CN103374658A - Ultrafine lead oxide prepared from desulfurated lead plaster by means of three-stage process and method thereof - Google Patents
Ultrafine lead oxide prepared from desulfurated lead plaster by means of three-stage process and method thereof Download PDFInfo
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- CN103374658A CN103374658A CN2012101216659A CN201210121665A CN103374658A CN 103374658 A CN103374658 A CN 103374658A CN 2012101216659 A CN2012101216659 A CN 2012101216659A CN 201210121665 A CN201210121665 A CN 201210121665A CN 103374658 A CN103374658 A CN 103374658A
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
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- 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 ultrafine lead oxide prepared from desulfurated lead plaster by means of three-stage process and a method for preparing the ultrafine lead oxide. The method comprises the following steps of: carrying out a desulfurization and lead plaster acid leaching process by causing the desulfurated lead plaster to react with acid, simultaneously adding a reducing agent, and carrying out solid-liquid separation after the reaction is ended to obtain a plumbic acid containing solution; carrying out a lead carbonate preparation process by causing the plumbic acid containing solution to react with sodium carbonate, carrying out solid-liquid separation, washing and drying to obtain the lead carbonate; carrying out a roasting process by preparing the ultrafine lead carbonate by roasting the lead carbonate, wherein the ultrafine lead oxide can be PbO, Pb3O4, or the mixture of the PbO and the Pb3O4, the mean particle granularity of the ultrafine lead oxide is less than 2 mu m, and the nanocrystalline grain size is less than 500nm. Compared with the prior art, the preparation method of the ultrafine lead oxide disclosed by the invention has the following beneficial effects: the active material of the ultrafine lead oxide powder compound for the production of a storage battery enterprise can be directly prepared, lead volatilize quantity is small, the ash rate is low, the direct lead yield is high, the energy consumption is low, pollutants of sulfur dioxide and the like are not generated, and the like.
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, and the lead that it consumes accounts for 82% of the plumbous amount of the total consumption in the whole world.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 500-600 kg mark coal of 1 t, and the energy consumption of domestic professional secondary lead enterprise is at 130-310 kg/t, and the common level of at present external energy consumption reaches below 200 kg/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.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.
Present wet process and advanced method process alive all need first the lead plaster desulfurization, and then carry out galvanic deposit or pyrometallurgical smelting.Final product is the metal lead pig.And most of metallic lead also will be made into the making that lead powder is used for new battery.
It is raw material that CN1920065A adopts lead glance, obtains PbCl by leaching crystallization
2, adding sulfuric acid in the lead chloride solution and prepare lead sulfate, lead sulfate obtains the precursor lead carbonate by chemosynthesis, prepares at last β-PbO.CN101573461A adopts citric acid and Trisodium Citrate mixing solutions processing lead plaster to prepare ultra-fine lead oxide, and the citric acid that consumes simultaneously is more, and price is higher, reclaim(ed) sulfuric acid sodium difficulty.CN101514395A adopts the oxalic acid reduction, filters, and precipitation and nitric acid reaction are deposited in and volatile salt reacts, and filter, and precipitation also joins in the salpeter solution, and solution and ammoniacal liquor reaction are filtered, and the precipitation heat decomposition obtains plumbous oxide.The technique relative complex is simultaneously at larger medicaments of volatility such as reaction nitric acid, ammoniacal liquor.
In sum, how to provide that a kind of process is perfect, technique is simple, economize on resources, the energy and can not cause to environment the plumbic acid degree battery lead plaster treatment process of secondary pollution, has been the important topic that the technician studies this field in.
Summary of the invention
The object of the present invention is to provide a kind of ultra-fine lead oxide that utilizes the preparation of desulfurization lead plaster three-stage process, this ultra-fine lead oxide, its average grain granularity is less than 2 μ m, and nanocrystalline particle diameter is less than 500 nm.Described ultra-fine lead oxide can be PbO, Pb
3O
4, perhaps both mixtures.
The present invention also aims to provide the method for utilizing the desulfurization lead plaster three-stage process to prepare ultra-fine lead oxide, the lead plaster of the method after by the waste lead acid battery desulfurization prepares the ultra-fine lead oxide powder, its lead powder purity is high, simultaneously its Production Flow Chart is simple, non-environmental-pollution or environmental pollution is extremely low, lead recovery is high, reduce energy consumption and the environmental contamination reduction effect remarkable.
Technical scheme of the present invention is divided into several parts: the preparation of the preparation of desulfurization lead plaster, the leaching of lead plaster, the preparation of ultra-fine lead carbonate, ultra-fine lead powder and byproduct reclaim.Comprise operation
The desulfurization lead plaster Ore Leaching: desulfurization lead plaster and acid-respons, add simultaneously reductive agent, after reaction finished, solid-liquid separation got leaded acid solution; Operation
The preparation of lead carbonate: leaded acid solution and yellow soda ash reaction, after reaction finished, solid-liquid separation, washing, drying obtained lead carbonate; Operation
Roasting: lead carbonate makes ultra-fine lead oxide through after the roasting; Operation of the present invention
Reductive agent be solubility inorganic oxidizer.
