CN110587856A - Separation method of solar back panel film made of fluorine-containing material - Google Patents
Separation method of solar back panel film made of fluorine-containing material Download PDFInfo
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- CN110587856A CN110587856A CN201910885059.6A CN201910885059A CN110587856A CN 110587856 A CN110587856 A CN 110587856A CN 201910885059 A CN201910885059 A CN 201910885059A CN 110587856 A CN110587856 A CN 110587856A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
- B29B17/00—Recovery of plastics or other constituents of waste material containing plastics
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
- B29B17/00—Recovery of plastics or other constituents of waste material containing plastics
- B29B17/02—Separating plastics from other materials
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
- B29B17/00—Recovery of plastics or other constituents of waste material containing plastics
- B29B2017/001—Pretreating the materials before recovery
- B29B2017/0015—Washing, rinsing
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
- B29B17/00—Recovery of plastics or other constituents of waste material containing plastics
- B29B17/02—Separating plastics from other materials
- B29B2017/0213—Specific separating techniques
- B29B2017/0217—Mechanical separating techniques; devices therefor
- B29B2017/0237—Mechanical separating techniques; devices therefor using density difference
- B29B2017/0244—Mechanical separating techniques; devices therefor using density difference in liquids
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/62—Plastics recycling; Rubber recycling
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- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Mechanical Engineering (AREA)
- Separation, Recovery Or Treatment Of Waste Materials Containing Plastics (AREA)
Abstract
The invention discloses a separation method of a solar back plate membrane containing a fluorine material, which comprises the following steps of treating a separation liquid consisting of 20-500 parts of water, 1-50 parts of alkali, 0.1-5 parts of penetrating agent and 1-60 parts of organic solvent on the solar back plate material at 30-100 ℃ for 0.1-72 hours, then cleaning the separated back plate membrane with water, selecting an inorganic salt solution as a centrifugal separation liquid, and adjusting the density of the centrifugal separation liquid at 5 ~ 80 ℃ to be 1.2 ~ 2.0.0 g/cm3(ii) a And adding the obtained mixed membrane and the obtained centrifugal separation liquid into a centrifugal machine, centrifuging, standing, and performing layering separation to obtain the fluorine-containing material film and the PET film. The invention adopts the method that in high inorganic salt solution, due to different densities, the water floats on the centrifugal liquid surface and sinks to the bottom of the centrifugal liquid during centrifugation, thereby achieving the purpose of separation, the separation equipment is simple and commonly used, and the invention has the advantages of simple process, low cost of raw materials and manpower, no pollution and the like.
Description
Technical Field
The invention relates to the field of recycling of high polymer materials, in particular to a method for separating and recycling a solar back panel film made of a fluorine-containing material.
Background
Most of the photovoltaic modules have the service life of 20-25 years, and with the rapid development of the photovoltaic industry in China, the recovery of the photovoltaic modules becomes a serious problem for limiting the survival and development of the photovoltaic industry in three to five years. The solar back plate film is an important product after splitting of a photovoltaic module, is positioned on the back of a solar panel, plays a role in protecting and supporting a cell piece, and is required to have reliable insulativity, water resistance and ageing resistance. Most of back plate films have a three-layer structure (PVDF/PET/PVDF), the outer layer is PVDF and has good environmental erosion resistance, the middle layer is a PET polyester film and has good insulating property, and the inner layer and the outer layer are bonded by adhesives such as EVA and the like. The existing treatment is generally to generate electricity or fill by burning, and because the chemical property of the fluorine-containing compound is very stable, the fluorine-containing compound can not be decomposed only by filling, so that a large amount of land resources are occupied; and the incineration can generate highly toxic hydrogen fluoride gas. In addition, the fluorine-containing polymer material has a great economic value, and if the fluorine-containing polymer material is only buried or burned, the fluorine-containing polymer material can cause great waste of resources.
The Chinese invention patent (Zuodongxian, et al, a recovery method of a solar backboard material, 201710343354. X) discloses a separation method of a solar backboard material, which can successfully peel a fluorine-containing material and a PET film layer which are bonded together with the solar backboard material by using separation liquids with different surface activities based on the difference of different plastic interface properties. However, the peeled fluorine-containing material and the PET film are mixed together, and due to the density and the proximity thereof, the fluorine-containing material and the PET film cannot be effectively separated by common technologies such as air blowing screening, infrared recognition separation and cyclone separation. Therefore, how to easily and effectively separate the peeled mixed film is a key for recycling and resource utilization of the solar back sheet film.
