CN113621812A - Lead oxide preparation process based on waste lead-acid storage battery lead plaster - Google Patents
Lead oxide preparation process based on waste lead-acid storage battery lead plaster Download PDFInfo
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- CN113621812A CN113621812A CN202110944886.5A CN202110944886A CN113621812A CN 113621812 A CN113621812 A CN 113621812A CN 202110944886 A CN202110944886 A CN 202110944886A CN 113621812 A CN113621812 A CN 113621812A
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- 229910000464 lead oxide Inorganic materials 0.000 title claims abstract description 45
- YEXPOXQUZXUXJW-UHFFFAOYSA-N oxolead Chemical compound [Pb]=O YEXPOXQUZXUXJW-UHFFFAOYSA-N 0.000 title claims abstract description 44
- 239000002699 waste material Substances 0.000 title claims abstract description 39
- 239000002253 acid Substances 0.000 title claims abstract description 38
- 238000003860 storage Methods 0.000 title claims abstract description 32
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 239000011505 plaster Substances 0.000 title claims description 24
- 238000006243 chemical reaction Methods 0.000 claims abstract description 89
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 42
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 27
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 20
- 238000006477 desulfuration reaction Methods 0.000 claims abstract description 14
- 230000023556 desulfurization Effects 0.000 claims abstract description 14
- 239000011259 mixed solution Substances 0.000 claims abstract description 12
- 239000003513 alkali Substances 0.000 claims abstract description 11
- 238000000034 method Methods 0.000 claims abstract description 11
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000012716 precipitator Substances 0.000 claims abstract description 9
- 238000000498 ball milling Methods 0.000 claims abstract description 7
- 238000003756 stirring Methods 0.000 claims description 118
- 239000000543 intermediate Substances 0.000 claims description 96
- 239000000243 solution Substances 0.000 claims description 77
- YYROPELSRYBVMQ-UHFFFAOYSA-N 4-toluenesulfonyl chloride Chemical compound CC1=CC=C(S(Cl)(=O)=O)C=C1 YYROPELSRYBVMQ-UHFFFAOYSA-N 0.000 claims description 51
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 51
- 239000007795 chemical reaction product Substances 0.000 claims description 46
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 39
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 35
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 32
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 30
- 238000001914 filtration Methods 0.000 claims description 29
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 25
- 238000010992 reflux Methods 0.000 claims description 22
- 238000001035 drying Methods 0.000 claims description 20
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 20
- 238000002390 rotary evaporation Methods 0.000 claims description 20
- 238000010438 heat treatment Methods 0.000 claims description 19
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 18
- 238000001816 cooling Methods 0.000 claims description 18
- 239000008367 deionised water Substances 0.000 claims description 18
- 229910021641 deionized water Inorganic materials 0.000 claims description 18
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 17
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 16
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 16
- 239000012065 filter cake Substances 0.000 claims description 15
- 239000000706 filtrate Substances 0.000 claims description 15
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 14
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 claims description 14
- BNWCETAHAJSBFG-UHFFFAOYSA-N tert-butyl 2-bromoacetate Chemical compound CC(C)(C)OC(=O)CBr BNWCETAHAJSBFG-UHFFFAOYSA-N 0.000 claims description 13
- 239000005457 ice water Substances 0.000 claims description 12
- 238000001291 vacuum drying Methods 0.000 claims description 11
- 238000005406 washing Methods 0.000 claims description 11
- 238000004519 manufacturing process Methods 0.000 claims description 10
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 10
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 9
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 8
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 claims description 8
- 239000012153 distilled water Substances 0.000 claims description 8
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 claims description 8
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 claims description 7
- 238000001704 evaporation Methods 0.000 claims description 7
- 238000000605 extraction Methods 0.000 claims description 7
- DYUWTXWIYMHBQS-UHFFFAOYSA-N n-prop-2-enylprop-2-en-1-amine Chemical compound C=CCNCC=C DYUWTXWIYMHBQS-UHFFFAOYSA-N 0.000 claims description 7
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 6
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 6
- 239000012074 organic phase Substances 0.000 claims description 6
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 claims description 5
- 235000019441 ethanol Nutrition 0.000 claims description 5
- 239000012071 phase Substances 0.000 claims description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 4
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 claims description 4
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 4
- 239000013078 crystal Substances 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- 238000001953 recrystallisation Methods 0.000 claims description 4
- AKEJUJNQAAGONA-UHFFFAOYSA-N sulfur trioxide Chemical compound O=S(=O)=O AKEJUJNQAAGONA-UHFFFAOYSA-N 0.000 claims description 4
- 238000003828 vacuum filtration Methods 0.000 claims description 4
- 238000005303 weighing Methods 0.000 claims description 4
- 239000001569 carbon dioxide Substances 0.000 claims description 3
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 3
- 238000002425 crystallisation Methods 0.000 claims description 3
- 230000008025 crystallization Effects 0.000 claims description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 3
- LRWZZZWJMFNZIK-UHFFFAOYSA-N 2-chloro-3-methyloxirane Chemical compound CC1OC1Cl LRWZZZWJMFNZIK-UHFFFAOYSA-N 0.000 claims description 2
- UFQDKRWQSFLPQY-UHFFFAOYSA-N 4,5-dihydro-1h-imidazol-3-ium;chloride Chemical compound Cl.C1CN=CN1 UFQDKRWQSFLPQY-UHFFFAOYSA-N 0.000 claims description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 2
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 2
- 239000002244 precipitate Substances 0.000 claims description 2
- 238000011084 recovery Methods 0.000 abstract description 11
- YADSGOSSYOOKMP-UHFFFAOYSA-N dioxolead Chemical compound O=[Pb]=O YADSGOSSYOOKMP-UHFFFAOYSA-N 0.000 abstract description 6
- 150000002500 ions Chemical class 0.000 abstract description 5
- 230000008569 process Effects 0.000 abstract description 5
- 238000004090 dissolution Methods 0.000 abstract description 3
- PIJPYDMVFNTHIP-UHFFFAOYSA-L lead sulfate Chemical compound [PbH4+2].[O-]S([O-])(=O)=O PIJPYDMVFNTHIP-UHFFFAOYSA-L 0.000 abstract description 3
- 238000001556 precipitation Methods 0.000 abstract description 3
- 239000000428 dust Substances 0.000 abstract description 2
- 238000005265 energy consumption Methods 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 12
- 238000009833 condensation Methods 0.000 description 11
- 230000005494 condensation Effects 0.000 description 11
- 239000000047 product Substances 0.000 description 6
- 239000000203 mixture Substances 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- 229910052799 carbon Inorganic materials 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 239000006080 lead scavenger Substances 0.000 description 3
- 230000009471 action Effects 0.000 description 2
