CN112442603A - Method for desulfurizing lead waste - Google Patents
Method for desulfurizing lead waste Download PDFInfo
- Publication number
- CN112442603A CN112442603A CN202011072373.1A CN202011072373A CN112442603A CN 112442603 A CN112442603 A CN 112442603A CN 202011072373 A CN202011072373 A CN 202011072373A CN 112442603 A CN112442603 A CN 112442603A
- Authority
- CN
- China
- Prior art keywords
- lead
- desulfurizing
- ammonium bicarbonate
- waste
- desulfurization
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- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- 239000002699 waste material Substances 0.000 title claims abstract description 22
- 238000000034 method Methods 0.000 title claims abstract description 18
- 230000003009 desulfurizing effect Effects 0.000 title claims abstract description 16
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims abstract description 20
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims abstract description 19
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 claims abstract description 19
- 235000012538 ammonium bicarbonate Nutrition 0.000 claims abstract description 19
- 239000001099 ammonium carbonate Substances 0.000 claims abstract description 19
- 238000006477 desulfuration reaction Methods 0.000 claims abstract description 17
- 230000023556 desulfurization Effects 0.000 claims abstract description 17
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 claims abstract description 15
- 229910052921 ammonium sulfate Inorganic materials 0.000 claims abstract description 15
- 235000011130 ammonium sulphate Nutrition 0.000 claims abstract description 15
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 claims abstract description 12
- 229910000019 calcium carbonate Inorganic materials 0.000 claims abstract description 10
- 239000012452 mother liquor Substances 0.000 claims abstract description 10
- 229910000003 Lead carbonate Inorganic materials 0.000 claims abstract description 7
- MFEVGQHCNVXMER-UHFFFAOYSA-L 1,3,2$l^{2}-dioxaplumbetan-4-one Chemical compound [Pb+2].[O-]C([O-])=O MFEVGQHCNVXMER-UHFFFAOYSA-L 0.000 claims abstract description 5
- 239000007788 liquid Substances 0.000 claims abstract description 5
- 238000000926 separation method Methods 0.000 claims abstract description 5
- 238000006243 chemical reaction Methods 0.000 claims description 17
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 16
- 239000011505 plaster Substances 0.000 claims description 10
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 8
- 239000001569 carbon dioxide Substances 0.000 claims description 7
- 238000000227 grinding Methods 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 7
- 238000000498 ball milling Methods 0.000 claims description 3
- 238000010008 shearing Methods 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 2
- 239000002253 acid Substances 0.000 description 7
- 235000010216 calcium carbonate Nutrition 0.000 description 6
- 230000008929 regeneration Effects 0.000 description 4
- 238000011069 regeneration method Methods 0.000 description 4
- 229910001868 water Inorganic materials 0.000 description 4
- 230000018109 developmental process Effects 0.000 description 3
- PIJPYDMVFNTHIP-UHFFFAOYSA-L lead sulfate Chemical compound [PbH4+2].[O-]S([O-])(=O)=O PIJPYDMVFNTHIP-UHFFFAOYSA-L 0.000 description 3
- 239000011268 mixed slurry Substances 0.000 description 3
- KEQXNNJHMWSZHK-UHFFFAOYSA-L 1,3,2,4$l^{2}-dioxathiaplumbetane 2,2-dioxide Chemical compound [Pb+2].[O-]S([O-])(=O)=O KEQXNNJHMWSZHK-UHFFFAOYSA-L 0.000 description 2
- 238000003723 Smelting Methods 0.000 description 2
- 229910052924 anglesite Inorganic materials 0.000 description 2
- 229910052925 anhydrite Inorganic materials 0.000 description 2
- 238000004891 communication Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical class N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- 235000019738 Limestone Nutrition 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- BIGPRXCJEDHCLP-UHFFFAOYSA-N ammonium bisulfate Chemical compound [NH4+].OS([O-])(=O)=O BIGPRXCJEDHCLP-UHFFFAOYSA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000007123 defense Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 239000006028 limestone Substances 0.000 description 1
- VUZPPFZMUPKLLV-UHFFFAOYSA-N methane;hydrate Chemical compound C.O VUZPPFZMUPKLLV-UHFFFAOYSA-N 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000002161 passivation Methods 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 159000000000 sodium salts Chemical group 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
Images
Classifications
-
- 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
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F11/00—Compounds of calcium, strontium, or barium
- C01F11/46—Sulfates
-
- 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
-
- 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
-
- 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
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Metallurgy (AREA)
- Geology (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Inorganic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Processing Of Solid Wastes (AREA)
Abstract
The invention relates to a method for desulfurizing lead waste, which is characterized by comprising the following steps: step 1: reacting the lead waste with ammonium bicarbonate for desulfurization; step 2, obtaining lead carbonate and ammonium sulfate mother liquor after solid-liquid separation; step 3, adding calcium carbonate into the ammonium sulfate mother liquor to react to obtain ammonium bicarbonate and calcium sulfate; and 4, returning the ammonium bicarbonate obtained in the step 3 to the step 1 to continue desulfurization. The method for desulfurizing the lead waste can be recycled, and has high efficiency and low cost.
