of producing are bigger than normal, although and the particle size of Daojin lead powder is less, but energy consumption is relatively high.
Lead powder is as the fertile material of lead acid cell formation battery lead plate active substance, and the character of lead powder and quality control play an important role for the performance raising of whole lead acid cell.Superfine powder is the problem that the investigator pays close attention to the performance impact of electrode materials always.International Lead and Zinc Study Group (ILZRO) sets up great special project to carry out the research of lead acid cell active substance, there are some researches show, the lead acid cell of ultra-fine PbO particle preparation has heavy body and length discharges and recharges the advantages such as life-span, and shortcoming is that preparation ultra-fine lead oxide cost is too high.From scrap battery, reclaim in the lead plaster at present ultra-fine lead oxide technology report seldom.CN101573461A adopts citric acid and Trisodium Citrate mixing solutions processing lead plaster to prepare ultra-fine lead oxide, although this method single step reaction, but the reaction times is longer, and the reaction of actual lead plaster more than the 8h, contains citric acid, Trisodium Citrate, sodium sulfate separation difficulty in the simultaneously final filtrate at least.
The article of at present desulfurization is relatively many, but adopts most of yellow soda ash desulfurization of adopting, when the yellow soda ash desulfurization dosage hour, contingent reaction equation is (1)
PbSO
4+Na
2CO
3→PbCO
3+Na
2SO
4 (1)
The product that generates is lead carbonate, but desulfurization degree is lower, and residual lead sulfate is more, still can affect the process of follow-up operation.
When the dosage of yellow soda ash is larger, the pH of solution may the formation reaction equation be (2)-(3) greater than in 10 situations
3PbSO
4+3Na2CO
3+H
2O→Pb
3(CO
3)
2(OH)
2+3Na
2SO
4+CO
2 (2)
Pb
3(CO
3)
2(OH)
2+2Na
2CO
3→3NaPb
2(CO
3)
2OH+NaOH (3)
The product that generates also has Pb
3(CO
3)
2(OH)
2, NaPb
2(CO
3)
2OH, Pb
10O (CO
3)
6(OH)
6Deng.Compound N aPb particularly
2(CO
3)
2OH occurs, and the introducing meeting of sodium element is made troubles to follow-up pyrogenic attack or wet processing.Therefore how to adopt effective sweetening agent can guarantee that desulfuration efficiency can guarantee that the quality of product is an important problem simultaneously.
Summary of the invention
The object of the invention is to provide a kind of lead storage battery active substance ultra-fine lead oxide by the preparation of scrap lead cream.
Another purpose of the present invention is to provide the method for above-mentioned ultra-fine lead oxide, and the method Production Flow Chart is simple, non-environmental-pollution or environmental pollution is extremely low, lead recovery is high, reduce energy consumption and environmental contamination reduction.
Technical scheme of the present invention is: comprise 1. desulfurization of operation, scrap lead cream with contain desulfurization agent aqueous solution and mix, react; Filter after the reaction, remove desulfurization filtrate, obtain desulfurization lead plaster (filter residue); 2. operation leaches crystallization conversion, gets operation desulfurization lead plaster 1. and adds citric acid solution, reductive agent, after described desulfurization lead plaster reacts with citric acid solution, after filtration, washing, drying obtain lead citrate; Operation is roasting 3., and lead citrate makes ultra-fine lead oxide (PbO/Pb) through after the roasting;
Operation of the present invention sweetening agent 1. is the mixture of yellow soda ash, sodium bicarbonate;
Operation of the present invention reductive agent 2. is solubility inorganic oxidizer.Such as sodium peroxide, hydrogen peroxide or oxalic acid.
Operation of the present invention is when 2. reductive agent is hydrogen peroxide, PbO
2With the molar ratio of hydrogen peroxide be 1: 1.2-3.
The molar ratio of institute of the present invention sweetening agent yellow soda ash and sodium bicarbonate is 1: 1.5～5.
Operation of the present invention 1. in, the ingredient proportion of scrap lead cream and sweetening agent is the S in the scrap lead cream: the mol ratio of the Na in the sweetening agent is 1: 3-8; Scrap lead cream is 1 with the mass ratio that contains desulfurization agent aqueous solution: 10-30; Sweetening agent adds water and is mixed with desulfuration solution, and desulfurization temperature is room temperature-70 ℃; Desulfurization time is 1-8h.