- 238000004891 communication Methods 0.000 description 2
- 230000000536 complexating effect Effects 0.000 description 2
- 230000036541 health Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 230000001376 precipitating effect Effects 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 238000003723 Smelting Methods 0.000 description 1
- 238000007792 addition Methods 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000013522 chelant Substances 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 150000002611 lead compounds Chemical class 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
- 239000002994 raw material Substances 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 238000010517 secondary reaction Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- DZCAZXAJPZCSCU-UHFFFAOYSA-K sodium nitrilotriacetate Chemical compound [Na+].[Na+].[Na+].[O-]C(=O)CN(CC([O-])=O)CC([O-])=O DZCAZXAJPZCSCU-UHFFFAOYSA-K 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
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
- 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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G21/00—Compounds of lead
- C01G21/02—Oxides
- C01G21/06—Lead monoxide [PbO]
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F126/00—Homopolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen
- C08F126/02—Homopolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen by a single or double bond to nitrogen
- C08F126/04—Diallylamine
-
- 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
- C22B1/00—Preliminary treatment of ores or scrap
- C22B1/02—Roasting processes
-
- 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
- C22B1/00—Preliminary treatment of ores or scrap
- C22B1/11—Removing sulfur, phosphorus or arsenic other than by roasting
-
- 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
- C22B13/02—Obtaining lead by dry processes
- C22B13/025—Recovery from waste materials
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B13/00—Obtaining lead
- C22B13/04—Obtaining lead by wet processes
- C22B13/045—Recovery from waste materials
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
- C22B7/001—Dry 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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- Geochemistry & Mineralogy (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Electrochemistry (AREA)
- Inorganic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Secondary Cells (AREA)
Abstract
The invention discloses a lead oxide preparation process based on waste lead-acid storage battery lead paste, which relates to the technical field of waste storage battery treatment, wherein the waste lead-acid storage battery lead paste and alkali liquor are fed into a ball mill for ball milling to obtain a pre-desulfurization paste body, lead sulfate is formed to generate lead oxide, then the pre-desulfurization paste body, hydrogen peroxide, a lead capture agent and water are stirred to react with hydrogen peroxide to react lead and lead dioxide to generate lead oxide, then the newly generated active lead oxide and the lead capture agent are subjected to a complex dissolution reaction to obtain lead complex ions to obtain a mixed solution, finally a precipitator is fed into the mixed solution, and a precipitation product is roasted to obtain lead oxide; the lead oxide preparation process has the advantages of low energy consumption, reduction of secondary pollution caused by lead dust and sulfur dioxide, short process flow, high recovery rate and high recovery purity, and the lead capture agent and the precipitator are recycled, so that the process is an efficient, environment-friendly and energy-saving lead oxide preparation process.
Description
Technical Field
The invention relates to the technical field of waste storage battery treatment, in particular to a lead oxide preparation process based on waste lead-acid storage battery lead plaster.
Background
Lead-acid batteries are closely related to the development of the industries such as electric power, traffic, information and the like of the nationality and the civilization, and are indispensable products for social production and operation and human life, along with the rapid development of the fields such as related electric power-assisted vehicles, electric tricycles, electric automobiles, energy storage communication, electric power and the like, the lead-acid batteries are still continuously increased, so that the recycling of a large number of scrapped batteries becomes a huge social problem, the scrapping period of the lead-acid batteries per se caused by corrosion, passivation and the like is generally 3-5 years, in recent years, the number of scrapped lead-acid batteries replaced from vehicles, ships and communication base stations in China is huge, the scrapped batteries not only seriously waste resources, but also seriously threaten the ecological environment and the human health;
lead is a metal harmful to the environment and human health, the basic raw materials for manufacturing the lead-acid storage battery are metal lead and sulfuric acid, and along with the scrapping of the lead-acid storage battery, various lead wastes can cause great harm to the environment and human bodies if not reasonably recycled. At present, waste lead-acid batteries mainly comprise waste lead grids and lead plaster, wherein the lead plaster accounts for about 60-65% of the lead used by the lead-acid batteries, and compared with the simple direct smelting and recovery of lead from the waste lead grids, the waste lead plaster contains lead and lead compound substances thereof in various forms, such as lead, lead sulfate, lead oxide and lead dioxide, and the recovery of lead is difficult;
therefore, a process for reasonably recovering lead plaster of waste lead-acid storage batteries and preparing lead oxide for recycling is needed to solve the problems.
Disclosure of Invention
In order to overcome the technical problems, the invention aims to provide a lead oxide preparation process based on waste lead-acid storage battery lead plaster, which comprises the following steps: the method comprises the steps of feeding waste lead-acid storage battery lead paste and alkali liquor into a ball mill for ball milling to obtain a pre-desulfurization paste body, stirring and reacting the pre-desulfurization paste body, hydrogen peroxide, a lead catching agent and water to obtain a mixed solution, introducing a precipitator into the mixed solution, and roasting a precipitation product to obtain lead oxide.
The purpose of the invention can be realized by the following technical scheme:
a lead oxide preparation process based on waste lead-acid storage battery lead plaster comprises the following steps:
the method comprises the following steps: weighing 50-100 parts of waste lead-acid storage battery lead plaster, 50-100 parts of alkali liquor, 10-50 parts of lead capture agent and 800 parts of water according to parts by weight for later use;
step two: feeding the waste lead-acid storage battery lead paste and alkali liquor into a ball mill for ball milling for 1-2h to obtain a pre-desulfurization paste body;
step three: stirring and reacting the pre-desulfurization paste, hydrogen peroxide, a lead capture agent and water for 5-20h under the condition that the stirring speed is 400-;
step four: and introducing a precipitator into the mixed solution, and roasting the precipitate to obtain the lead oxide.
As a further scheme of the invention: the alkali liquor is one of sodium hydroxide solution, potassium hydroxide solution, ammonia water and sodium carbonate solution with the mass fraction of 1-50%.
As a further scheme of the invention: the precipitator is one of carbon dioxide, sulfur dioxide and sulfur trioxide.
