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WO2025003748A1 - Procédé de recyclage de déchets de séparateur de batteries au plomb-acide sur la base d'une purification par un solvant et un four de pyrolyse - Google Patents

Procédé de recyclage de déchets de séparateur de batteries au plomb-acide sur la base d'une purification par un solvant et un four de pyrolyse Download PDF

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Publication number
WO2025003748A1
WO2025003748A1 PCT/IB2023/058552 IB2023058552W WO2025003748A1 WO 2025003748 A1 WO2025003748 A1 WO 2025003748A1 IB 2023058552 W IB2023058552 W IB 2023058552W WO 2025003748 A1 WO2025003748 A1 WO 2025003748A1
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WO
WIPO (PCT)
Prior art keywords
purification
nanosilica
lead
separator
stage
Prior art date
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.)
Pending
Application number
PCT/IB2023/058552
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English (en)
Inventor
Masoud Panahi
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Saya Petro Polymer Syca
Original Assignee
Saya Petro Polymer Syca
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Saya Petro Polymer Syca filed Critical Saya Petro Polymer Syca
Publication of WO2025003748A1 publication Critical patent/WO2025003748A1/fr
Anticipated expiration legal-status Critical
Pending legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B33/00—Silicon; Compounds thereof
    • C01B33/113—Silicon oxides; Hydrates thereof
    • C01B33/12—Silica; Hydrates thereof, e.g. lepidoic silicic acid
    • C01B33/18—Preparation of finely divided silica neither in sol nor in gel form; After-treatment thereof
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
    • B09B—DISPOSAL OF SOLID WASTE NOT OTHERWISE PROVIDED FOR
    • B09B3/00—Destroying solid waste or transforming solid waste into something useful or harmless
    • B09B3/30—Destroying solid waste or transforming solid waste into something useful or harmless involving mechanical treatment
    • B09B3/35—Shredding, crushing or cutting
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
    • B09B—DISPOSAL OF SOLID WASTE NOT OTHERWISE PROVIDED FOR
    • B09B3/00—Destroying solid waste or transforming solid waste into something useful or harmless
    • B09B3/40—Destroying solid waste or transforming solid waste into something useful or harmless involving thermal treatment, e.g. evaporation
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
    • B09B—DISPOSAL OF SOLID WASTE NOT OTHERWISE PROVIDED FOR
    • B09B2101/00—Type of solid waste
    • B09B2101/15—Electronic waste
    • B09B2101/16—Batteries
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/80—Compositional purity
    • 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