Operation of the present invention
Acid be acetic acid or nitric acid; Described leaded acid solution is lead acetate or lead nitrate solution.
Described operation
In, desulfurization lead plaster with acid ingredient proportion be in the desulfurization lead plaster lead with acid molar ratio be l:2-5, preferably 1:2.5; Desulfurization lead plaster is 1:3-30 with the mass ratio that contains aqueous acid; 1:10 preferably; Temperature of reaction is room temperature-50 ℃; Reaction times is 0.5-3 h, and the reaction times is 1 h preferably.
Operation of the present invention
Middle solubility inorganic oxidizer is hydrogen peroxide, the PbO in the desulfurization lead plaster
2With the molar ratio of hydrogen peroxide be 1:1-8, preferential 1:1.5.
Operation of the present invention
In leaded acid solution, add the yellow soda ash reaction, the molar ratio of leaded acid solution and yellow soda ash is 1:1.5-3, leaded acid solution and yellow soda ash reaction times are 0.1-2 h, preferred 0.5 h, temperature of reaction is room temperature-50 ℃, guarantees that simultaneously the pH of solution is less than 10.
Operation of the present invention
In leaded acid solution, add the yellow soda ash reaction, can add simultaneously the structure directing agent polyoxyethylene glycol of the plumbous weight 1-5% in the leaded acid solution.
Operation
The maturing temperature of middle lead carbonate is 250-500 ℃, and roasting time is 0.5-6 h, and final product is ultra-fine lead oxide.
The desulfurization lead plaster product of use of the present invention can be PbCO
3, Pb
3(CO
3)
2(OH), Pb
10O (CO
3)
6(OH)
6, NaPb
2(CO
3)
2OH, Pb (OH)
2And do not react Pb, PbO, PbO
2, may not have the lead sulfate of a small amount of complete reaction and their mixture.
Adopt the ultra-fine lead oxide powder (PbO) of the inventive method preparation, its average grain granularity is less than 2 μ m, and nanocrystalline particle diameter is less than 500 nm, and purity is greater than 99.8%, and the rate of recovery of whole technological process lead surpasses 97%.
Lead compound in the desulfurization lead plaster of the present invention all can react fast with acetic acid or nitric acid.Continuously reuse of filtrate in the conversion process is leached in step in technological process (1) and (2), when sodium acetate acquires a certain degree, can reclaim sodium acetate.
Compared with prior art, the invention has the beneficial effects as follows: have direct preparation battery manufacturers production usefulness active substance ultra-fine lead oxide efflorescence compound, plumbous volatile quantity is little, dust rate is low, vertical yield is high, energy consumption is low and do not produce the characteristics such as sulfur dioxide pollution.
Description of drawings
Fig. 1 is the XRD figure of lead carbonate product of the present invention.
Fig. 2 is the SEM figure of lead carbonate product of the present invention.
Fig. 3 is the XRD figure of 320 ℃ of ultra-fine lead oxides of the present invention.
Fig. 4 is the SEM figure (5000 times of magnifications) of 320 ℃ of ultra-fine lead oxides of the present invention.
Fig. 5 is the SEM figure (20000 times of magnifications) of 320 ℃ of ultra-fine lead oxides of the present invention.
Fig. 6 is the XRD figure of ultra-fine lead oxide of the present invention 450 ℃.
Fig. 7 is the SEM figure (5000 times of magnifications) of 450 ℃ of ultra-fine lead oxides of the present invention.
Fig. 8 is the SEM figure (20000 times of magnifications) of 450 ℃ of ultra-fine lead oxides of the present invention.
Embodiment
Below the present invention will be further described.
Embodiment 1:
(1) preparation of desulfurization lead plaster
Waste lead accumulator falls after the acid treatment, processes through cracking and sorting, and screening obtains scrap lead cream; Scrap lead cream after the pre-treatment is added in the solution of sweetening agent, sweetening agent yellow soda ash commonly used, sodium bicarbonate, volatile salt etc., desulfurization is carried out solid-liquid separation after finishing.