As a further scheme of the invention: the preparation method of the lead catching agent comprises the following steps:
a1: adding diethanolamine and triethylamine into a three-neck flask provided with a stirrer, a condensation reflux pipe, a thermometer and a constant pressure dropping funnel, dropwise adding a solution a of p-toluenesulfonyl chloride under stirring at the stirring speed of 100-200r/min at the temperature of 0-5 ℃, controlling the dropwise adding speed to be 1 drop/s, continuing stirring and reacting for 4-6 hours under the condition of heating to 20-25 ℃ after the dropwise adding is finished, adding a reaction product into ice water after the reaction is finished, separating an organic phase, washing the organic phase for 2-3 times by using dilute hydrochloric acid and distilled water, drying the organic phase by using anhydrous magnesium sulfate, filtering, and rotationally evaporating the filtrate to remove the solvent to obtain an intermediate 1;
the reaction principle is as follows:
a2: adding diethylenetriamine into a three-neck flask provided with a stirrer, a condensation reflux pipe, a thermometer and a constant pressure dropping funnel, stirring while dropwise adding a p-toluenesulfonyl chloride solution b and an anhydrous potassium carbonate solution under the conditions that the temperature is 0-5 ℃ and the stirring rate is 100-200r/min, controlling the dropwise adding rate to be 1 drop/s, heating to 20-25 ℃ after the dropwise adding is finished, continuing stirring for reaction for 2-4h, adding a reaction product into ice water after the reaction is finished, filtering, adding a filter cake into anhydrous ethanol for recrystallization, and drying to obtain an intermediate 2;
the reaction principle is as follows:
a3: adding the intermediate 1, the intermediate 2, anhydrous potassium carbonate and N, N-dimethylformamide into a three-neck flask provided with a stirrer, a thermometer and a constant-pressure dropping funnel, stirring at a constant temperature of 100-;
the reaction principle is as follows:
a4: adding concentrated sulfuric acid of the intermediates 3 and 2/3 into a three-neck flask provided with a stirrer, a thermometer, a condensation reflux pipe and a constant pressure dropping funnel, stirring at a constant temperature of 100-105 ℃ and a stirring rate of 200-300r/min for 40-50h, cooling a reaction product in an ice water bath after the reaction is finished, adding absolute ethyl alcohol while stirring to separate out crystals, performing vacuum filtration, adding a filter cake into deionized water, stirring at a constant temperature of 90-93 ℃ and a stirring rate of 200-300r/min until the solution is clear, cooling to 75-80 ℃, adding active carbon, performing heating reflux reaction for 20-40min, filtering, adding the rest 1/3 concentrated sulfuric acid into the filtrate, cooling for crystallization, filtering, placing the filter cake into a vacuum drying box, drying to constant weight at a temperature of 60-70 ℃, obtaining an intermediate 4;
the reaction principle is as follows:
a5: adding the intermediate 4 and acetonitrile into a three-neck flask provided with a stirrer, a thermometer and a constant-pressure dropping funnel, stirring for 10-20min at room temperature and at a stirring speed of 400-500r/min, then dropwise adding a tert-butyl bromoacetate solution while stirring, controlling the dropwise adding speed to be 1 drop/s, continuing stirring for reaction for 20-30h after the dropwise adding is finished, performing rotary evaporation on a reaction product after the reaction is finished to remove the solvent, then adding deionized water, adjusting the pH of the reaction system to be 3 by using a hydrochloric acid solution, then extracting for 2-3 times by using anhydrous ether, collecting a water phase, adjusting the pH to be 8 by using a sodium hydroxide solution, adding dichloromethane for extracting for 2-3 times, drying a dichloromethane extraction solution by using anhydrous sodium sulfate, filtering, and performing rotary evaporation to remove dichloromethane to obtain an intermediate 5;
the reaction principle is as follows:
a6: adding tetrahydrofuran of the intermediates 5 and 1/2 into a three-neck flask provided with a stirrer, a thermometer, a condensation reflux pipe and a constant pressure dropping funnel, stirring for 10-20min under the conditions that the temperature is 50-70 ℃ and the stirring speed is 350-450r/min, then dropwise adding epoxy chloropropane while stirring, controlling the dropwise adding speed to be 1 drop/s, continuing to stir for reaction for 6-10h after the dropwise adding is finished, washing the reaction product with acetone for 2-3 times after the reaction is finished, then adding the reaction product and the rest 1/2 of tetrahydrofuran into the three-neck flask, dropwise adding a sodium hydroxide solution while stirring, controlling the dropwise adding speed to be 1 drop/s, continuing to stir for reaction for 2-3h after the dropwise adding is finished, adjusting the pH of the reaction product to be 7 by using a hydrochloric acid solution after the reaction is finished, filtering, carrying out rotary evaporation on the filtrate to obtain an intermediate 6;
the reaction principle is as follows:
a7: adding the intermediate 6 and tetrahydrofuran into a three-neck flask provided with a stirrer, a thermometer, a condensation reflux pipe and a constant-pressure dropping funnel, stirring for 10-20min at room temperature and at a stirring speed of 350-450r/min, then dropwise adding diallylamine while stirring, controlling the dropping speed to be 1 drop/s, heating to 50-70 ℃ after dropwise adding, continuing stirring for reaction for 6-10h, and rotationally evaporating a reaction product after the reaction is finished to remove a solvent to obtain an intermediate 7;
the reaction principle is as follows:
a8: adding the intermediate 7 and trifluoroacetic acid into a flask provided with a stirrer, stirring and reacting for 3-4h at room temperature and a stirring speed of 1000-1200r/min, and performing rotary evaporation on a reaction product after the reaction is finished to obtain an intermediate 8;
the reaction principle is as follows:
a9: adding the intermediate 8, deionized water and azodiisobutyl imidazoline hydrochloride into a three-neck flask provided with a stirrer, a thermometer and a gas guide tube, introducing nitrogen for protection, stirring and reacting for 8-10h under the conditions that the temperature is 60-75 ℃ and the stirring speed is 550-750r/min, placing a reaction product in a vacuum drying box after the reaction is finished, and drying to constant weight under the condition that the temperature is 60-70 ℃ to obtain the lead capture agent.
The reaction principle is as follows:
as a further scheme of the invention: the dosage ratio of the diethanolamine solution to the triethylamine solution to the p-toluenesulfonyl chloride solution in the step A1 is 0.1 mol: 50mL of: 150mL, the p-toluenesulfonyl chloride solution a is p-toluenesulfonyl chloride according to the molar ratio of 0.11 mol: 50mL of solution formed by dissolving in dichloromethane, wherein the mass fraction of the dilute hydrochloric acid is 10%.