Operation of the present invention is middle preferred value 1., and the ingredient proportion of scrap lead cream and sweetening agent is the S in the scrap lead cream: the Na of v is 1: 4 in the sweetening agent; Scrap lead cream is 1: 10 with the mass ratio that contains desulfurization agent aqueous solution; Desulfurization temperature is 35 ℃; Desulfurization time is 2h.
Operation of the present invention 2. in the feed ratio of desulfurization lead plaster and citric acid be lead in the desulfurization lead plaster: the mol ratio of citric acid is 1: 1.5-4; The mass ratio of desulfurization lead plaster and citric acid solution is 1: 3-15; The pH of citric acid solution is 2.0-5.0; Reaction times is 0.5-4h.
Operation of the present invention is middle preferred value 2.: the feed ratio of desulfurization lead plaster and citric acid is the lead in the desulfurization lead plaster: the amount ratio of citric acid is 1: 2; Desulfurization lead plaster and citric acid solution mass ratio be 1: 5; Reaction times is 1-2h.
The operation of the present invention 3. maturing temperature of middle lead citrate is 300-500 ℃, and preferred maturing temperature is 350-400 ℃; Roasting time is 0.5-6h, and preferred roasting time is 0.3-1h.
Technical solution of the present invention comprises that also pre-treatment and the byproduct before the desulfurization reclaims.
Pre-treatment before the desulfurization is: the lead plaster pre-treatment before the desulfurization is taken out for the lead plaster with waste lead acid battery, and washing is to neutral oven dry, and grinding to form granularity is the above lead plaster powder of 100 orders.
Final product of the present invention is ultra-fine lead oxide (PbO/Pb), is mainly mixture plumbous and plumbous oxide, and oxidisability is 65-100%.Its average grain granularity is less than 1 micron, and nanocrystalline particle diameter is at 200-500nm.
Being recovered as of byproduct: desulfurization with leach the crystallization conversion process in the desulfurization filtrate that produces and to leach filtrate component relative simple, can distinguish reuse, simultaneously desulfurization filtrate can be reclaimed byproduct sulfite when sodium sulfate is enriched to a certain degree.
Design philosophy of the present invention is to adopt the composite desulfurizing agent of yellow soda ash and sodium bicarbonate to carry out first desulfurization, guarantees that desulfurization product is pure, and leaching and transforming sequestrant is citric acid, and the reductive agent that uses is H
2O
2, the lead plaster after its desulfurization carries out crystallization conversion in citric acid solution, and filtrate is divided open cycle, reclaims ultra-fine lead oxide powder (PbO/Pb).
The inventive method is held lead plaster by scrap lead and is prepared ultra-fine lead oxide, and two step leaching process filtrate components are simple, can recycle.Its technological process energy consumption is low, and equipment is simple, and lead recovery is high, and ultra-fine plumbous quality product is high.It is simple and convenient that the present invention also has technique, it is fast to have speed of response, the resource recovering effect is good, filtrate recycle is easy, the production process environmental protection is pollution-free, the characteristics that meet cleaner production, compared with prior art, the invention has the beneficial effects as follows that desulfurization and extract technology equipment are simple, respectively reuse of filtrate, by-product recovery is convenient, simultaneously directly the preparation lead storage battery with the active substance ultra-fine lead oxide, unleaded volatile quantity is little, dust rate is low, vertical yield height, energy consumption is low and do not produce the characteristics such as sulfur dioxide pollution.
Description of drawings
Fig. 1 is the process route view that the present invention prepares ultra-fine lead oxide powder (PbO/Pb).
Fig. 2 is X-ray diffraction (XRD) figure of desulfurization lead plaster.
Fig. 3 is X-ray diffraction (XRD) figure of lead citrate.
Fig. 4 is field emission scanning electron microscope (SEM) figure of lead citrate.
Fig. 5 is X-ray diffraction (XRD) figure of ultra-fine lead oxide powder (PbO/Pb).
Fig. 6 is field emission scanning electron microscope (SEM) figure of ultra-fine lead oxide powder (PbO/Pb).
