CN101121289A - Method for recovering and treating waste flexible circuit board - Google Patents
Method for recovering and treating waste flexible circuit board Download PDFInfo
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- CN101121289A CN101121289A CNA2007101220901A CN200710122090A CN101121289A CN 101121289 A CN101121289 A CN 101121289A CN A2007101220901 A CNA2007101220901 A CN A2007101220901A CN 200710122090 A CN200710122090 A CN 200710122090A CN 101121289 A CN101121289 A CN 101121289A
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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
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- Y02W30/62—Plastics recycling; Rubber recycling
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Abstract
A recycle and treatment method of abandoned flexible circuit board belongs to the technical field of abandoned electronic product resource recycling. At present, the special patent technology of recycling and treating the flexible circuit board has not appeared in and abroad; the method of burning to recycle the metal will easily pollute the air. The present invention, aiming at the structural features of the flexible circuit board, adopts the method of solution to dissolve or the method of hydrolization to treat the polymer layer in the flexible circuit board to separate the metal and non-mental parts of the flexible circuit board with certain processing conditions and realize the separation and recycle of the metal part of the flexible circuit board. The separation and recycle method of the present invention, compared with the method of burning and mechanical crushing, boasts of high recycle rate, low energy consumption and little pollution. Compared with the pickling method and corrosion method, the present invention boasts of simple process flow and little waste liquid.
Description
Technical field
Belong to waste electronic product resource recycling technical field, to ensure the pollution-free sustainable development of electronic industry.
Background technology
The present invention is a kind of recovery and treatment method at the flexible PCB in the electron wastes.Circuit board in the electron wastes is divided into two kinds, and a kind of is hard circuit board (hardboard), and a kind of is flexible PCB (soft board).Flexible PCB is laminated with flexible insulation film and metal forming together by adhesive and makes.Insulation film commonly used has polyimides (PI) film and polyester (PET) film, and metal forming commonly used is a Copper Foil.Except that Copper Foil, noble metals such as gold are also contained in junctions such as flexible PCB pad, have very high recovery value.Flexible PCB has adapted to the needs of electronic product to light, small-sized, high density, high reliability development, become indispensable important component part in the electronic product, occupy wherein being electrically connected of the overwhelming majority as flexible PCB in the light products such as notebook computer, mobile phone, digital camera, so flexible PCB fields such as car industry, military project, space flight, computer, telecommunication, medical treatment and consumer electronics have been widely used in.
The recycling of waste electronic product is the problem that all is faced with of All Countries in the world.In order and to reduce the pollution of venomous injurant confrontation environment such as heavy metal element with resource recycling, the research of electron wastes being carried out recycling treatment has very practical meaning.At present, the technology that reclaims copper from useless circuit board mainly concentrates on the processing of hardboard, and processing method comprises three classes: the one, and heat treating process comprises burning, cracking, direct smelting etc.; The 2nd, method of chemical treatment comprises pickling, corrosion etc.; The 3rd, the physical mechanical facture comprises pulverizing and sorting etc.Useless circuit board can produce toxic and harmful substance usually in heat treatment process, and the processing cost height.Method of chemical treatment comprises acid wash and corrosion method, and acid wash is that the waste printed circuit board that contains noble metal is handled with strong acid or strong oxidizer, obtains the waste acid liquor of peeling off the lower metal of sediment and cupric and other value ratio of noble metal; Again respectively with noble metal peel off sediment reduction, obtain metal product; And contain the waste acid liquor of high copper ion concentration, recyclable is copper sulphate or cathode copper.The corrosion method reclaims the waste printed circuit board material contain copper as copper chloride corrosion method, is to be placed in the copper chloride corrosion liquid, and with the copper corrosion, and noble metal is insoluble under suitable oxidation reduction potential control, thereby carries out the recovery of noble metal.The waste liquid that method of chemical treatment produces causes secondary pollution through regular meeting.Physical mechanical facture method has characteristics such as small investment, environmental pollution be little, but needs special equipment.