As a further scheme of the invention: the dosage ratio of the diethylenetriamine, the p-toluenesulfonyl chloride solution b and the anhydrous potassium carbonate solution in the step A2 is 0.1 mol: 150mL of: 100mL, the p-toluenesulfonyl chloride solution b is p-toluenesulfonyl chloride according to the molar ratio of 0.11 mol: 50mL of a solution formed by dissolving in acetone, the anhydrous potassium carbonate solution being anhydrous potassium carbonate in a weight ratio of 27.8 g: 50mL of a solution obtained by dissolving the above components in distilled water.
As a further scheme of the invention: the dosage ratio of the intermediate 1, the intermediate 2, anhydrous potassium carbonate and N, N-dimethylformamide in the step A3 is 0.02 mol: 0.02 mol: 0.06 mol: 100mL, wherein the mass fraction of the ethanol solution is 90-95%.
As a further scheme of the invention: the dosage ratio of the intermediate 3, concentrated sulfuric acid, absolute ethyl alcohol, deionized water and activated carbon in the step A4 is 30 g: 100mL of: 200mL of: 80mL of: 4g, wherein the mass fraction of the concentrated sulfuric acid is 97%.
As a further scheme of the invention: the dosage ratio of the intermediate 4, the acetonitrile, the bromoacetic acid tert-butyl ester solution and the deionized water in the step A5 is 7.5 g: 100mL of: 100mL of: 100mL, wherein the tert-butyl bromoacetate solution is tert-butyl bromoacetate according to the weight ratio of 8.5 g: 20mL of solution formed by dissolving in acetonitrile, wherein the molar concentrations of the hydrochloric acid solution and the sodium hydroxide solution are both 1 mol/L.
As a further scheme of the invention: the dosage ratio of the intermediate 5, tetrahydrofuran, epichlorohydrin and sodium hydroxide solution in the step A6 is 0.08 mol: 50mL of: 0.1 mol: 120mL, and the molar concentrations of the sodium hydroxide solution and the hydrochloric acid solution are both 1 mol/L.
As a further scheme of the invention: the dosage ratio of the intermediate 6, tetrahydrofuran and diallylamine in the step A7 is 0.1 mol: 50mL of: 0.1 mol.
As a further scheme of the invention: the amount ratio of the intermediate 7 to trifluoroacetic acid in step A8 was 17.45 mmol: 100 mL.
As a further scheme of the invention: the dosage ratio of the intermediate 8, the deionized water and the azobisisobutylimidazoline hydrochloride in the step A9 is 15 g: 100mL of: 0.3 g.
The invention has the beneficial effects that:
the lead plaster of the waste lead-acid storage battery and alkali liquor are fed into a ball mill for ball milling to obtain a pre-desulfurization plaster body, lead sulfate is formed to generate lead oxide, then the pre-desulfurization plaster body, hydrogen peroxide, a lead capture agent and water are stirred to react with hydrogen peroxide to react lead and lead dioxide to generate lead oxide, and then the newly generated active lead oxide and the lead capture agent are subjected to a complexing dissolution reaction to obtain lead complex ions, so that the selective complexing dissolution of lead oxide effectively avoids the generation of Pb under an alkaline condition3O4Precipitating to obtain a mixed solution, finally introducing a precipitator into the mixed solution, and roasting the precipitated product to obtain lead oxide and a new precipitator, wherein the newly generated precipitator can be recycled; the lead oxide preparation process has low energy consumption, reduces secondary pollution caused by lead dust and sulfur dioxide, simultaneously does not need to consume a large amount of electric energy due to electrolytic refining, has short process flow, high recovery rate and high recovery purity, avoids the use of sulfuric acid, avoids the discharge of waste acid in the production process, recycles the used lead catching agent and precipitating agent, and is an efficient, environment-friendly and energy-saving lead oxide preparation process;
the lead capturing agent is prepared in the lead oxide preparation process, an intermediate 1 is generated through the reaction of diethanolamine and p-toluenesulfonyl chloride, an intermediate 2 is generated through the reaction of diethylenetriamine and p-toluenesulfonyl chloride, an intermediate 3 is generated through the reaction of the intermediate 1 and the intermediate 2, an intermediate 4 is generated through the intermediate 3 under the action of concentrated sulfuric acid, an intermediate 5 is generated through the reaction of the intermediate 4 and tert-butyl bromoacetate, an intermediate 6 is generated through the reaction of the intermediate 5 and epichlorohydrin, an intermediate 7 is generated through the reaction of the intermediate 6 and diallylamine, an intermediate 8 is generated through the intermediate 7 under the action of trifluoroacetic acid, the intermediate 8 is a molecular structure containing unsaturated bonds and polycarboxyl, finally the intermediate 8 is polymerized by taking azobisisobutylimidazoline hydrochloride as an initiator to form a macromolecular polymer, a large number of carboxylate radicals contained on the macromolecular polymer can coordinate with lead ions, the lead ions can be effectively captured to form a chelate, the polycarboxylic acid group and the lead ions fully react to avoid the secondary reaction, the subsequent lead recovery is facilitated, a precipitation product is formed under the synergistic effect of the lead capturing agent and the precipitating agent, the solid-liquid separation is facilitated, the high-purity lead oxide is finally generated, and the recovery rate of the lead oxide is high.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1:
the embodiment is a preparation method of a lead capture agent, comprising the following steps:
a1: adding 0.1mol of diethanolamine and 50mL of triethylamine into a three-neck flask provided with a stirrer, a reflux condenser, a thermometer and a constant pressure dropping funnel, and dropwise adding 150mL of paratoluensulfonyl chloride under stirring at a stirring speed of 100r/min at a temperature of 0 ℃ according to 0.11 mol: 50mL of p-toluenesulfonyl chloride solution a formed by dissolving dichloromethane is added at a dropping rate of 1 drop/s, the mixture is heated to 20 ℃ after the dropping is finished, the mixture is continuously stirred and reacts for 4 hours, a reaction product is added into ice water after the reaction is finished, an organic phase is separated, diluted hydrochloric acid with the mass fraction of 10% and distilled water are used for washing for 2 times, then anhydrous magnesium sulfate is used for drying, filtering is carried out, and the filtrate is subjected to rotary evaporation to obtain an intermediate 1;