(2) preparation plumbic acetate solution
The desulfurization lead plaster of (1) is added in the acetic acid solution, and the ingredient proportion of desulfurization lead plaster and acetic acid is that lead in the desulfurization lead plaster and the molar ratio of acetic acid are 1:2.5, adds simultaneously the reductive agent hydrogen peroxide, the PbO in the desulfurization lead plaster
2With the molar ratio of hydrogen peroxide be the 1:1.5 reaction, react the rear filtering separation behind 0.5 h, obtain lead acetate solution.The contingent reaction equation of desulfurization lead plaster and acetic acid solution may be:
PbCO
3+2CH
3COOH→Pb(CH
3COO)
2+H
2O+ CO
2 (1)
PbO+2CH
3COOH→Pb(CH
3COO)
2+H
2O (2)
PbO
2+2CH
3COOH +H
2O
2→Pb(CH
3COO)
2+2H
2O+ O
2 (3)
Pb
3(CO
3)
2(OH)
2+6CH
3COOH→3Pb(CH
3COO)
2+4H
2O+2CO
2 (4)
Pb
10O(CO
3)
6(OH)
6+20CH
3COOH→10Pb(CH
3COO)
2+13H
2O+6CO
2 (5)
NaPb
2(CO
3)
2OH+5CH
3COOH→2Pb(CH
3COO)
2+H
2O+2CO
2+Na(CH
3COO) (6)
Pb(OH)
2+2CH
3COOH→Pb(CH
3COO)
2+2H
2O (7)
(3) preparation of lead carbonate
The yellow soda ash that adds in the lead acetate solution with (2), plumbous and yellow soda ash mol ratio are 1:1.5, and the reaction times is 0.5h, solid-liquid separation, and the lead carbonate that obtains, the XRD of lead carbonate sees Fig. 1, SEM figure sees Fig. 2.
Pb(CH
3COO)
2+Na
2CO
3 →PbCO
3+2Na(CH
3COO) (8)
(4) roasting prepares ultra-fine lead powder
Product lead carbonate after the oven dry in (3) is put into stoving oven, at 320 ℃ of roasting 1 h, obtain the ultra-fine lead oxide compound products, its XRD sees Fig. 3, and SEM figure sees Fig. 4, Fig. 5.
Adopt the ultra-fine lead oxide powder (PbO) of the inventive method preparation, its average grain granularity is less than 2 μ m, and nanocrystalline particle diameter is less than 500 nm, and purity is greater than 99.8%, and the rate of recovery of whole technological process lead surpasses 97%.
Embodiment 2:
Difference from Example 1 is: leaching agent is nitric acid, and the ingredient proportion of desulfurization lead plaster and nitric acid is that lead in the desulfurization lead plaster and the molar ratio of nitric acid are 1:2.5, adds simultaneously the reductive agent hydrogen peroxide, the PbO in the desulfurization lead plaster
2With the molar ratio of hydrogen peroxide be the 1:1.5 reaction, react the rear filtering separation behind 0.5 h, obtain lead nitrate solution.The contingent reaction equation of desulfurization lead plaster and salpeter solution may be:
PbCO
3+2HNO
3→Pb(NO
3)
2+H
2O+ CO
2 (9)
PbO+2HNO
3→Pb(NO
3)
2+H
2O (10)
PbO
2+2HNO
3 +H
2O
2→Pb(NO
3)
2+2H
2O+ O
2 (11)
Pb
3(CO
3)
2(OH)
2+6HNO
3→3Pb(NO
3)
2+4H
2O+2CO
2 (12)
Pb
10O(CO
3)
6(OH)
6+20HNO
3→10Pb(NO
3)
2+13H
2O+6CO
2 (13)
NaPb
2(CO
3)
2OH+5HNO
3→2Pb(NO
3)
2+3H
2O+2CO
2 + NaNO
3 (14)
Pb(OH)
2+2HNO
3→Pb(NO
3)
2+2H
2O (15)
The yellow soda ash that adds in the lead nitrate solution, plumbous and yellow soda ash mol ratio is 1:1.5, the reaction times is 0.5h, solid-liquid separation, the lead carbonate that obtains.Reactional equation is 16
Pb(NO
3)
2+Na
2CO
3 →PbCO
3+2NaNO
3 (16)
Other material finally obtain ultra-fine lead oxide powder product, raw material availability 98.3%, yield are 99.0%.Other is identical with embodiment 1, and the technique significant parameter sees Table 1.
Embodiment 3:
Difference from Example 1 is: maturing temperature is 450 ℃, finally obtains red ultra-fine lead oxide compound products, and XRD sees Fig. 6, and SEM sees Fig. 7, Fig. 8, and raw material availability 98.0%, yield are 99.2%.Other is identical with embodiment 1, and the technique significant parameter sees Table 1.
[0036]
Embodiment 4:
Difference from Example 1 is: the dosage of acetic acid is lead in the desulfurization lead plaster and the molar ratio 1:3 of acetic acid during Ore Leaching, and solid-to-liquid ratio is 1:15 during desulfurization, finally obtains ultra-fine lead oxide powder product, raw material availability 98.1%, yield 95.6%.Other is identical with embodiment 2, and the technique significant parameter sees Table 1.