Disclosure of Invention
The invention aims to provide a method for separating and recovering a solar back plate film made of a fluorine-containing material.
In order to achieve the purpose, the invention adopts the following technical scheme:
a method of separating a solar back sheet film, comprising the steps of:
the separation method of the solar back panel membrane containing the fluorine material comprises the following steps of using 100 parts of solar back panel material, 20-500 parts of water, 1-50 parts of alkali, 0.1-5 parts of penetrating agent, 1-60 parts of organic solvent and 30 ~ 2000 parts of centrifugal separation liquid according to the weight part;
the method comprises the following steps:
(1) treating 100 parts of solar backboard material by using a separation solution consisting of 20-500 parts of water, 1-50 parts of alkali, 0.1-5 parts of penetrating agent and 1-60 parts of organic solvent at 30-100 ℃ for 0.1-72 hours, and then cleaning the separated backboard membrane by using water;
(2) selecting inorganic salt solution as centrifugate, and adjusting the density of centrifugate at 5 ~ 80 deg.C to 1.2 ~ 2.0.0 g/cm3；
(3) Adding the mixed membrane obtained in the step (1) and 30 ~ 2000 parts of the centrifugal separation liquid obtained in the step (2) into a centrifugal machine, centrifuging for 0.1 ~ 60 minutes at 10 ~ 20000 rpm, standing for 0.1 ~ 100 hours, and then carrying out layering separation.
The alkali is one or a combination of more of sodium hydroxide, potassium hydroxide, calcium hydroxide and ammonia water; the penetrating agent is one or a combination of a plurality of nonionic surfactants, anionic surfactants and fluorine surfactants. The non-ionic surfactant is one or a combination of more of JFC-1, JFC-E and JFC-2. The anionic surfactant is one or a combination of more of a rapid penetrant T, an alkali-resistant penetrant OEP-70, an alkali-resistant penetrant AEP and a high-temperature penetrant JFC-M. The fluorine surfactant is one or a combination of more of a sodium perfluorooctanoate surfactant, a sodium perfluorooctyl sulfonate surfactant, an ethoxy fluorocarbon surfactant and a fluorine-containing polyoxyethylene ether surfactant. The organic solvent is one or a combination of several of methanol, ethanol, N-methyl pyrrolidone, ethylene glycol phenyl ether, N-dimethylformamide, dimethyl sulfoxide, hexafluoroisopropanol, acetone, benzyl alcohol, toluene and ethyl acetate.
The inorganic salt is BaCl2、CaCl2、KCl、MgCl、NaCl、Na2SO4、MgSO4、CaSO4、NaNO3、Mg(NO3)2、KNO3Or Ca (NO)3)2One or a combination of several of them.
The invention has the following remarkable advantages:
(1) compared with the traditional centrifugal separation technology, the invention provides a technology for effectively separating base materials with different densities by adjusting the density of the inorganic salt water solution, and the separation efficiency can reach 100%;
(2) the separation equipment is simple and commonly used, and has the advantages of simple process, low cost of raw materials and manpower, no pollution and the like. The separation treatment method disclosed by the invention has important application value for the coming climax of solar component recycling.
Drawings
FIG. 1 shows an infrared spectrum of a thin film settled to the bottom of the centrifugate;
FIG. 2 is an infrared spectrum of a thin film floating on the surface of the centrifugate.
Detailed Description
In order to further explain the technical solution of the present invention, the present invention is explained in detail by the following specific examples.
Example 1
(1) Treating 100 parts of solar backboard material by using a separation solution consisting of 20 parts of water, 50 parts of sodium hydroxide, 5 parts of JFC-1 and 60 parts of acetone at 30 ℃ for 0.1 hour, and then cleaning the separated backboard membrane by using water;
(2) selection of BaCl2The aqueous solution of (2) was used as a centrifuged liquid, and the density of the centrifuged liquid at 5 ℃ was adjusted to 1.2 g/cm3；
(3) And (3) adding the mixed membrane obtained in the step (1) and 200 parts of the centrifugal separation liquid obtained in the step (2) into a centrifugal machine, centrifuging for 0.1 minute at 10 revolutions per minute, standing for 0.1 hour, and then carrying out layer separation.