Definitions

  • the technical field of this invention relates to the new process for recycling the wastes and residues of the separator plates from the old and worn-out lead-acid battery based on the purification method using solvent and pyrolysis, which allows the conversion of the lead-acid battery separator waste into nanosilica with a purity of more than 98%.
  • Chambers et al in 2017, filed a patent entitled “Batteries, separators, components, and compositions with heavy metal removal capability and related methods”.
  • This patent is related to the formulation of PIMS mineral material (containing apatite) as a replacement for silica filler and heavy metals in lead acid battery separators.
  • the purpose of the above invention is to improve the properties of separator plates for installation in lead-acid batteries, while the purpose of the new invention is to recycle the silica contained in waste separators of lead-acid batteries and produce nanosilica with a purity of more than 98%.
  • a patent entitled "Separating and melting system and method for waste lead grid in waste lead acid storage battery recycling” was filed by Yang Chunming in 2022, which it is related to providing a device and method for separating lead from lead-acid batteries.
  • the device components include a dust remover, a flue gas duct, a lead-containing liquid mixer, a lead grid circulation box, a lead grid barrier plate, an ash discharge pipe, an automatic ash collection machine, and a lead ash conveyor, a copper terminal separator, a lead mud tank, a lead mud stirrer, a copper parts collection box, a circulating water treatment device, a melting device, a spiral feeder and a drying drum.
  • lead is separated from the liquid waste of acid-lead batteries, while the purpose of the new invention is to provide a method to recycle battery separator waste and produce nanosilica with a purity of more than 98%.
  • Lead-acid batteries dominate a major part of the global battery market and have a short service life such that after reaching the end of their life cycle, they wear out and become unusable. These batteries are considered special waste, and because of the high level of poisoning nature and the threat to the health of humans and the environment, the recycling of lead-acid batteries is obligatory. At present, lead plates are recycled again and applied in the production of new batteries.
  • separator is a polymer membrane that is placed between the anode with a positive charge and the cathode with a negative charge to prevent an electrical short circuit.
  • separator is a polymer membrane that is placed between the anode with a positive charge and the cathode with a negative charge to prevent an electrical short circuit.
  • These plates are made of polymer materials that have mesoporous pores and micro silica is usually used to make them (1 ).
  • separator plates are collected as waste and deposited in the environment. At present, there is no method for recycling these plates, as these plate due to having lead, sulfur, and iron cause environmental pollution. In the past years, ignoring the battery separators and improper disposal has caused environmental pollution on the one hand and the loss of a valuable source of silica on the other hand.
  • Separator plates of lead-acid batteries are produced of polyethylene, DOP oil, and micro-silica, which contains 55% of micro-silica. This invention aims to provide a method in order to recycle separator waste of lead-acid batteries, extract separator silica, and produce high-purity nanosilica.
  • the main issues are the environmental pollution caused by the improper disposal of PE battery separators from lead-acid batteries, as well as the lack of a suitable and cost-effective method to recycle such lead-acid battery wastes.
  • the first stage of purification In this stage, the metal impurities in the polyethylene separator, including lead oxides, iron oxides, and calcium oxide, are reduced from 9-6 to 2-3% with the abrasion mechanism. At this stage, the ground plates enter a tank with a mixer, which contains sand and water. In this device, a process similar to the sandblasting process is performed in the presence of water solvent for 1 hour, which reduces the mentioned oxide impurities to about 2-3%.
  • the second stage of purification in this stage, as one of the main stages of recycling separator plates and producing nanosilica, metal impurities including lead oxide, sulfur compounds, manganese, and iron oxides present in polyethylene separator plates from 2-3% is reduced to less than 0.2%.
  • metal impurities including lead oxide, sulfur compounds, manganese, and iron oxides present in polyethylene separator plates from 2-3% is reduced to less than 0.2%.
  • nitric acid, water, citric acid solvent in a ratio of 1 :2:1 is poured into the tank, and after the solution becomes uniform, the crushed plates are poured into the flat tank and for 4 to 5 hours are stirred inside the tank and these solvents reduce the interaction between metal impurities and the polymer and silica substrate, and on the other hand, by increasing the solubility of these impurities, it separates the impurities from silica and polymer.
  • salt is added to the flat tank in the amount of 10% of the weight of the solvents, and after 1 hour, the crushed parts are removed from the tank
  • the third stage of purification is also one of the main stages of separator recycling, in which the polymer is separated from silica and the microsilica in the separator waste is converted into nanosilica.
  • the crushed pieces are put inside the pyrolysis furnace and placed under a temperature of 800 to 900 C for 5 hours so that the polymers are burned and separated from the microsilica in the separators in the form of soot, and simultaneously, the size of the particles is reduced from micro to nanoscale.
  • nitrogen gas and argon gas are injected into the furnace with a ratio of 2:1 to adjust the atmosphere of the furnace, which prevents the sintering and agglomeration process of nanoparticles due to superficial melting and maintains the size of the particles in the nano-scale.