Claims (8)
1. a ultra-fine lead oxide that utilizes the preparation of desulfurization lead plaster three-stage process is characterized in that described ultra-fine lead oxide can be PbO, Pb
3O
4, perhaps both mixtures, its average grain granularity is less than 2 μ m, and nanocrystalline particle diameter is less than 500 nm.
2. one kind is utilized the desulfurization lead plaster three-stage process to prepare the ultra-fine lead oxide method, it is characterized in that: comprise operation
The desulfurization lead plaster Ore Leaching: desulfurization lead plaster and acid-respons, add simultaneously reductive agent, after reaction finished, solid-liquid separation got leaded acid solution; Operation
The preparation of lead carbonate: leaded acid solution and yellow soda ash reaction, solid-liquid separation, washing, drying obtain lead carbonate; Operation
Roasting: lead carbonate makes ultra-fine lead oxide through after the roasting; Described operation
Reductive agent be solubility inorganic oxidizer.
3. utilize as claimed in claim 2 the desulfurization lead plaster three-stage process to prepare the method for ultra-fine lead oxide, it is characterized in that: described operation
Acid be acetic acid or nitric acid; Described operation
Leaded acid solution be lead acetate or lead nitrate solution.
4. as described in claim 2 or 3, utilize the desulfurization lead plaster three-stage process to prepare the method for ultra-fine lead oxide, it is characterized in that: described operation
In, desulfurization lead plaster with acid ingredient proportion be in the desulfurization lead plaster lead with acid molar ratio be l:2-5; Desulfurization lead plaster is 1:3-30 with the mass ratio that contains aqueous acid; Temperature of reaction is room temperature-50 ℃; Reaction times is 0.5-3 h, and the reaction times is 1 h preferably.
5. as described in claim 2 or 3, utilize the desulfurization lead plaster three-stage process to prepare the method for ultra-fine lead oxide, it is characterized in that: operation
Middle solubility inorganic oxidizer is hydrogen peroxide, the PbO in the desulfurization lead plaster
2With the molar ratio of hydrogen peroxide be 1:1-8, preferential 1:1.5.
6. as described in claim 2 or 3, utilize the desulfurization lead plaster three-stage process to prepare the method for ultra-fine lead oxide, it is characterized in that: operation
In leaded acid solution, add the yellow soda ash reaction, the molar ratio of leaded acid solution and yellow soda ash is 1:1.5-3, leaded acid solution and yellow soda ash reaction times are 0.1-2 h, preferred 0.5 h, temperature of reaction is room temperature-50 ℃.
7. as described in claim 2 or 3, utilize the desulfurization lead plaster three-stage process to prepare the method for ultra-fine lead oxide, it is characterized in that: operation
In leaded acid solution, add the yellow soda ash reaction, add simultaneously the structure directing agent polyoxyethylene glycol of the plumbous weight 1-5% in the leaded acid solution.
8. as described in claim 2 or 3, utilize the desulfurization lead plaster three-stage process to prepare the method for ultra-fine lead oxide, it is characterized in that: operation
The maturing temperature of middle lead carbonate is 250-500 ℃, and roasting time is 0.5-6 h, and final product is ultra-fine lead oxide.
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Cited By (9)
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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 |
| CN106319225A (en) * | 2016-08-20 | 2017-01-11 | 超威电源有限公司 | Method for wet recovery of high-purity lead oxide from waste lead paste of lead-acid storage batteries |
| 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 |
| CN110127753A (en) * | 2019-05-23 | 2019-08-16 | 昆明理工大学 | A method of lead oxide is recycled by waste and old lead acid accumulator |
| CN110137452A (en) * | 2019-04-26 | 2019-08-16 | 浙江工业大学 | A kind of preparation method and application of Nanometer sized lead oxide/carbon composite |
| CN112939067A (en) * | 2021-01-20 | 2021-06-11 | 生态环境部华南环境科学研究所 | Method for producing nano high-purity lead oxide by resource treatment of waste lead paste |
| CN113136492A (en) * | 2021-03-30 | 2021-07-20 | 广西大学 | Method for recovering lead from waste lead paste |
| CN113277550A (en) * | 2021-05-24 | 2021-08-20 | 湖北华德莱节能减排科技有限公司 | Lead-containing solid waste treatment method, and preparation method and application of lead dioxide powder |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
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| CN113136492A (en) * | 2021-03-30 | 2021-07-20 | 广西大学 | Method for recovering lead from waste lead paste |
| CN113277550A (en) * | 2021-05-24 | 2021-08-20 | 湖北华德莱节能减排科技有限公司 | Lead-containing solid waste treatment method, and preparation method and application of lead dioxide powder |
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