Description
Technical Field
The invention relates to the technical field of waste treatment.
Background
The lead-acid battery has excellent charge and discharge performance, strong temperature adaptability, low price, safety and reliability, so the lead-acid battery is widely applied in the fields of energy storage, communication base stations, national defense equipment, automobiles, electric vehicles, motorcycles and the like. Along with the rapid development of economy in China in recent years, the basic industries of automobiles, communication, electric power, traffic, railways, computers and the like are increasing at a high speed, the demand on lead-acid storage batteries is continuously increased, the increasing speed reaches 10% in the last decade, and the development of the lead-acid storage battery industry is greatly promoted. The scrapping period of the lead-acid storage battery per se caused by corrosion, passivation and the like is generally 3-5 years, more than 1.1 hundred million lead-acid storage batteries are scrapped every year, and the lead content is as high as 380 million tons, so that the regeneration of the waste lead-acid storage battery has great significance for environmental protection and lead resource circulation. At present, the industrial policy and technical equipment system of green cycle of waste lead storage battery resources are preliminarily established in China, and the cleaning process of mechanical crushing and sorting, pre-desulfurization and low-temperature smelting is generally implemented. Wherein, two links of mechanical crushing and sorting and low-temperature smelting are supported by fully advanced and efficient technical equipment. The process commonly adopted in the 'lead plaster pre-desulfurization' link is sodium salt and ammonia salt desulfurization, high-melting point lead sulfate is converted into low-melting point lead carbonate, efficient and thorough desulfurization is realized, the environmental benefit is outstanding, but the by-product needs to be prepared into sodium sulfate or ammonium sulfate after high-energy-consumption concentration crystallization due to high raw material value, the value is low, the economic benefit is not good, and further development of the waste lead storage battery regeneration industry is restricted. The invention provides a high-cleanness low-cost storage battery desulfurization method.
Disclosure of Invention
In order to solve the technical problem, the invention provides a method for desulfurizing lead waste, which is characterized by comprising the following steps: step 1: reacting the lead waste with ammonium bicarbonate for desulfurization; step 2, obtaining lead carbonate and ammonium sulfate mother liquor after solid-liquid separation; step 3, adding calcium carbonate into the ammonium sulfate mother liquor to react to obtain ammonium bicarbonate and calcium sulfate; and 4, returning the ammonium bicarbonate obtained in the step 3 to the step 1 to continue desulfurization.
Further, in the step 3, calcium carbonate is added into the ammonium sulfate mother liquor for reaction, and carbon dioxide gas generated in the step 1 is introduced at the same time.
Further, in the step 1, the waste lead plaster and the ammonium bicarbonate are mixed according to a molar mass ratio of 1:2 to 1: 5, putting the mixture into a ball milling or shearing reaction tank, and then adding a mixture of the mixture and waste lead paste in a mass ratio of 2: 1, grinding, desulfurizing and converting for 10-60min at the temperature of 0-45 ℃ for desulfurizing.