The IR spectrum of the separated film is shown in FIGS. 1 and 2. FIG. 1 is an infrared spectrum of the film settled to the bottom of the centrifugate, and as can be seen from FIG. 1, the film has a wave number of 2954 cm-1If a characteristic absorption peak exists, C-H stretching vibration exists; at 1405 cm-1Has a characteristic absorption peak at 1405 cm-1If there is a characteristic absorption peak, it indicates that there is-CH2A deformation vibration absorption peak of (1); at a wave number of 1155 cm-1When a characteristic absorption peak is present, it indicates that-CF is present2The stretching vibration of (2) exists. So the backsheet material can be judged to be PVDF;
FIG. 2 is an infrared spectrum of a thin film floating on the surface of the centrifugate, as seen from FIG. 2, at a wave number of 1716 cm-1If a characteristic absorption peak exists, the existence of stretching vibration of ester carbonyl C = O can be indicated; at wave number of 1300-1000 cm-1If a characteristic absorption peak appears, C-O stretching vibration is indicated, and the compound is an ester compound; at a wave number of 2968 cm-1If a characteristic absorption peak appears, C-H stretching vibration is indicated; and at 800--1The absorption peak indicates that the film material of the layer is polyethylene terephthalate (PET).
Example 2
(1) Treating 100 parts of solar backboard material by using a separation solution consisting of 500 parts of water, 1 part of potassium hydroxide, 0.1 part of JFC-E and 10 parts of ethanol at 100 ℃ for 72 hours, and then cleaning the separated backboard membrane by using water;
(2) selecting CaCl2High salt water solution is used as centrifugate, and the density of the centrifugate at 80 deg.C is adjusted to 2.0g/cm3；
(3) Adding the mixed membrane obtained in the step (1) and 30 parts of the centrifugal separation liquid obtained in the step (2) into a centrifugal machine, centrifuging for 60 minutes at 20000 revolutions per minute, standing for 100 hours, and then carrying out layering separation.
Example 3
(1) Treating 100 parts of solar backboard material by using a separation solution consisting of 100 parts of water, 20 parts of calcium hydroxide, 1 part of JFC-2 and 20 parts of methanol at 50 ℃ for 10 hours, and then cleaning the separated backboard membrane by using water;
(2) selecting KCl high-salt water solution as centrifugate, and adjusting the density of centrifugate at 20 deg.C to 1.5g/cm3；
(3) Adding the mixed membrane obtained in the step (1) and 2000 parts of the centrifugal separation liquid obtained in the step (2) into a centrifugal machine, centrifuging for 5 minutes at 10000 r/min, standing for 0.5, and performing layered separation.
Example 4
(1) Treating 100 parts of solar backboard material by using a separation solution consisting of 100 parts of water, 20 parts of ammonia water, 1 part of rapid penetrating agent T, 0.5 part of fluorine-containing polyoxyethylene ether surfactant and 20 parts of N-methyl pyrrolidone at 50 ℃ for 10 hours, and then cleaning the separated backboard membrane by using water;
(2) selecting KCl, NaCl and Na2SO4The high salt solution of (2) was used as a centrifuged liquid, and the centrifuged liquid was adjusted to have a density of 1.5g/cm at 8 deg.C3；
(3) Adding the mixed membrane obtained in the step (1) and 300 parts of the centrifugal separation liquid obtained in the step (2) into a centrifugal machine, centrifuging for 20 minutes at 7000 r/min, standing for 20 hours, and then carrying out layer separation.
Example 5
(1) Treating 100 parts of solar backboard material by using a separation solution consisting of 100 parts of water, 20 parts of ammonia water, 5 parts of sodium hydroxide, 1 part of alkali-resistant penetrating agent OEP-70 and 20 parts of ethylene glycol phenyl ether at 70 ℃ for 10 hours, and then washing the separated backboard membrane with water;
(2) selection of MgCl2The high-salt aqueous solution of (2) was used as a centrifuged liquid, and the centrifuged liquid was adjusted to have a density of 1.8 g/cm at 55 DEG C3；
(3) Adding the mixed membrane obtained in the step (1) and 400 parts of the centrifugal separation liquid obtained in the step (2) into a centrifugal machine, centrifuging for 20 minutes at 5000 revolutions per minute, standing for 1 hour, and performing layered separation.