Patent related to the present invention mainly is the recovery technology at discarded printed circuit boards, patent CN1611309A (a kind of method that reclaims valuable resource in the waste and old printed circuit board, open day on May 4th, 2005) provides a kind of, adopted magnetic separator to sub-elect the separation and recovery method of ferromagnetic material (copper etc.) and nonmetal composition (plastics) after the waste and old printed circuit board pulverizing.Patent CN1899712A (a kind of waste and old printed circuit board resource recycling method, open day on January 24th, 2007) providing a kind of separates the method that combines with pyrolysis with Mechanical Crushing with magnetic separation, the metal in the waste and old printed circuit board is separated with nonmetal composition and reclaims.
Foregoing invention at be hard circuit board.And flexible PCB is different with the structure of printed substrate (hardboard), hardboard have certain thickness (usually＞=1mm), rigidity is better, Copper Foil and resin substrate are bonded together, during Mechanical Crushing, because resin substrate is mingled with glass fibre, so metallic copper and substrate are easy to broken apart.Although flexible PCB also is a layer structure, but there are not thick resin substrate and glass fibre, wherein Copper Foil is closely surrounded by the polymeric layer of toughness, whole flexible PCB is thin (usually＜0.5mm), has good toughness, directly carry out comparatively difficulty of mechanical crushing, and the polymer film of thin layer can not separate with Copper Foil yet after pulverizing, therefore the mechanical processing method in above-mentioned two patents is not suitable for the recycling of flexible board.Also do not recycle the special patented technology of FPC at present both at home and abroad.It is reported that the report that has is to adopt burning method recovery metal wherein.But burn and to control burning process well, otherwise be easy to generate atmosphere pollution.
Summary of the invention
Based on above technology, the present invention is intended to invent the separation method of insulating materials and metal ingredient in the flexible PCB of a kind of low cost, environment-friendly type, in the hope of reclaiming valuable resource.
The recovery and treatment method of waste flexible circuit board provided by the present invention, Fig. 1 is seen in its technological process, may further comprise the steps:
1) difference according to the used insulation film of flexible PCB is divided into A and B two class soft boards with waste flexible circuit board, the category-A soft board is to adopt polyimides (PI) film to make the flexible PCB of insulating materials, and the category-B soft board is to adopt polyester (PET) film to make the flexible PCB of insulating materials.
Mixing the mixing soft board of forming by category-A soft board and category-B soft board can not classify yet and handles.
2) the category-A soft board that obtains after the classification, employing method I carries out the lift-off processing of soft board: the category-A soft board is put in the alkali lye soaked, insulation film and metal material are peeled off, separate obtaining Metal Flake thing, metal fragment or metal dust, nonmetal sheet thing, and the turbid liquid that contains flocculent deposit.
The category-B soft board that obtains after the classification, employing method II carries out the lift-off processing of soft board: the category-B soft board is put in the amide-type organic solvent soaked, insulation film and metal material are peeled off, separate obtaining Metal Flake thing, metal fragment or metal dust, non-metallic solid residue, and polyester liquid.
Non-classified mixing soft board, can adopt the lift-off processing of category-A soft board in the advanced Xingqi of method I: will mix soft board and put in the alkali lye and soak, wherein the insulation film of category-A soft board and metal material are peeled off, separate obtaining Metal Flake thing, metal fragment or metal dust, nonmetal sheet thing and unstripped residue soft board (category-B soft board), and the turbid liquid that contains flocculent deposit.The soft board do not peeled off of residue then further adopts method II to carry out the separating treatment of soft board: will remain soft board (category-B soft board) and put in the amide-type organic solvent and soak, insulation film and metal material are peeled off, separate obtaining Metal Flake thing, metal fragment or metal dust and non-metallic solid residue, and polyester liquid.