  • oxygen gas is blown into the furnace to remove soot and polymer impurities in a controlled manner from inside the furnace, because soot resulting from burning polymer materials inside the furnace react with the nanosilica particles and causes color change and impurity in the produced nanosilica.
  • the separator of lead-acid batteries which is currently disposed of as unused waste in nature, is converted into a valuable material of nanosilica, which has many applications in various industries, such as rubber, plastic, construction materials, pharmaceuticals, catalysts, fillers in composite materials, etc.
  • nanosilica The most important parameter in the technical specifications of nanosilica is its purity, particle size, and specific surface area, and the most final properties of nanosilica are related to these three parameters and according to the results of analyzes and microscopic images, the nanosilica resulted from this process has a purity of more than 98%, size of 25-30 nm and specific surface area of 100-120 m2/g.
  • One of the innovations of the claimed invention is to provide a new method for recycling separator waste of lead-acid batteries and producing nanosilica with a purity of over 98%, while currently lead-acid battery separators after separation are deposited in nature as unused waste.
  • Another innovation is to present a purification method with the abrasion mechanism and using sand, which, in combination with water as a solvent, removes the metal impurities of the separator plates and impurities include lead oxides, iron oxides, and calcium oxides. It reduces impurities from 6-9 % to 2-3% so that the simultaneous use of sand as an abrasive method along with the solvent to increase the speed of separation of impurities is one of the innovations of this stage that was not observed in the prior art.
  • the other innovation of the new method is presenting a purification process and using nitric acid, water, and citric acid solvents to reduce the metal impurity percentage from 2-3 to below 0.2%, as well as using salt to separate surface impurities.
  • One of the other innovations of the new invention is the addition of oxygen gas to the pyrolysis furnace to quickly remove soot from the furnace, as the soot resulting from the burning of polymer materials reacts with nanosilica particles and causes color change and impurities in the produced nanosilica and should be taken out of the furnace quickly, while in the prior art, oxygen is used as fuel and to supply the temperature of the burner, which is very dangerous and sensitive.
  • Fig 1 Illustrates lead-acid battery
  • Fig 2 Production process of nanosilica from lead-acid battery waste
  • Fig 4 IPC-OES analysis sheet.
  • Figure 1 this figure illustrates a schematic of the different parts of the lead- acid battery so that the separator is embedded between the positive and negative plates of a polymer membrane and is placed between the anode with a positive charge and the cathode with a negative charge to prevent electrical short circuit.
  • Terminal (1) Fill Cap (2), Strap (3), Negative (4), Separator (5), Positive plate (6), Glass mat (7), Battery enclosure (8), Minimum liquid fill line (9), Maximum liquid fill line (10).
  • FIG 2 this figure shows the new production process of nanosilica from lead-acid battery waste. This process involves the stages of washing the plates with water to separate the dust, crushing the plates with a grinder, the first stage of purification using water and sand solvent, second stage of purification by nitric acid solvent, water, citric acid, and salt, the stage of drying plates in a continuous dryer, the process of separating micro-silica from polymer and converting the size of particles from micro to nano scale inside the pyrolysis furnace and finally crushing using a hammer mill.
  • part a is related to the image of nanosilica extracted from separator plates
  • part b is related to the FESEM test from the scanning electron microscope
  • parts c and d are related to the results of the TEM test, which shows that the size of the extracted silica particles are 25-30 nm, implying that the silica particles are nanoparticles.
  • Table 1 presents the technical specifications of nanosilica extracted from the wastes of lead-acid battery separator plates by the new method.
  • separator wastes from lead-acid batteries are purchased from battery manufacturing and recycling companies.
  • the plates are washed with water to remove dust.
  • the plates are crushed into smaller sizes and poured into a tank with a mixer containing sand and water, so that a percentage of the metal impurities of the separator plates are dissolved in the solvent by combining the dissolvation and abrasion methods.
  • the plates are placed into a tank with another mixer to reduce their metal impurities below 0.2% with nitric acid, water, citric acid, and salt.
  • the plates After drying the crushed plates in a continuous dryer, the plates are placed into the pyrolysis furnace to be separated from the polymer at a temperature of 800 to 900 C for 6 hours exposed to argon, nitrogen, and oxygen gases, and the size of the silica particles is reduced from micro to nanoscale and in the last step, nanosilica is converted into powder using a hammer mill and finally, it is packed in 10 kg bags.
  • Nanosilica produced in this process is used in many fields, including rubber, plastic, construction materials, pharmaceuticals, catalysts, fillers in composite materials, etc. Some of the uses of this product are as follows:
  • Rubber industry In this industry, nanosilica is used as a filler, which eliminates the environmental problems caused by soot and also improves the physical and mechanical properties of rubber.
  • Nanosilicas are placed between hydrated calcium silicate gel particles and fill the gel particles due to their high fineness and good adhesion of the particles. This improves the integrity of hydrated calcium gel and increases the durability of concrete.
  • Nanosilica in the three forms of powder, gel, and colloid are utilized in the paint industry as a flatting agent, and concentrator and enhances environmental resistance and wear properties.
  • Plastic industry They are used as fillers to improve the quality of the surface and increase the strength and dimensional stability of the product.