Example 6
(1) Treating 100 parts of solar backboard material by using a separation solution consisting of 100 parts of water, 20 parts of ammonia water, 5 parts of sodium hydroxide, 1 part of alkali-resistant penetrating agent OEP-70, 1 part of alkali-resistant penetrating agent AEP, 20 parts of ethylene glycol phenyl ether and 10 parts of N, N-dimethylformamide at 60 ℃ for 10 hours, and then cleaning the separated backboard membrane by using water;
(2) selection of MgCl2And BaCl2The high-salt aqueous solution of (2) was used as a centrifuged liquid, and the centrifuged liquid was adjusted to have a density of 1.6g/cm at 45 ℃3；
(3) Adding the mixed membrane obtained in the step (1) and 100 parts of the centrifugal separation liquid obtained in the step (2) into a centrifugal machine, centrifuging for 15 minutes at 8000 rpm, standing for 5 hours, and performing layering separation.
Example 7
(1) Treating 100 parts of solar backboard material by using a separation solution consisting of 100 parts of water, 20 parts of sodium hydroxide, 1 part of alkali-resistant penetrating agent AEP, 1 part of high-temperature penetrating agent JFC-M, 20 parts of dimethyl sulfoxide and 10 parts of hexafluoroisopropanol at 60 ℃ for 10 hours, and then cleaning the separated backboard membrane by using water;
(2) selecting CaCl2、MgSO4And CaSO4The high-salt aqueous solution of (2) was used as a centrifuged liquid, and the density of the centrifuged liquid at 30 ℃ was adjusted to 1.6g/cm3；
(3) Adding the mixed membrane obtained in the step (1) and 50 parts of the centrifuged liquid obtained in the step (2) into a centrifuge, centrifuging for 20 minutes at 15000 rpm, standing for 20 hours, and then carrying out layer separation.
Example 8
(1) Treating 100 parts of solar backboard material by using a separation solution consisting of 100 parts of water, 20 parts of sodium hydroxide, 1 part of sodium perfluorooctanoate, 1 part of sodium perfluorooctyl sulfonate, 5 parts of benzyl alcohol and 10 parts of toluene as an organic solvent at 60 ℃ for 10 hours, and then cleaning the separated backboard membrane by using water;
(2) selection of NaNO3And Mg (NO)3)2The high-salt aqueous solution of (2) was used as a centrifuged liquid, and the density of the centrifuged liquid at 60 ℃ was adjusted to 1.7g/cm3；
(3) Adding the mixed membrane obtained in the step (1) and 150 parts of the centrifugal separation liquid obtained in the step (2) into a centrifugal machine, centrifuging for 30 minutes at 10000 rpm, standing for 15 hours, and then carrying out layered separation.
Example 9
(1) Treating 100 parts of solar backboard material by using a separation solution consisting of 100 parts of water, 20 parts of sodium hydroxide, 1 part of ethoxy fluorocarbon surfactant, 5 parts of ethyl acetate and 10 parts of toluene at 60 ℃ for 10 hours, and then cleaning the separated backboard membrane by using water;
(2) selecting KNO3And Ca (NO)3)2The high-salt aqueous solution of (2) is used as a centrifuged liquid, and the density of the centrifuged liquid at 10 ℃ is adjusted to 1.5g/cm3；
(3) Adding the mixed membrane obtained in the step (1) and 250 parts of the centrifugal separation liquid obtained in the step (2) into a centrifugal machine, centrifuging for 50 minutes at 2000 rpm, standing for 1 hour, and then carrying out layer separation.
The above embodiments are not intended to limit the form and style of the present invention, and any suitable changes or modifications made by those skilled in the art should be considered as not departing from the scope of the present invention.