Non-classified mixing soft board, also can adopt the lift-off processing of category-B soft board in the advanced Xingqi of method II: will mix soft board and put in the amide-type organic solvent and soak, wherein the insulation film of category-B soft board and metal material are peeled off, separate obtaining Metal Flake thing, metal fragment or metal dust, non-metallic solid residue and unstripped residue soft board (category-A soft board), and polyester liquid.The soft board that residue is not peeled off further adopts method I to carry out the separating treatment of soft board: will remain soft board (category-A soft board) and put in the alkali lye and soak, insulation film and metal material are peeled off, separate obtaining Metal Flake thing, metal fragment or metal dust, nonmetal sheet thing, and the turbid liquid that contains flocculent deposit.
3) separate the non-metallic solid residue that obtains after the immersion and be mainly polymer, become the single polymers material after the collection;
4) turbid liquid that contains flocculent deposit that obtains after method I separates step 2) filters, filter residue be the low molecular product 4,4 that obtains of polymeric material degrades '-diaminodiphenyl ether, through cleaning-drying, as Organic Chemicals.Rest solution with in the hydrochloric acid and after, heating concentrates, wherein water-fast material is separated out from filtrate, filters, and obtains pale yellow powder shape solid after the oven dry, is Pyromellitic Acid.Main sodium chloride-containing in the residue mother liquor can be used as accessory substance and concentrates collection.If rest solution still also has certain hydroxide ion (being alkali lye), then can be back to use step 2) in, recycle;
Step 2) solution that obtains after separating in method II in is polyester liquid, adopts distillating method, isolates polyester and organic solvent, and organic solvent can be back to use step 2) in, recycle.
The sorting technique of the waste flexible circuit board above-mentioned steps 1) can be classified according to the hot property (DSC curve) of soft board.
Above-mentioned steps 2) if the soft board size is decreased to the 5-10 millimeter, peeling off of metal forming in the subsequent process will be helped more in.
Above-mentioned steps 2) can accelerate stripping process by mechanical agitation in.
Above-mentioned steps 2) alkali lye in can be selected the aqueous solution of NaOH, potassium hydroxide or lithium hydroxide for use, and the concentration of hydroxide ion is between 1-10N in the alkali lye, and alkali liquid temperature is a room temperature-100 ℃.
Above-mentioned steps 3) the amide-type organic solvent in can be selected formamide, N-NMF, N for use, dinethylformamide, N, N-DEF, acetamide, N-methylacetamide, N, N-dimethylacetylamide, 2-Pyrrolidone, N-N-methyl-2-2-pyrrolidone N-can use or mix use separately.
The principle of system of selection of the present invention
The present invention is directed to the design feature of flexible PCB, the method of employing dissolution with solvents or hydrolysis is handled the polymeric layer in the flexible PCB, the metal part of flexible PCB is peeled off with non-metallic part, thereby the separation that realizes metal ingredient in the flexible PCB is reclaimed.Insulation film in the flexible PCB mainly adopts polyimides (PI) film and polyester (PET) film, metal material is mainly Copper Foil, the place also has noble metals such as a small amount of gold at pad, also has a small amount of adhesive in addition, and noble metals such as Copper Foil wherein and gold have very high recovery value.The recovery method that adopts is a burning method at present, and this method can reclaim metals such as copper, but the polymer of circuit board can produce pollution in burning process.