Further, in the step 3, calcium carbonate is added, and carbon dioxide gas generated in the step 1 is introduced under the stirring or grinding condition, the reaction temperature is 0-50 ℃, and the reaction time is 15-60 min.
The method for desulfurizing the lead waste can be recycled, and has high efficiency and low cost.
Drawings
FIG. 1 is a flow diagram of the desulfurization of lead scrap in accordance with the present invention.
Detailed Description
The invention is further described below with reference to the specific drawings.
As shown in fig. 1, the method for desulfurizing lead scrap according to the present invention comprises the following steps:
step 1 desulfurization of waste lead plaster and ammonium bicarbonate
Putting waste lead plaster (calculated by lead sulfate) and ammonium bicarbonate into a ball milling or shearing reaction tank according to a molar mass ratio (1:2-5), and then adding a mixture of the waste lead plaster and the ammonium bicarbonate, wherein the mass ratio of the waste lead plaster to the waste lead plaster is 2: 1, grinding, desulfurizing and converting the pure water at the temperature of 0-45 ℃ for 10-60min to generate lead carbonate, ammonium sulfate, carbon dioxide and water, and trapping the carbon dioxide for the next step for reuse. The conversion efficiency of the lead sulfate is more than 99.5 percent, and the mixed slurry is transferred to a buffer tank for standby after the grinding reaction is finished.
The desulfurization process occurs as follows.
The reaction equation is as follows: PbSO4+2NH4HCO3 → PbCO3+ (NH4)2SO4+ H2O + CO2 step 2 solid-liquid separation of mixed slurry
And carrying out filter pressing on the mixed slurry in the buffer tank for solid-liquid separation to obtain the desulfurized lead plaster and the ammonium sulfate solution.
Step 3 regeneration of ammonium bicarbonate mother liquor
Putting the ammonia sulfate mother liquor after the lead plaster desulfurization into a reaction kettle, adding calcium carbonate, slowly introducing carbon dioxide gas generated in the first step into the reaction kettle under the stirring or grinding condition, reacting at the temperature of 0-50 ℃ for 15-60 min to generate calcium sulfate precipitate and ammonium bicarbonate, wherein the conversion efficiency of the ammonium sulfate is more than 99%, and in the process, 1% of regeneration and conversion are incomplete, and the ammonium sulfate precipitate and the ammonium bicarbonate are supplemented with new ammonium bicarbonate for balance. The reaction is as follows:
the reaction equation is as follows:
(NH4)2SO4+CaCO3+Co2+H2O→2NH4HCO3+CaSO4↓
and 4, returning the ammonium bicarbonate obtained in the step 3 to the step 1 to continue desulfurization.
Combining the above reaction equations: the PbSO4+ CaCO3 → PbCO3+ CaSO4 raw materials are only limestone which is cheap and easy to obtain, and equivalent calcium sulfate can be obtained, so the desulfurization method is the most economic method in the storage battery industry at present.
The above-described embodiments are only preferred embodiments of the present invention, and are not intended to limit the present invention in any way, and other variations and modifications may be made without departing from the spirit of the invention as set forth in the claims.
Claims (4)
1. A method for desulfurizing lead scrap is characterized by comprising the following steps: step 1: reacting the lead waste with ammonium bicarbonate for desulfurization; step 2, obtaining lead carbonate and ammonium sulfate mother liquor after solid-liquid separation; step 3, adding calcium carbonate into the ammonium sulfate mother liquor to react to obtain ammonium bicarbonate and calcium sulfate; and 4, returning the ammonium bicarbonate obtained in the step 3 to the step 1 to continue desulfurization.
2. The method for desulfurizing lead scrap according to claim 1, wherein in the step 3, the carbon dioxide gas generated in the step 1 is introduced while calcium carbonate is added to the ammonium sulfate mother liquor for reaction.