Claims (8)
1. The separation method of the solar back panel membrane containing the fluorine material is characterized in that the raw materials used in the separation method comprise, by weight, 100 parts of the solar back panel material, 20-500 parts of water, 1-50 parts of alkali, 0.1-5 parts of penetrating agent, 1-60 parts of organic solvent and 30 ~ 2000 parts of centrifugal separation liquid;
the method comprises the following steps:
(1) treating 100 parts of solar backboard material by using a separation solution consisting of 20-500 parts of water, 1-50 parts of alkali, 0.1-5 parts of penetrating agent and 1-60 parts of organic solvent at 30-100 ℃ for 0.1-72 hours, and then cleaning the separated backboard membrane by using water;
(2) selecting inorganic salt solution as centrifugate, and adjusting the density of centrifugate at 5 ~ 80 deg.C to 1.2 ~ 2.0.0 g/cm3；
(3) Adding the mixed membrane obtained in the step (1) and 30 ~ 2000 parts of the centrifugal separation liquid obtained in the step (2) into a centrifugal machine, centrifuging for 0.1 ~ 60 minutes at 10 ~ 20000 rpm, standing for 0.1 ~ 100 hours, and then carrying out layering separation.
2. The method for separating a solar back sheet film containing a fluorine material according to claim 1, wherein: the alkali is one or a combination of more of sodium hydroxide, potassium hydroxide, calcium hydroxide and ammonia water.
3. The method for separating a solar back sheet film containing a fluorine material according to claim 1, wherein: the penetrating agent is one or a combination of a plurality of nonionic surfactants, anionic surfactants and fluorine surfactants.
4. The method for separating a solar back sheet film containing a fluorine material according to claim 3, wherein: the non-ionic surfactant is one or a combination of more of JFC-1, JFC-E and JFC-2.
5. The method for separating a solar back sheet film containing a fluorine material according to claim 3, wherein: the anionic surfactant is one or a combination of more of a rapid penetrant T, an alkali-resistant penetrant OEP-70, an alkali-resistant penetrant AEP and a high-temperature penetrant JFC-M.
6. The method for separating a solar back sheet film containing a fluorine material according to claim 3, wherein: the fluorine surfactant is one or a combination of more of a sodium perfluorooctanoate surfactant, a sodium perfluorooctyl sulfonate surfactant, an ethoxy fluorocarbon surfactant and a fluorine-containing polyoxyethylene ether surfactant.
7. The method for separating a solar back sheet film containing a fluorine material according to claim 1, wherein: the organic solvent is one or a combination of several of methanol, ethanol, N-methyl pyrrolidone, ethylene glycol phenyl ether, N-dimethylformamide, dimethyl sulfoxide, hexafluoroisopropanol, acetone, benzyl alcohol, toluene and ethyl acetate.
8. The method for separating a solar back sheet film containing a fluorine material according to claim 1, wherein: the inorganic salt is BaCl2、CaCl2、KCl、MgCl、NaCl、Na2SO4、MgSO4、CaSO4、NaNO3、Mg(NO3)2、KNO3Or Ca (NO)3)2One or a combination of several of them.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114012936A (en) * | 2021-11-10 | 2022-02-08 | 泉州师范学院 | Method for separating and recovering solar backboard composite EVA (ethylene vinyl acetate) adhesive film leftover material based on low-temperature grinding method |
| CN114012935A (en) * | 2021-11-10 | 2022-02-08 | 泉州师范学院 | Separation and recovery method of solar backboard composite EVA (ethylene vinyl acetate) adhesive film leftover material |
| TWI816190B (en) * | 2020-12-01 | 2023-09-21 | 財團法人工業技術研究院 | Swelling agent and recycling method for sheet structure using the same |
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| CN107214878A (en) * | 2017-05-16 | 2017-09-29 | 泉州师范学院 | A kind of recovery method of solar energy back veneer material |
| EP3501775A1 (en) * | 2017-12-22 | 2019-06-26 | Rhodia Operations | Method of separating materials from an object |
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| CN107214878A (en) * | 2017-05-16 | 2017-09-29 | 泉州师范学院 | A kind of recovery method of solar energy back veneer material |
| EP3501775A1 (en) * | 2017-12-22 | 2019-06-26 | Rhodia Operations | Method of separating materials from an object |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| TWI816190B (en) * | 2020-12-01 | 2023-09-21 | 財團法人工業技術研究院 | Swelling agent and recycling method for sheet structure using the same |
| CN114012936A (en) * | 2021-11-10 | 2022-02-08 | 泉州师范学院 | Method for separating and recovering solar backboard composite EVA (ethylene vinyl acetate) adhesive film leftover material based on low-temperature grinding method |
| CN114012935A (en) * | 2021-11-10 | 2022-02-08 | 泉州师范学院 | Separation and recovery method of solar backboard composite EVA (ethylene vinyl acetate) adhesive film leftover material |
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