Embodiment
The present invention will be further described below in conjunction with Fig. 1.
Embodiment 1:
(1) pre-treatment before the desulfurization is: the lead plaster pre-treatment before the desulfurization is taken out for the lead plaster with waste lead acid battery, and washing is to neutral oven dry, and grinding to form granularity is the above scrap lead cream powder of 100 orders, and wherein lead sulfate content is 64.5%.
(2) preparation of this ultra-fine lead oxide (PbO/Pb)
2.1 desulfurization transforms
The molar ratio that the scrap lead cream of 100g is added to total 55g yellow soda ash and sodium bicarbonate is (wherein the S in the scrap lead cream: the mol ratio of the Na in the sweetening agent is 1: 4) in 1: 2 the composite desulfate solution, the desulfuration solution solid-to-liquid ratio is 1: 10, makes mixed solution in 35 ℃ of lower reaction 2h; The desulfurization degree of scrap lead cream is more than 98.5%.Get desulfurization lead plaster, the XRD of gained desulfurization lead plaster sees Fig. 2, can find out on scheming, and main composition is lead carbonate and plumbic oxide.
2PbSO
4+Na
2CO
3+2NaHCO
3→2PbCO
3+2Na
2SO
4+CO
2+H
2O (4)
2.2 leach preparation lead citrate presoma
With 2.1 mixed solution precipitate and separate, filtrate is got back to the desulfurization transformation stage, rear Separation and Recovery byproduct acquires a certain degree, remaining filter residue is the water that desulfurization lead plaster adds 5 times of weight, add citric acid and reductive agent hydrogen peroxide, the lead in the desulfurization lead plaster: the amount ratio of citric acid is 1: 2, the 20g of 30% hydrogen peroxide, filtering separation after the reaction regular hour, the filter residue that obtains is lead citrate (PbC
6H
6O
7H
2O), 65 ℃ of oven dry.Wherein the feed ratio of desulfurization lead plaster and citric acid is the lead in the lead plaster after the desulfurization: the mol ratio of citric acid is 1: 2; The dosage that is citric acid is 105g, and the reaction times is 1.5h, and temperature of reaction is room temperature.Can find out that from reaction equation (5)-(8) product only has lead citrate, water and carbonic acid gas the leaching conversion process, it is very pure that lead citrate separates rear filtrate, leaches filtrate and get back to reuse in the leaching reduction system.
PbO+C
6H
8O
7·H
2O→Pb(C
6H
6O
7)·H
2O+H
2O (5)
PbO
2+C
6H
8O
7·H
2O+H
2O
2→Pb(C
6H
6O
7)·H
2O+O
2+2H
2O (6)
PbCO
3+C
6H
8O
7·H
2O→Pb(C
6H
6O
7)·H
2O+H
2O+CO
2 (7)
Pb
3(CO
3)
2(OH)
2+3C
6H
8O
7·H
2O→3Pb(C
6H
6O
7)·H
2O+3CO
2+4H
2O (8)
Product after the described desulfurization is that desulfurization lead plaster is PbCO
3, Pb
3(CO
3)
2(OH) and not react Pb, PbO, PbO
2Described lead citrate is Pb (C
6H
6O
7) and hydrate, the XRD of lead citrate sees Fig. 3.
2.3 roasting prepares ultra-fine lead oxide (PbO/Pb).Product after (2.2) oven dry is put into stoving oven, at 375 ℃ of roasting 1h, obtain the ultra-fine lead oxide product.Described lead citrate is at 375 ℃ of roasting 1h, finally obtain light yellow ultra-fine lead oxide (PbO/Pb) product, the XRD of ultra-fine lead oxide (PbO/Pb) sees Fig. 5, the SEM of ultra-fine lead oxide sees Fig. 6, can find out on scheming, and the main component of ultra-fine lead oxide is the mixture of plumbous oxide and metallic lead, the lead powder particle diameter is less between 100-500nm, the oxidisability of ultra-fine lead oxide is 78%, raw material availability 97.6%, the yield 98.2% of lead citrate.