Although the polymer insulation film ratio of components that adopts in the flexible PCB is more single, be mainly polyimides (PI) film and polyester (PET) film, the recovery method of these two kinds of different materials is different.PI can hydrolysis in alkali lye, and PET can dissolve in amide solvent.PI and PET difference aspect hot property is obvious, and PI is not having tangible heat deflection below 300 ℃, and the fusing point of PET is between 250 ℃-260 ℃.Therefore,, investigate its hot property, determine the classification of insulating materials, and adopt corresponding method to handle by heat analysis method (as differential scanning calorimeter, i.e. DSC) to waste flexible circuit board of the same type.Realize that insulating materials and peeling off of metal material are keys of the present invention, classify according to the difference of insulation film and handle the use that can reduce chemicals, and make that the organic material purity that reclaims is higher, improve the use value of salvage material.Certainly, because polyimides (PI) film only and alkaline reaction, in the amide-type organic solvent, do not change, and polyester (PET) film can be dissolved in the amide-type organic solvent, but not react with alkali lye, therefore the soft board of mixed type can not classified yet, and by elder generation and alkaline reaction, perhaps elder generation and the effect of amide-type organic solvent reach the purpose of peeling off respectively, can simplify the step of mixing the recycling of class soft board like this, reach the recycling effect equally.Simultaneously because soft board is the layer structure that different materials is formed, particularly contain noble metal on the pad, the noble metal on the common pad of cause and the adhesion of metallic copper are relatively poor, when soaking (particularly being with mechanical agitation), come off easily and become metal fragment or metal dust (mainly being noble metal), leave standstill postprecipitation in the solution bottom, therefore will pay special attention to the collection of noble metal fragment (powder).Adopt the recovering and processing discarded flexible PCB of said method, the rate of recovery of metal can reach more than 90%.Removal process all can be carried out under normal pressure, and simultaneous temperature is at normal temperature-100 ℃, and typical temperature is high more, need the time just short more, but total reaction temperature is all lower, so energy consumption is little.Do not have the gas discharging in the process, the alkali lye and the organic solvent that separate in the removal process all can be recycled, and can reduce discharging to greatest extent.
Therefore, separation and recovery method of the present invention is compared with mechanical crushing method with burning method, have rate of recovery height, energy consumption low, pollute little advantage.Compare with the corrosion method with acid wash, have the advantage that technological process is simple, waste liquid is few.
The present invention has used for reference the recovery method of polyimides and polyester, is used for the material of recovering and processing discarded circuit board soft board.Different with the recovery and treatment method of single polyimides or single polyester is, of the invention process to liking discarded circuit board soft board, its structure and material and single polyimides or single polyester are different, the layer structure that the circuit board soft board is made up of the material of unlike material, tenor is more than 50%, particularly metallic copper wherein and the noble metal on the pad are the emphasis that the present invention reclaims, therefore do not need the Kapton complete hydrolysis in the processing procedure to monomer, do not need to be dissolved in polyester film in the organic solvent fully yet, only need to realize that polymer insulation film and peeling off of metal get final product, the medicine of Shi Yonging is few like this, recycled materials purity is higher, cost is low, and discharging is few.
Description of drawings
Fig. 1 technological process of the present invention
The specific embodiment
Processing example below by concrete illustrates effect of the present invention.
Example 1
1 of waste flexible circuit board, about 12 restrain, and taking a sample from edge is used for the measurement of DSC curve, and heating rate is 20 ℃/min.The result is presented at below 300 ℃, and this sample does not have heat deflection to take place, and differentiates that its insulation film is Kapton (a category-A soft board).This soft board has been laminated with Copper Foil, also has noble metals such as a small amount of gold in addition on the pad.This soft board is cut into 5 millimeter, puts into 200 milliliters of the sodium hydrate aqueous solutions of 10N, added hot reflux 2 hours, metal part is wherein peeled off fully with insulation film.After being cooled to room temperature sheet metal and noble metal fragment (powder) are collected, heavily about 8 grams are collected about 0.5 gram of insulation film.Surplus solution filters floccule, and filter residue is washed with deionized water, obtains yellow powder powder solid after the oven dry, heavily about 2 grams, be 4,4 '-diaminodiphenyl ether, purity 90%.Filtrate neutralizes with hydrochloric acid, and heating concentrates, and wherein water-fast material is separated out from filtrate, filters, and obtains pale yellow powder shape solid after the oven dry, and heavily about 1 gram is Pyromellitic Acid, purity 85%.Main sodium chloride-containing concentrates collection as accessory substance in the residue mother liquor.