a2: 0.1mol of diethylenetriamine was charged into a three-necked flask equipped with a stirrer, a reflux condenser, a thermometer and a constant pressure dropping funnel, and 150mL of p-toluenesulfonyl chloride was added dropwise while stirring at a temperature of 0 ℃ and a stirring rate of 100r/min in an amount of 0.11 mol: 50mL of p-toluenesulfonyl chloride solution b dissolved in acetone and 100mL of anhydrous potassium carbonate were mixed in a ratio of 27.8 g: 50mL of anhydrous potassium carbonate solution formed by dissolving in distilled water, controlling the dropping rate to be 1 drop/s, heating to 20 ℃ after the dropping is finished, continuing stirring for reaction for 2 hours, adding a reaction product into ice water after the reaction is finished, filtering, adding a filter cake into anhydrous ethanol for recrystallization, and drying to obtain an intermediate 2;
a3: adding 0.02mol of the intermediate 1, 0.02mol of the intermediate 2, 0.06mol of anhydrous potassium carbonate and 100mLN, N-dimethylformamide into a three-neck flask provided with a stirrer, a thermometer and a constant-pressure dropping funnel, stirring at a constant temperature of 100 ℃ and a stirring speed of 300r/min for reaction for 2 hours, cooling a reaction product to room temperature after the reaction is finished, filtering, rotatably evaporating filtrate, dropwise adding anhydrous methanol, controlling the dropwise adding speed to be 1mL/min, heating to reflux reaction, stopping heating, stopping the reaction, cooling the reaction product to room temperature, filtering, washing a filter cake with an ethanol solution with the mass fraction of 90%, then placing in a vacuum drying oven, and drying at the temperature of 100 ℃ to constant weight to obtain an intermediate 3;
a4: adding 30g of intermediate 3 and 60mL of concentrated sulfuric acid into a three-neck flask provided with a stirrer, a thermometer, a condensation reflux pipe and a constant-pressure dropping funnel, stirring at a constant temperature of 100 ℃ and a stirring rate of 200r/min for 40 hours, cooling a reaction product in an ice water bath after the reaction is finished, adding 200mL of absolute ethyl alcohol while stirring to separate out crystals, carrying out vacuum filtration, adding a filter cake into 80mL of deionized water, stirring at a constant temperature of 90 ℃ and a stirring rate of 200r/min until the solution is clear, cooling to 75 ℃, adding 4g of active carbon, carrying out heating reflux reaction for 20 minutes, filtering, adding 40mL of concentrated sulfuric acid into the filtrate, cooling to crystallize, filtering, placing the filter cake into a vacuum drying oven, and drying to constant weight at a temperature of 60 ℃ to obtain an intermediate 4;
a5: 7.5g of intermediate 4, 100mL of acetonitrile were charged into a three-necked flask equipped with a stirrer, a thermometer and a constant pressure dropping funnel, stirred at room temperature and a stirring rate of 400r/min for 10min, and then 100mL of t-butyl bromoacetate was added dropwise with stirring in an amount of 8.5 g: 20mL of a tert-butyl bromoacetate solution formed by dissolving acetonitrile, controlling the dropping rate to be 1 drop/s, continuing stirring and reacting for 20 hours after the dropping is finished, rotationally evaporating a reaction product to remove a solvent after the reaction is finished, adding 100mL of deionized water, adjusting the pH of a reaction system to be 3 by using a hydrochloric acid solution with the molar concentration of 1mol/L, extracting for 2 times by using anhydrous ether, collecting a water phase, adjusting the pH to be 8 by using a sodium hydroxide solution with the molar concentration of 1mol/L, adding dichloromethane for extracting for 2 times, drying a dichloromethane extraction liquid by using anhydrous sodium sulfate, filtering, and rotationally evaporating to obtain an intermediate 5;
a6: adding 0.08mol of intermediate 5 and 25mL of tetrahydrofuran into a three-neck flask provided with a stirrer, a thermometer, a condensation reflux pipe and a constant-pressure dropping funnel, stirring for 10min under the conditions that the temperature is 50 ℃ and the stirring speed is 350r/min, then dropwise adding 0.1mol of epichlorohydrin while stirring, controlling the dropwise adding speed to be 1 drop/s, continuing to stir for reaction for 6h after the dropwise adding is finished, washing the reaction product for 2 times by using acetone after the reaction is finished, then adding the reaction product and 25mL of tetrahydrofuran into the three-neck flask, dropwise adding 120mL of sodium hydroxide solution with the molar concentration of 1mol/L while stirring, controlling the dropwise adding speed to be 1 drop/s, continuing to stir for reaction for 2-3h after the dropwise adding is finished, adjusting the pH of the reaction product to be 7 by using hydrochloric acid solution with the molar concentration of 1mol/L after the reaction is finished, filtering, and carrying out rotary evaporation on the filtrate to obtain an intermediate 6;
a7: adding 0.1mol of intermediate 6 and 50mL of tetrahydrofuran into a three-neck flask provided with a stirrer, a thermometer, a condensation reflux pipe and a constant-pressure dropping funnel, stirring for 10min at room temperature and at a stirring speed of 350r/min, then dropwise adding 0.1mol of diallylamine while stirring, controlling the dropwise adding speed to be 1 drop/s, heating to 50 ℃ after the dropwise adding, continuing stirring for reaction for 6h, and carrying out rotary evaporation on a reaction product after the reaction is finished to obtain an intermediate 7;
a8: adding 17.45mmol of intermediate 7 and 100mL of trifluoroacetic acid into a flask provided with a stirrer, stirring and reacting for 3 hours at room temperature and at a stirring speed of 1000r/min, and performing rotary evaporation on a reaction product after the reaction is finished to obtain an intermediate 8;
a9: adding 15g of the intermediate 8, 100mL of deionized water and 0.3g of azobisisobutyrimidazoline hydrochloride into a three-neck flask provided with a stirrer, a thermometer and a gas guide tube, introducing nitrogen for protection, stirring and reacting for 8 hours at the temperature of 60 ℃ and the stirring speed of 550r/min, placing a reaction product in a vacuum drying oven after the reaction is finished, and drying to constant weight at the temperature of 60 ℃ to obtain the lead capture agent.