The recovery of 3 byproducts
Desulfurization with leach the crystallization conversion process in the desulfurization filtrate that produces and to leach filtrate component relative simple, can distinguish reuse, simultaneously desulfurization filtrate can be reclaimed byproduct sulfite when sodium sulfate is enriched to a certain degree.
Embodiment 2:
Difference from Example 1 is: yellow soda ash and sodium bicarbonate mol ratio are 1: 3, and desulfurization time is 3h, finally obtain light yellow lead powder (PbO/Pb) product, raw material availability 98.3%, the yield 97.5% of lead citrate.Other is identical with embodiment 1, and the technique significant parameter sees Table 1.
Embodiment 3:
Difference from Example 1 is: lead and citric acid mol ratio in the citric acid leaching step in the desulfurization lead plaster are 1: 3, raw material availability 98.5%, the yield 97.8% of lead citrate.Other is identical with embodiment 1, and the technique significant parameter sees Table 1.
Embodiment 4:
Difference from Example 1 is: maturing temperature is 400 ℃, and the oxidisability of the ultra-fine lead oxide powder that obtains is 70% raw material availability 98.5%, yield 97.8%.Other is identical with embodiment 1, and the technique significant parameter sees Table 1.
[0046] the technical parameter contrast table of embodiment 1-4
The technical parameter contrast table of embodiment 1-4
Claims (10)
1. ultra-fine lead oxide that utilizes scrap lead cream preparation, it is characterized in that: described ultra-fine lead oxide is plumbous (Pb) mixture with plumbous oxide (PbO), oxidisability is 65-100%, and its average grain granularity is less than 1 micron, and nanocrystalline particle diameter is at 200-500 nm.
2. a method of utilizing scrap lead cream to prepare ultra-fine lead oxide is characterized in that: comprise operation
Desulfurization, scrap lead cream with contain desulfurization agent aqueous solution and mix, react; Filter after the reaction, remove desulfurization filtrate, obtain desulfurization lead plaster; Operation
Leach crystallization conversion, get operation
Desulfurization lead plaster add citric acid solution, reductive agent reacts; After the reaction, after filtration, washing, drying obtain lead citrate; Operation
Roasting, lead citrate makes ultra-fine lead oxide through after the roasting; Described operation
Sweetening agent be the mixture of yellow soda ash and sodium bicarbonate; Described operation
Reductive agent be solubility inorganic oxidizer.
3. utilize as claimed in claim 2 scrap lead cream to prepare the method for ultra-fine lead oxide, it is characterized in that: the molar ratio of institute's sweetening agent yellow soda ash and sodium bicarbonate is 1:1.5 ~ 5.
4. utilize as claimed in claim 2 scrap lead cream to prepare the method for ultra-fine lead oxide, it is characterized in that: described operation
In, the ingredient proportion of scrap lead cream and sweetening agent is the S in the scrap lead cream: the mol ratio of the Na in the sweetening agent is l:3-8; Scrap lead cream is 1:10-30 with the mass ratio that contains desulfurization agent aqueous solution; Desulfurization temperature is room temperature-70 ℃; Desulfurization time is 1-8 h.
5. utilize as claimed in claim 2 scrap lead cream to prepare the method for ultra-fine lead oxide, it is characterized in that: described operation
In, the ingredient proportion of scrap lead cream and sweetening agent is the S in the scrap lead cream: the Na in the sweetening agent is 1:4; Scrap lead cream is 1:10 with the mass ratio that contains desulfurization agent aqueous solution; Desulfurization temperature is 35 ℃; Desulfurization time is 2 h.
6. utilize as claimed in claim 2 scrap lead cream to prepare the method for ultra-fine lead oxide, it is characterized in that: described operation
The feed ratio of middle desulfurization lead plaster and citric acid is the lead in the desulfurization lead plaster: the mol ratio of citric acid is l:1.5-4; The mass ratio of desulfurization lead plaster and citric acid solution is 1:3-15; The pH of citric acid solution is 2.0-5.0; Reaction times is 0.5-4 h.
7. utilize as claimed in claim 2 scrap lead cream to prepare the method for ultra-fine lead oxide, it is characterized in that: described operation
The feed ratio of middle desulfurization lead plaster and citric acid is the lead in the desulfurization lead plaster: the amount of citric acid is than being 1:2; Desulfurization lead plaster and citric acid solution mass ratio be 1:5; Reaction times is 1-2 h.