Example 2
1 of waste flexible circuit board, about 6 restrain, and taking a sample from edge is used for the measurement of DSC curve, and heating rate is 20 ℃/min.The result is presented at below 300 ℃, and this sample does not have heat deflection to take place, and differentiates that its insulation film is Kapton (a category-A soft board), has been laminated with Copper Foil, also has noble metals such as a small amount of gold in addition on the pad.This soft board is put into 200 milliliters of the potassium hydroxide aqueous solutions of 1N, heat 50 ℃, through 24 hours, metal part was wherein peeled off fully with insulation film.After being cooled to room temperature sheet metal and noble metal fragment (powder) are collected, heavily about 4 grams are collected about 0.5 gram of insulation film.Surplus solution filters floccule, and filter residue is washed with deionized water, obtains yellow powder powder solid after the oven dry, heavily about 0.5 gram, be 4,4 '-diaminodiphenyl ether, purity 90%.Filtrate neutralizes with hydrochloric acid, and heating concentrates, and wherein water-fast material is separated out from filtrate, filters, and obtains pale yellow powder shape solid after the oven dry, and heavily about 0.5 gram is Pyromellitic Acid, purity 90%.Mainly contain potassium chloride in the residue mother liquor, concentrate as accessory substance and collect.
Example 3
1 of waste flexible circuit board, about 8 restrain, and taking a sample from edge is used for the measurement of DSC curve, and heating rate is 20 ℃/min.The result is presented at below 300 ℃, and this sample does not have heat deflection to take place, and differentiates that its insulation film is Kapton (a category-A soft board), has been laminated with Copper Foil, also has noble metals such as a small amount of gold in addition on the pad.This soft board is put into 200 milliliters of the lithium hydroxide aqueous solutions of 5N, soak at room temperature 7 days, metal part is wherein peeled off fully with insulation film.Sheet metal and noble metal fragment (powder) are collected, and heavily about 6 grams are collected about 1 gram of insulation film.Surplus solution filters floccule, and filter residue is washed with deionized water, obtains yellow powder powder solid after the oven dry, heavily about 0.5 gram, be 4,4 '-diaminodiphenyl ether, purity 80%.Filtrate neutralizes with hydrochloric acid, and heating concentrates, and wherein water-fast material is separated out from filtrate, filters, and obtains pale yellow powder shape solid after the oven dry, and heavily about 0.5 gram is Pyromellitic Acid, purity 80%.The concentration of hydroxide ion is 2.5N in the filtrate, continues to be used as the next round soak.
Example 4
1 of waste flexible circuit board, about 10 restrain, and taking a sample from edge is used for the measurement of DSC curve, and heating rate is 20 ℃/min.The result is presented at 256 ℃, and melting transition appears in this sample, is judged as the category-B soft board, and its insulating materials mainly is a polyester film, has been laminated with Copper Foil, also has noble metals such as a small amount of gold in addition on the pad.Put it in 150 milliliters of N-N-methyl-2-2-pyrrolidone N-s and soaked 3 hours, metal part is wherein peeled off fully with polyester film.Sheet metal is collected and noble metal fragment (powder), and heavily about 8.5 grams are collected about 1 gram of insulation film.Be dissolved with small amount of polyester in the remaining organic solvent.This solution is distilled, isolate polyester, heavily about 0.5 gram is isolated solvent N-N-methyl-2-2-pyrrolidone N-and polyester, and solvent N-N-methyl-2-2-pyrrolidone N-can continue to recycle.