Example 2:
the embodiment is a preparation method of a lead capture agent, comprising the following steps:
a1: 0.1mol of diethanolamine and 50mL of triethylamine were added to a three-necked flask equipped with a stirrer, a reflux condenser, a thermometer and a constant pressure dropping funnel, and 150mL of p-toluenesulfonyl chloride was added dropwise under stirring at a stirring rate of 200r/min at a temperature of 5 ℃ in an amount of 0.11 mol: 50mL of p-toluenesulfonyl chloride solution a formed by dissolving in dichloromethane is added at a dropping rate of 1 drop/s, the mixture is heated to 25 ℃ after the dropping is finished, the mixture is continuously stirred and reacts for 6 hours, a reaction product is added into ice water after the reaction is finished, an organic phase is separated, diluted hydrochloric acid with the mass fraction of 10% and distilled water are used for washing for 3 times, then anhydrous magnesium sulfate is used for drying, filtering is carried out, and the filtrate is subjected to rotary evaporation to obtain an intermediate 1;
a2: 0.1mol of diethylenetriamine was charged into a three-necked flask equipped with a stirrer, a reflux condenser, a thermometer and a constant pressure dropping funnel, and 150mL of p-toluenesulfonyl chloride was added dropwise while stirring at a temperature of 5 ℃ and a stirring rate of 200r/min in an amount of 0.11 mol: 50mL of p-toluenesulfonyl chloride solution b dissolved in acetone and 100mL of anhydrous potassium carbonate were mixed in a ratio of 27.8 g: 50mL of anhydrous potassium carbonate solution formed by dissolving in distilled water, controlling the dropping rate to be 1 drop/s, heating to 25 ℃ after the dropping is finished, continuing stirring for reaction for 4 hours, adding a reaction product into ice water after the reaction is finished, filtering, adding a filter cake into anhydrous ethanol for recrystallization, and drying to obtain an intermediate 2;
a3: adding 0.02mol of the intermediate 1, 0.02mol of the intermediate 2, 0.06mol of anhydrous potassium carbonate and 100mLN, N-dimethylformamide into a three-neck flask provided with a stirrer, a thermometer and a constant-pressure dropping funnel, stirring and reacting at a constant temperature of 105 ℃ and a stirring speed of 500r/min for 3 hours, cooling a reaction product to room temperature after the reaction is finished, filtering, rotatably evaporating filtrate, dropwise adding anhydrous methanol, controlling the dropwise adding speed to be 5mL/min, heating to reflux reaction, stopping heating, stopping the reaction, cooling the reaction product to room temperature, filtering, washing a filter cake with an ethanol solution with the mass fraction of 95%, then placing in a vacuum drying box, and drying to constant weight at the temperature of 105 ℃ to obtain an intermediate 3;
a4: adding 30g of intermediate 3 and 60mL of concentrated sulfuric acid into a three-neck flask provided with a stirrer, a thermometer, a condensation reflux pipe and a constant-pressure dropping funnel, stirring at a constant temperature of 105 ℃ and a stirring rate of 300r/min for reaction for 50 hours, cooling a reaction product in an ice-water bath after the reaction is finished, adding 200mL of absolute ethyl alcohol while stirring to separate out crystals, carrying out vacuum filtration, adding a filter cake into 80mL of deionized water, stirring at a constant temperature of 90-93 ℃ and a stirring rate of 300r/min until the solution is clear, cooling to 80 ℃, adding 4g of active carbon, carrying out heating reflux reaction for 40 minutes, filtering, adding 40mL of concentrated sulfuric acid into a filtrate, cooling for crystallization, filtering, placing the filter cake into a vacuum drying oven, and drying at a temperature of 70 ℃ to constant weight to obtain an intermediate 4;
a5: 7.5g of intermediate 4, 100mL of acetonitrile were charged into a three-necked flask equipped with a stirrer, a thermometer and a constant pressure dropping funnel, stirred at room temperature and a stirring rate of 500r/min for 20min, and then 100mL of t-butyl bromoacetate was added dropwise with stirring in an amount of 8.5 g: 20mL of a tert-butyl bromoacetate solution formed by dissolving acetonitrile is added at a dropping rate of 1 drop/s, the mixture is continuously stirred and reacted for 30 hours after the dropping is finished, the reaction product is subjected to rotary evaporation to remove the solvent after the reaction is finished, then 100mL of deionized water is added, the pH of the reaction system is adjusted to 3 by using a hydrochloric acid solution with the molar concentration of 1mol/L, then anhydrous ether is used for extraction for 3 times, the water phase is collected, the pH of the water phase is adjusted to 8 by using a sodium hydroxide solution with the molar concentration of 1mol/L, dichloromethane is added for extraction for 3 times, the dichloromethane extraction liquid is dried by using anhydrous sodium sulfate, filtered and subjected to rotary evaporation to obtain an intermediate 5;
a6: adding 0.08mol of intermediate 5 and 25mL of tetrahydrofuran into a three-neck flask provided with a stirrer, a thermometer, a condensation reflux pipe and a constant-pressure dropping funnel, stirring for 20min under the conditions that the temperature is 70 ℃ and the stirring speed is 450r/min, then dropwise adding 0.1mol of epichlorohydrin while stirring, controlling the dropwise adding speed to be 1 drop/s, continuing to stir for reaction for 10h after the dropwise adding is finished, washing the reaction product for 3 times by using acetone after the reaction is finished, then adding the reaction product and 25mL of tetrahydrofuran into the three-neck flask, dropwise adding 120mL of sodium hydroxide solution with the molar concentration of 1mol/L while stirring, controlling the dropwise adding speed to be 1 drop/s, continuing to stir for reaction for 3h after the dropwise adding is finished, adjusting the pH of the reaction product to be 7 by using hydrochloric acid solution with the molar concentration of 1mol/L after the reaction is finished, and filtering, carrying out rotary evaporation on the filtrate to obtain an intermediate 6;
a7: adding 0.1mol of intermediate 6 and 50mL of tetrahydrofuran into a three-neck flask provided with a stirrer, a thermometer, a condensation reflux pipe and a constant-pressure dropping funnel, stirring for 20min at room temperature and at a stirring speed of 450r/min, then dropwise adding 0.1mol of diallylamine while stirring, controlling the dropwise adding speed to be 1 drop/s, heating to 70 ℃ after the dropwise adding, continuing stirring for reaction for 10h, and carrying out rotary evaporation on a reaction product after the reaction is finished to obtain an intermediate 7;
a8: adding 17.45mmol of intermediate 7 and 100mL of trifluoroacetic acid into a flask provided with a stirrer, stirring and reacting for 4 hours at room temperature and at the stirring speed of 1200r/min, and performing rotary evaporation on a reaction product after the reaction is finished to obtain an intermediate 8;
a9: adding 15g of the intermediate 8, 100mL of deionized water and 0.3g of azobisisobutyrimidazoline hydrochloride into a three-neck flask provided with a stirrer, a thermometer and a gas guide tube, introducing nitrogen for protection, stirring and reacting for 10 hours at the temperature of 75 ℃ and the stirring speed of 750r/min, placing a reaction product in a vacuum drying oven after the reaction is finished, and drying to constant weight at the temperature of 70 ℃ to obtain the lead capture agent.