8. utilize as claimed in claim 2 scrap lead cream to prepare the method for ultra-fine lead oxide, it is characterized in that: described operation
Reductive agent is solubility inorganic oxidizer, such as sodium peroxide, hydrogen peroxide or oxalic acid.
9. utilize as claimed in claim 8 scrap lead cream to prepare the method for ultra-fine lead oxide, it is characterized in that: described operation
When reductive agent is hydrogen peroxide, PbO
2With the molar ratio of hydrogen peroxide be 1:1.2-3.
10. utilize as claimed in claim 1 scrap lead cream to prepare the method for ultra-fine lead oxide, it is characterized in that: described operation
The maturing temperature of middle lead citrate is 300-500 ℃, and preferred maturing temperature is 350-400 ℃; Roasting time is 0.5-6 h, and preferred roasting time is 0.5-1 h.
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| CN105655581A (en) * | 2015-11-26 | 2016-06-08 | 湖北金洋冶金股份有限公司 | Method of preparing ultrafine lead powder from organic acid-lead complex under regulation atmosphere |
| CN105655661A (en) * | 2016-01-06 | 2016-06-08 | 湘潭大学 | Lead plaster pre-desulphurization method based on limestone |
| CN105755290A (en) * | 2016-05-12 | 2016-07-13 | 南通职业大学 | Waste lead acid accumulator lead paste reduction method |
| CN105886766A (en) * | 2014-12-12 | 2016-08-24 | 中国人民解放军63971部队 | Method for preparing high-purity PbO on basis of ion exchange method |
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| CN105923649A (en) * | 2016-04-14 | 2016-09-07 | 扬州大学 | Method for removing barium sulfate impurity from lead dioxide |
| CN106252776A (en) * | 2016-08-31 | 2016-12-21 | 超威电源有限公司 | A kind of technique utilizing useless positive and negative electrode active substance to prepare battery cathode powder |
| CN106929685A (en) * | 2017-02-08 | 2017-07-07 | 河南城建学院 | The method that scrap lead cream wet method prepares high-quality lead citrate |
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| US9828654B2 (en) | 2014-02-21 | 2017-11-28 | Chilwee Power Co. Ltd & Beijing University Of Chemical Technology | Method for directly recovering lead oxide used for a lead-acid battery cathode from waste lead paste |
| US9828653B2 (en) | 2014-02-21 | 2017-11-28 | Chilwee Power Co. Ltd & Beijing University Of Chemical Technology | Method for recycling lead oxide-containing waste material |
| US10135100B2 (en) | 2014-08-20 | 2018-11-20 | Beijing University Of Chemical Technology | Method for recovering lead oxide from waste lead paste |
| CN109399698A (en) * | 2018-09-30 | 2019-03-01 | 超威电源有限公司 | A method of utilizing leaching clay standby four basic lead sulphates of lead plumbate |
| CN110171846A (en) * | 2019-05-17 | 2019-08-27 | 华中科技大学 | A method of preparation lead oxide powder being roasted by ullrasonic spraying using scrap lead cream |
| CN110745862A (en) * | 2019-11-05 | 2020-02-04 | 湖南工业大学 | Method for producing nano lead oxide by cleaning transformation-microwave pyrolysis of lead sulfate paste |
| CN113088684A (en) * | 2021-03-18 | 2021-07-09 | 华中科技大学 | Method for preparing lead powder by wet recovery of waste lead paste with acid leaching circulation |
| CN113136492A (en) * | 2021-03-30 | 2021-07-20 | 广西大学 | Method for recovering lead from waste lead paste |
| CN113677812A (en) * | 2019-01-21 | 2021-11-19 | 奥勒留环保有限公司 | Recovery of lead-containing waste |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| RU2213698C2 (en) * | 2001-11-30 | 2003-10-10 | Институт химии и химической технологии СО РАН | Method of preparing solution for lead salt production |
| CN1728445A (en) * | 2004-07-20 | 2006-02-01 | 恩吉泰克有限公司 | Desulfurization process of pastel and grids of lead accumulators |