Example 5
1 of waste flexible circuit board, about 10 restrain, and taking a sample from edge is used for the measurement of DSC curve, and heating rate is 20 ℃/min.The result is presented at 254 ℃, and melting transition appears in this sample, is judged as the category-B soft board, and its insulating materials mainly is a polyester film, has been laminated with Copper Foil, also has noble metals such as a small amount of gold in addition on the pad.Put it into 150 milliliters of N, soaked 3 hours in the N-DEF, metal part is wherein peeled off fully with polyester film.Sheet metal is collected and noble metal fragment (powder), and heavily about 8.5 grams are collected about 1 gram of insulation film.Be dissolved with small amount of polyester in the remaining organic solvent.This solution is distilled, isolate polyester, heavily about 0.5 gram is isolated solvent N, N-DEF and polyester, and solvent N, N-DEF can continue to recycle.
Example 6
2 of waste flexible circuit boards, about 15 restrain, and taking a sample from edge is used for the measurement of DSC curve, and heating rate is 20 ℃/min.The result is presented at 254 ℃, and melting transition appears in this sample, is judged as the category-B soft board, and its insulating materials mainly is a polyester film, has been laminated with Copper Foil, also has noble metals such as a small amount of gold in addition on the pad.Put it into 210 milliliters of formamides, N, soaked 4 hours in the mixed solvent of N-dimethylacetylamide, 2-Pyrrolidone (mixed volume was than 1: 1: 1), metal part is wherein peeled off fully with polyester film.Sheet metal is collected and noble metal fragment (powder), and heavily about 12 grams are collected about 2 grams of insulation film.Be dissolved with small amount of polyester in the remaining organic solvent.This solution is distilled, isolate polyester, heavily about 1.5 grams, isolated solvent is formamide, N, the mixed solution of N-dimethylacetylamide, 2-Pyrrolidone, this solvent can continue to recycle.
Example 7
6 of waste flexible circuit boards, heavily about 50 grams, color and quality are different, and the existing Kapton of insulating materials wherein has polyester film again, and insulation film is laminated with Copper Foil is in the same place, and also has noble metals such as a small amount of gold in addition on the pad.At first the soft board of sheet is cut into 1 * 1 centimetre fragment, these fragments are put into 500 milliliters of N-NMFs and N, soaked 3 hours in the mixed solvent of dinethylformamide (mixed volume was than 1: 1), metal part on the fragment that wherein has is peeled off fully with insulation film, collect sheet metal and unstripped soft board respectively, obtain sheet metal 18 grams, collect about 2 grams of insulation film.Surplus solution is distilled, isolate polyester, heavily about 1 gram, isolating solvent is N-NMF and N, the mixed solution of dinethylformamide, this solvent can continue to recycle.Unstripped soft board fragment continues to put into 500 milliliters of the sodium hydrate aqueous solutions of 6N, adds hot reflux 2 hours, and wherein metal and insulation film are peeled off fully.After being cooled to room temperature sheet metal and noble metal fragment (powder) are collected, obtain metal 22 grams, collect about 2 grams of insulation film.Surplus solution filters floccule, and filter residue is washed with deionized water, obtains yellow powder powder solid after the oven dry, heavily about 1.5 grams, be 4,4 '-diaminodiphenyl ether, purity 80%.Filtrate neutralizes with hydrochloric acid, and heating concentrates, and wherein water-fast material is separated out from filtrate, filters, and obtains pale yellow powder shape solid after the oven dry, and heavily about 2 grams are Pyromellitic Acid, purity 85%.The concentration of hydroxide ion is 2N in the filtrate, continues to be used as the next round soak.