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  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Environmental & Geological Engineering (AREA)
  • Organic Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Processing Of Solid Wastes (AREA)

Abstract

La plaque séparatrice de batteries au plomb-acide est constituée de polyéthylène, d'huile DOP et de micro-silice, et actuellement, les séparateurs sont déposés dans la nature sous forme de déchets après séparation des batteries usées qui à leur tour provoquent une pollution environnementale due à l'existence de polyéthylène, de plomb et de fer. Dans la présente invention, un nouveau procédé de recyclage de ces déchets basé sur la purification par un solvant et un four de pyrolyse est présenté, qui conduit à la production de nanosilice avec une pureté supérieure à 98%. Dans les première et deuxième étapes de purification utilisant des solvants acide nitrique, eau, acide citrique et sels, les impuretés métalliques du séparateur sont réduites de 6-9% à moins de 0,2% et dans la troisième étape de purification dans le four de pyrolyse, les impuretés polymères sont séparées de la micro-silice sous la forme de suie, et la nanosilice est retirée du four.
PCT/IB2023/058552 2023-06-25 2023-08-30 Procédé de recyclage de déchets de séparateur de batteries au plomb-acide sur la base d'une purification par un solvant et un four de pyrolyse Pending WO2025003748A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
IR14023002226 2023-06-25
IR140250140003002226 2023-06-25

Publications (1)

Publication Number Publication Date
WO2025003748A1 true WO2025003748A1 (fr) 2025-01-02

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PCT/IB2023/058552 Pending WO2025003748A1 (fr) 2023-06-25 2023-08-30 Procédé de recyclage de déchets de séparateur de batteries au plomb-acide sur la base d'une purification par un solvant et un four de pyrolyse

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Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20070280871A1 (en) * 2004-02-11 2007-12-06 Kandy S.A. Process For Recovery Of The Silica Present In The Separators Between The Elements Of Lead-Acid Batteries

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20070280871A1 (en) * 2004-02-11 2007-12-06 Kandy S.A. Process For Recovery Of The Silica Present In The Separators Between The Elements Of Lead-Acid Batteries

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
PIRCHERAGHI G.; NOWROUZI M.; NEMATI SH.: "Fabrication of polyethylene separator for lead-acid batteries from waste and recycled silica and investigation of its performance", JOURNAL OF CLEANER PRODUCTION, ELSEVIER, AMSTERDAM, NL, vol. 250, 3 December 2019 (2019-12-03), AMSTERDAM, NL , XP086015454, ISSN: 0959-6526, DOI: 10.1016/j.jclepro.2019.119535 *
SHOJAEI MOHAMMAD REZA, PIRCHERAGHI GHOLAMREZA, ALINOORI AMIR: "Sustainable SBR/silica nanocomposites prepared using high-quality recycled nanosilica from lead-acid battery separators", JOURNAL OF CLEANER PRODUCTION, ELSEVIER, AMSTERDAM, NL, vol. 370, 1 October 2022 (2022-10-01), AMSTERDAM, NL , pages 133316, XP093257722, ISSN: 0959-6526, DOI: 10.1016/j.jclepro.2022.133316 *

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