3. The method for desulfurizing lead scrap according to claim 1 or 2, wherein in the step 1, the waste lead plaster and the ammonium bicarbonate are mixed according to a molar mass ratio of 1:2 to 1: 5, putting the mixture into a ball milling or shearing reaction tank, and then adding a mixture of the mixture and waste lead paste in a mass ratio of 2: 1, grinding, desulfurizing and converting for 10-60min at the temperature of 0-45 ℃ for desulfurizing.
4. The method for desulfurizing lead scrap according to claim 1 or 2, wherein calcium carbonate is added in the step 3, and carbon dioxide gas generated in the step 1 is introduced under stirring or grinding conditions, and the reaction temperature is 0-50 ℃ and the reaction time is 15-60 min.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011072373.1A CN112442603A (en) | 2020-10-09 | 2020-10-09 | Method for desulfurizing lead waste |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011072373.1A CN112442603A (en) | 2020-10-09 | 2020-10-09 | Method for desulfurizing lead waste |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN112442603A true CN112442603A (en) | 2021-03-05 |
Family
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202011072373.1A Pending CN112442603A (en) | 2020-10-09 | 2020-10-09 | Method for desulfurizing lead waste |
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| CN (1) | CN112442603A (en) |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1619261A1 (en) * | 2004-07-20 | 2006-01-25 | ENGITEC S.r.l. | Desulfurization process of pastel and grids of lead accumulators |
| US20110083970A1 (en) * | 2007-11-30 | 2011-04-14 | Engitec Technologies S.P.A. | Process for producing metallic lead starting from desulfurized pastel |
| CN103794834A (en) * | 2014-03-04 | 2014-05-14 | 襄阳远锐资源工程技术有限公司 | Method for recycling used lead-acid batteries in full circulation mode |
| CN105280976A (en) * | 2014-10-27 | 2016-01-27 | 李洪亮 | Environmental-friendly and high-efficiency processing method of waste lead-acid storage battery |
| CN105655661A (en) * | 2016-01-06 | 2016-06-08 | 湘潭大学 | Lead plaster pre-desulphurization method based on limestone |
| CN106222425A (en) * | 2016-08-31 | 2016-12-14 | 株洲鼎端装备股份有限公司 | The sulfur method of lead plaster in a kind of waste and old lead acid accumulator |
| CN106498167A (en) * | 2016-10-31 | 2017-03-15 | 湘潭大学 | A kind of diachylon desulphurization method of intensified by ultrasonic wave ammonium hydrogen carbonate for desulfurizing agent |
| CN110669924A (en) * | 2019-10-31 | 2020-01-10 | 湘潭大学 | Based on CO2Recycling lead plaster desulfurization method |
-
2020
- 2020-10-09 CN CN202011072373.1A patent/CN112442603A/en active Pending
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1619261A1 (en) * | 2004-07-20 | 2006-01-25 | ENGITEC S.r.l. | Desulfurization process of pastel and grids of lead accumulators |
| US20110083970A1 (en) * | 2007-11-30 | 2011-04-14 | Engitec Technologies S.P.A. | Process for producing metallic lead starting from desulfurized pastel |
| CN103794834A (en) * | 2014-03-04 | 2014-05-14 | 襄阳远锐资源工程技术有限公司 | Method for recycling used lead-acid batteries in full circulation mode |
| CN105280976A (en) * | 2014-10-27 | 2016-01-27 | 李洪亮 | Environmental-friendly and high-efficiency processing method of waste lead-acid storage battery |
| CN105655661A (en) * | 2016-01-06 | 2016-06-08 | 湘潭大学 | Lead plaster pre-desulphurization method based on limestone |
| CN106222425A (en) * | 2016-08-31 | 2016-12-14 | 株洲鼎端装备股份有限公司 | The sulfur method of lead plaster in a kind of waste and old lead acid accumulator |
| CN106498167A (en) * | 2016-10-31 | 2017-03-15 | 湘潭大学 | A kind of diachylon desulphurization method of intensified by ultrasonic wave ammonium hydrogen carbonate for desulfurizing agent |
| CN110669924A (en) * | 2019-10-31 | 2020-01-10 | 湘潭大学 | Based on CO2Recycling lead plaster desulfurization method |
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