Example 8
10 of waste flexible circuit boards, heavily about 40 grams, color and quality are different, and the existing Kapton of insulating materials wherein has polyester film again, and insulation film is laminated with Copper Foil is in the same place, and also has noble metals such as a small amount of gold in addition on the pad.These soft boards are put into 500 milliliters of the sodium hydrate aqueous solutions of 6N, added hot reflux 2 hours, metal and insulation film on the fragment that wherein has are peeled off fully.After being cooled to room temperature sheet metal, noble metal fragment (powder), unstripped soft board are collected respectively, obtain metal 12 grams, collect about 1.5 grams of insulation film.Surplus solution filters floccule, and filter residue is washed with deionized water, obtains yellow powder powder solid after the oven dry, heavily about 1 gram, be 4,4 '-diaminodiphenyl ether, purity 85%.Filtrate neutralizes with hydrochloric acid, and heating concentrates, and wherein water-fast material is separated out from filtrate, filters, and obtains pale yellow powder shape solid after the oven dry, and heavily about 1.5 grams are Pyromellitic Acid, purity 80%.The concentration of hydroxide ion is 3N in the filtrate, continues to be used as the next round soak.The mixed solution (mixed volume was than 2: 1) that unstripped soft board fragment continues to put into 500 milliliters of acetamides and N-methylacetamide soaked 3 hours, the metal part is peeled off fully with insulation film, the sheet metal that collection is peeled off obtains sheet metal 20 grams, collects about 2 grams of insulation film.Surplus solution is distilled, isolate polyester, heavily about 1 gram, isolated solvent is the mixed solution of acetamide and N-methylacetamide, this solvent can continue to recycle.
Claims (6)
1. the recovery and treatment method of a waste flexible circuit board is characterized in that, may further comprise the steps:
1) difference according to the used insulation film of flexible PCB is divided into A and B two class soft boards with waste flexible circuit board, the category-A soft board is to adopt Kapton to make the flexible PCB of insulating materials, and the category-B soft board is to adopt polyester film to make the flexible PCB of insulating materials;
Perhaps mixing the mixing soft board of forming by category-A soft board and category-B soft board handles;
2) the category-A soft board that obtains after the classification, employing method I carries out the lift-off processing of soft board: method I and soaks in the alkali lye for the category-A soft board is put into, insulation film and metal material are peeled off, separate obtaining Metal Flake thing, metal fragment or metal dust, nonmetal sheet thing, and the turbid liquid that contains flocculent deposit;
The category-B soft board that obtains after the classification, employing method II carries out the lift-off processing of soft board: method II and soaks in the amide-type organic solvent for the category-B soft board is put into, insulation film and metal material are peeled off, separate obtaining Metal Flake thing, metal fragment or metal dust, non-metallic solid residue, and polyester liquid;
Non-classified mixing soft board, the lift-off processing of category-A soft board in the advanced Xingqi of employing method I: will mix soft board and put in the alkali lye and soak, wherein the insulation film of category-A soft board and metal material are peeled off, separate obtaining Metal Flake thing, metal fragment or metal dust, nonmetal sheet thing and unstripped residue category-B soft board, and the turbid liquid that contains flocculent deposit; The soft board do not peeled off of residue then further adopts method II to carry out the separating treatment of soft board: will remain the category-B soft board and put in the amide-type organic solvent and soak, insulation film and metal material are peeled off, separate obtaining Metal Flake thing, metal fragment or metal dust, non-metallic solid residue, and polyester liquid;
Non-classified mixing soft board, perhaps adopt the lift-off processing of category-B soft board in the advanced Xingqi of method II: will mix soft board and put in the amide-type organic solvent and soak, wherein the insulation film of category-B soft board and metal material are peeled off, separate obtaining Metal Flake thing, metal fragment or metal dust, non-metallic solid residue and unstripped residue category-A soft board, and polyester liquid; The soft board do not peeled off of residue further adopts method I to carry out the separating treatment of soft board: will remain the category-A soft board and put in the alkali lye and soak, insulation film and metal material are peeled off, separate obtaining Metal Flake thing, metal fragment or metal dust, nonmetal sheet thing, and the turbid liquid that contains flocculent deposit;
3) separate the non-metallic solid residue that obtains after the immersion and be mainly polymer, become the single polymers material after the collection;
Step 2) turbid liquid that contains flocculent deposit that obtains after method I separates in filters, filter residue be the low molecular product 4,4 that obtains of polymeric material degrades '-diaminodiphenyl ether;
If the hydroxide ion concentration in the filtrate then is back to use step 2 greater than 1N) in, recycle; If hydroxide ion concentration is less than 1N in the filtrate, then use in the hydrochloric acid and after, heating concentrates, wherein water-fast material is separated out from filtrate, filters, and obtains pale yellow powder shape solid after the oven dry, is Pyromellitic Acid; The residue mother liquor concentrates as accessory substance and collects;
Step 2) solution that obtains after separating in method II in is polyester liquid, adopts distillating method, isolates polyester and organic solvent.