| WO2008056125A1 (en) * | 2006-11-08 | 2008-05-15 | Cambridge Enterprise Limited | Lead recycling |
| CN101857919A (en) * | 2010-06-25 | 2010-10-13 | 合肥工业大学 | Method for preparing lead nitrate and lead oxide by using lead plaster of waste lead accumulator |
-
2012
- 2012-04-24 CN CN2012101216362A patent/CN103374657A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| RU2213698C2 (en) * | 2001-11-30 | 2003-10-10 | Институт химии и химической технологии СО РАН | Method of preparing solution for lead salt production |
| CN1728445A (en) * | 2004-07-20 | 2006-02-01 | 恩吉泰克有限公司 | Desulfurization process of pastel and grids of lead accumulators |
| WO2008056125A1 (en) * | 2006-11-08 | 2008-05-15 | Cambridge Enterprise Limited | Lead recycling |
| CN101857919A (en) * | 2010-06-25 | 2010-10-13 | 合肥工业大学 | Method for preparing lead nitrate and lead oxide by using lead plaster of waste lead accumulator |
Non-Patent Citations (2)
| Title |
|---|
| XINFENG ZHU ETC.: "Preparation of basic lead oxide from spent lead acid battery paste via chemical conversion", 《HYDROMETALLURGY》, 4 February 2012 (2012-02-04) * |
| 朱新锋等: "废铅酸电池铅膏制备超细氧化铅粉末", 《资源再生》, 31 May 2010 (2010-05-31) * |
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| US9828654B2 (en) | 2014-02-21 | 2017-11-28 | Chilwee Power Co. Ltd & Beijing University Of Chemical Technology | Method for directly recovering lead oxide used for a lead-acid battery cathode from waste lead paste |
| US9828653B2 (en) | 2014-02-21 | 2017-11-28 | Chilwee Power Co. Ltd & Beijing University Of Chemical Technology | Method for recycling lead oxide-containing waste material |
| US10135100B2 (en) | 2014-08-20 | 2018-11-20 | Beijing University Of Chemical Technology | Method for recovering lead oxide from waste lead paste |
| CN104505511B (en) * | 2014-11-20 | 2016-08-31 | 华中科技大学 | A kind of lead carbon composite, its preparation method and the application in lead carbon battery |
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| CN106929685A (en) * | 2017-02-08 | 2017-07-07 | 河南城建学院 | The method that scrap lead cream wet method prepares high-quality lead citrate |
| CN106929685B (en) * | 2017-02-08 | 2018-09-11 | 河南城建学院 | The method that scrap lead cream wet method prepares high quality lead citrate |
| CN107134602A (en) * | 2017-03-30 | 2017-09-05 | 湖北绿色家园材料技术股份有限公司 | A kind of method that high activity ultra-fine lead oxide powder is synthesized with scrap lead cream |
| CN109399698A (en) * | 2018-09-30 | 2019-03-01 | 超威电源有限公司 | A method of utilizing leaching clay standby four basic lead sulphates of lead plumbate |
| CN113677812A (en) * | 2019-01-21 | 2021-11-19 | 奥勒留环保有限公司 | Recovery of lead-containing waste |
| CN110171846A (en) * | 2019-05-17 | 2019-08-27 | 华中科技大学 | A method of preparation lead oxide powder being roasted by ullrasonic spraying using scrap lead cream |
| CN110745862A (en) * | 2019-11-05 | 2020-02-04 | 湖南工业大学 | Method for producing nano lead oxide by cleaning transformation-microwave pyrolysis of lead sulfate paste |
| CN113088684A (en) * | 2021-03-18 | 2021-07-09 | 华中科技大学 | Method for preparing lead powder by wet recovery of waste lead paste with acid leaching circulation |
| CN113136492A (en) * | 2021-03-30 | 2021-07-20 | 广西大学 | Method for recovering lead from waste lead paste |
| CN114517262A (en) * | 2022-01-13 | 2022-05-20 | 骆驼集团(安徽)再生资源有限公司 | Process for recovering lead in waste lead storage battery |
| CN114517262B (en) * | 2022-01-13 | 2024-04-02 | 骆驼集团(安徽)再生资源有限公司 | Recovery process of lead in waste lead storage battery |
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