Example 3:
the embodiment is a lead oxide preparation process based on waste lead-acid storage battery lead plaster, which comprises the following steps:
the method comprises the following steps: weighing 50 parts of waste lead-acid storage battery lead paste, 10 parts of sodium carbonate solution with the mass fraction of 10%, 10 parts of lead capture agent from example 1 and 300 parts of water according to the parts by weight for later use;
step two: feeding the waste lead-acid storage battery lead paste and alkali liquor into a ball mill for ball milling for 1h to obtain a pre-desulfurization paste body;
step three: stirring and reacting the pre-desulfurization paste, hydrogen peroxide, a lead capturing agent and water for 5 hours under the condition that the stirring speed is 400r/min to obtain a mixed solution;
step four: and introducing carbon dioxide into the mixed solution, and roasting the precipitated product to obtain the lead oxide.
Example 4:
the embodiment is a lead oxide preparation process based on waste lead-acid storage battery lead plaster, which comprises the following steps:
the method comprises the following steps: weighing 100 parts of waste lead-acid storage battery lead paste, 100 parts of sodium hydroxide solution with the mass fraction of 30%, 50 parts of lead capture agent from example 2 and 800 parts of water for later use;
step two: feeding the waste lead-acid storage battery lead paste and alkali liquor into a ball mill for ball milling for 2 hours to obtain a pre-desulfurization paste body;
step three: stirring and reacting the pre-desulfurization paste, hydrogen peroxide, a lead capturing agent and water for 20 hours under the condition that the stirring speed is 600r/min to obtain a mixed solution;
step four: and introducing sulfur dioxide into the mixed solution, and roasting the precipitated product to obtain the lead oxide.
Comparative example 1:
comparative example 1 differs from example 4 in that diethanolamine is used instead of the lead scavenger.
Comparative example 2:
comparative example 2 differs from example 4 in that sodium nitrilotriacetate was used instead of the lead scavenger.
Comparative example 3:
comparative example 3 is lead oxide prepared from waste lead paste by the method of application No. CN 201911012330.1.
The lead oxides of examples 3 to 4 and comparative examples 1 to 3 were examined, and the examination results are as follows.
| Sample (I) | Example 3 | Example 4 | Comparative example 1 | Comparative example 2 | Comparative example 3 |
| Purity/%) | 99.97 | 99.98 | 87.86 | 91.42 | 99.91 |
| Percent recovery% | 99.68 | 99.82 | 85.77 | 92.11 | 99.55 |
Referring to the above data, it can be seen that the lead oxide process of the waste lead paste according to the present invention has higher recovery rate and purity than the prior art according to the comparison between the example and the comparative example 3, and it can be seen that the improvement of the recovery rate and purity of the lead oxide is an important role of the lead scavenger according to the comparison between the example and the comparative examples 1-2.
In the description herein, references to the description of "one embodiment," "an example," "a specific example" or the like are intended to mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the invention. In this specification, the schematic representations of the terms used above do not necessarily refer to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples.
The foregoing is illustrative and explanatory only and is not intended to be exhaustive or to limit the invention to the precise embodiments described, and various modifications, additions, and substitutions may be made by those skilled in the art without departing from the scope of the invention or exceeding the scope of the claims.
Claims (8)
1. A lead oxide preparation process based on waste lead-acid storage battery lead plaster is characterized by comprising the following steps:
the method comprises the following steps: weighing 50-100 parts of waste lead-acid storage battery lead plaster, 50-100 parts of alkali liquor, 10-50 parts of lead capture agent, 50-100 parts of hydrogen peroxide and 800 parts of water according to parts by weight for later use;
step two: feeding the waste lead-acid storage battery lead paste and alkali liquor into a ball mill for ball milling for 1-2h to obtain a pre-desulfurization paste body;
step three: stirring and reacting the pre-desulfurization paste, hydrogen peroxide, a lead capture agent and water for 5-20h under the condition that the stirring speed is 400-;
step four: and introducing a precipitator into the mixed solution, and roasting the precipitate to obtain the lead oxide.
2. The process for preparing lead oxide based on the lead plaster of the waste lead-acid storage batteries according to claim 1, wherein the alkali liquor is one of sodium hydroxide solution, potassium hydroxide solution, ammonia water and sodium carbonate solution with the mass fraction of 1-50%.
3. The process for preparing lead oxide based on lead plaster of waste lead-acid storage batteries according to claim 1, wherein the precipitant is one of carbon dioxide, sulfur dioxide and sulfur trioxide.
4. The process for preparing lead oxide based on waste lead-acid storage battery lead plaster according to claim 1, characterized in that the lead catching agent is prepared by the following steps:
a1: adding diethanolamine and triethylamine into a three-neck flask, dropwise adding a p-toluenesulfonyl chloride solution a under the condition of the temperature of 0-5 ℃ while stirring, heating to 20-25 ℃ after dropwise adding, continuously stirring for reaction for 4-6h, adding a reaction product into ice water after the reaction is finished, separating an organic phase, washing with dilute hydrochloric acid and distilled water for 2-3 times, drying with anhydrous magnesium sulfate, filtering, and carrying out rotary evaporation on the filtrate to obtain an intermediate 1;
a2: adding diethylenetriamine into a three-neck flask, dropwise adding a p-toluenesulfonyl chloride solution b and an anhydrous potassium carbonate solution while stirring at the temperature of 0-5 ℃, continuously stirring and reacting for 2-4 hours under the condition of heating to 20-25 ℃ after dropwise adding, adding a reaction product into ice water after the reaction is finished, filtering, adding a filter cake into anhydrous ethanol for recrystallization, and drying to obtain an intermediate 2;
a3: adding the intermediate 1, the intermediate 2, anhydrous potassium carbonate and N, N-dimethylformamide into a three-neck flask, stirring at a constant temperature of 100-105 ℃ for reaction for 2-3h, cooling a reaction product to room temperature after the reaction is finished, filtering, performing rotary evaporation on a filtrate, dropwise adding anhydrous methanol, heating to reflux reaction, stopping the reaction, cooling the reaction product to room temperature, filtering, washing a filter cake with an ethanol solution, and then placing in a vacuum drying oven to dry to constant weight to obtain an intermediate 3;
a4: adding concentrated sulfuric acid of the intermediates 3 and 2/3 into a three-neck flask, stirring and reacting at a constant temperature of 100-105 ℃ for 40-50h, cooling the reaction product in an ice water bath after the reaction is finished, adding absolute ethyl alcohol while stirring to separate out crystals, performing vacuum filtration, adding a filter cake into deionized water, stirring at a constant temperature of 90-93 ℃ until the solution is clear, cooling to 75-80 ℃, adding activated carbon, performing heating reflux reaction for 20-40min, filtering, adding the rest 1/3 concentrated sulfuric acid into the filtrate, cooling for crystallization, filtering, and drying the filter cake in a vacuum drying oven to constant weight to obtain an intermediate 4;
a5: adding the intermediate 4 and acetonitrile into a three-neck flask, stirring for 10-20min at room temperature, then dropwise adding a bromoacetic acid tert-butyl ester solution while stirring, continuously stirring for reaction for 20-30h after dropwise adding is finished, carrying out rotary evaporation on a reaction product after the reaction is finished, then adding deionized water, adjusting the pH of a reaction system to 3 by using a hydrochloric acid solution, then extracting for 2-3 times by using anhydrous ether, collecting a water phase, adjusting the pH to 8 by using a sodium hydroxide solution, adding dichloromethane for extraction for 2-3 times, drying the dichloromethane of an extraction liquid by using anhydrous sodium sulfate, filtering, and carrying out rotary evaporation to obtain an intermediate 5;
a6: adding tetrahydrofuran of the intermediates 5 and 1/2 into a three-neck flask, stirring for 10-20min at the temperature of 50-70 ℃, then dropwise adding epoxy chloropropane while stirring, continuously stirring for reacting for 6-10h after dropwise adding is finished, washing the reaction product for 2-3 times by using acetone after the reaction is finished, then adding the reaction product and the rest 1/2 of tetrahydrofuran into the three-neck flask while stirring, dropwise adding a sodium hydroxide solution while stirring, continuously stirring for reacting for 2-3h after dropwise adding is finished, adjusting the pH of the reaction product to 7 by using a hydrochloric acid solution after the reaction is finished, filtering, and rotatably evaporating the filtrate to obtain an intermediate 6;
a7: adding the intermediate 6 and tetrahydrofuran into a three-neck flask, stirring for 10-20min at room temperature, then dropwise adding diallylamine while stirring, heating to 50-70 ℃ after dropwise adding, continuing stirring for reaction for 6-10h, and performing rotary evaporation on a reaction product after the reaction is finished to obtain an intermediate 7;
a8: adding the intermediate 7 and trifluoroacetic acid into a flask, stirring and reacting for 3-4h at room temperature, and performing rotary evaporation on a reaction product after the reaction is finished to obtain an intermediate 8;
a9: and adding the intermediate 8, deionized water and azodiisobutyl imidazoline hydrochloride into a three-neck flask, introducing nitrogen for protection, stirring and reacting for 8-10 hours at the temperature of 60-75 ℃, and after the reaction is finished, placing a reaction product in a vacuum drying oven to be dried to constant weight to obtain the lead capture agent.
5. The process for preparing lead oxide based on lead plaster of waste lead-acid storage batteries according to claim 4, wherein the dosage ratio of the solution of diethanolamine, triethylamine and p-toluenesulfonyl chloride in the step A1 is 0.1 mol: 50mL of: 150mL, the p-toluenesulfonyl chloride solution a is p-toluenesulfonyl chloride according to the molar ratio of 0.11 mol: 50mL of solution formed by dissolving in dichloromethane, wherein the mass fraction of the dilute hydrochloric acid is 10%; the dosage ratio of the diethylenetriamine, the p-toluenesulfonyl chloride solution b and the anhydrous potassium carbonate solution in the step A2 is 0.1 mol: 150mL of: 100mL, the p-toluenesulfonyl chloride solution b is p-toluenesulfonyl chloride according to the molar ratio of 0.11 mol: 50mL of a solution formed by dissolving in acetone, the anhydrous potassium carbonate solution being anhydrous potassium carbonate in a weight ratio of 27.8 g: 50mL of a solution obtained by dissolving the above components in distilled water.
6. The process for preparing lead oxide based on lead plaster of waste lead-acid storage batteries according to claim 4, wherein the dosage ratio of the intermediate 1, the intermediate 2, anhydrous potassium carbonate and N, N-dimethylformamide in the step A3 is 0.02 mol: 0.02 mol: 0.06 mol: 100mL, wherein the mass fraction of the ethanol solution is 90-95%; the dosage ratio of the intermediate 3, concentrated sulfuric acid, absolute ethyl alcohol, deionized water and activated carbon in the step A4 is 30 g: 100mL of: 200mL of: 80mL of: 4g, wherein the mass fraction of the concentrated sulfuric acid is 97%.
7. The process for preparing lead oxide based on waste lead-acid storage battery lead plaster according to claim 4, characterized in that the dosage ratio of the intermediate 4, acetonitrile, bromoacetic acid tert-butyl ester solution and deionized water in the step A5 is 7.5 g: 100mL of: 100mL of: 100mL, wherein the tert-butyl bromoacetate solution is tert-butyl bromoacetate according to the weight ratio of 8.5 g: 20mL of solution formed by dissolving in acetonitrile, wherein the molar concentrations of the hydrochloric acid solution and the sodium hydroxide solution are both 1 mol/L; the dosage ratio of the intermediate 5, tetrahydrofuran, epichlorohydrin and sodium hydroxide solution in the step A6 is 0.08 mol: 50mL of: 0.1 mol: 120mL, and the molar concentrations of the sodium hydroxide solution and the hydrochloric acid solution are both 1 mol/L.
8. The process for preparing lead oxide based on lead plaster of waste lead-acid storage batteries according to claim 4, characterized in that the ratio of the intermediate 6, tetrahydrofuran and diallylamine in step A7 is 0.1 mol: 50mL of: 0.1 mol; the amount ratio of the intermediate 7 to trifluoroacetic acid in step A8 was 17.45 mmol: 100 mL; the dosage ratio of the intermediate 8, the deionized water and the azobisisobutylimidazoline hydrochloride in the step A9 is 15 g: 100mL of: 0.3 g.
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