2. the recovery and treatment method of waste flexible circuit board according to claim 1 is characterized in that, above-mentioned steps 1) in the hot property of classification criterion soft board of waste flexible circuit board classify.
3. the recovery and treatment method of waste flexible circuit board according to claim 1 is characterized in that, above-mentioned steps 2) in the soft board size is decreased to the 5-10 millimeter.
4. the recovery and treatment method of waste flexible circuit board according to claim 1 is characterized in that, above-mentioned steps 2) in by mechanical agitation.
5. the recovery and treatment method of waste flexible circuit board according to claim 1, it is characterized in that, above-mentioned steps 2) alkali lye in is selected the aqueous solution of NaOH, potassium hydroxide or lithium hydroxide for use, and the concentration of hydroxide ion is between 1-10N in the alkali lye, and alkali liquid temperature is a room temperature-100 ℃.
6. the recovery and treatment method of waste flexible circuit board according to claim 1, it is characterized in that, above-mentioned steps 3) the amide-type organic solvent in is selected formamide, N-NMF, N for use, dinethylformamide, N, N-DEF, acetamide, N-methylacetamide, N, N-dimethylacetylamide, 2-Pyrrolidone, N-N-methyl-2-2-pyrrolidone N-use separately or mix and use.
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102699011A (en) * | 2012-06-21 | 2012-10-03 | 上海大学 | Method for treating waste circuit board by using dimethyl sulfoxide |
| CN104194035A (en) * | 2014-08-13 | 2014-12-10 | 张春凡 | Degradation agent and method for making waste circuit boards and waste resin plates into plates |
| CN104448384A (en) * | 2014-08-13 | 2015-03-25 | 张春凡 | Method for producing plastic-fiber plates by utilizing waste circuit boards and waste resin materials |
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2007
- 2007-09-21 CN CNB2007101220901A patent/CN100513113C/en not_active Expired - Fee Related
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| CN102699011B (en) * | 2012-06-21 | 2014-10-01 | 上海大学 | Method for treating waste circuit board by using dimethyl sulfoxide |
| CN104194035A (en) * | 2014-08-13 | 2014-12-10 | 张春凡 | Degradation agent and method for making waste circuit boards and waste resin plates into plates |
| CN104448384A (en) * | 2014-08-13 | 2015-03-25 | 张春凡 | Method for producing plastic-fiber plates by utilizing waste circuit boards and waste resin materials |
| CN104194035B (en) * | 2014-08-13 | 2017-04-12 | 张春凡 | Degradation agent and method for making waste circuit boards and waste resin plates into plates |
| CN104448384B (en) * | 2014-08-13 | 2017-05-17 | 张春凡 | Method for producing plastic-fiber plates by utilizing waste circuit boards and waste resin materials |
| CN106239772A (en) * | 2016-08-03 | 2016-12-21 | 界首市钰泽塑业有限公司 | A kind of method of squash type separation blending medicated clothing composition |
| CN106239772B (en) * | 2016-08-03 | 2018-05-15 | 界首市钰泽塑业有限公司 | A kind of method that squash type separates blended clothing component |
| CN108568445A (en) * | 2017-03-07 | 2018-09-25 | 鹏鼎控股(深圳)股份有限公司 | Separate and recover the method and its separation equipment of material |
| CN106734121A (en) * | 2017-03-31 | 2017-05-31 | 歌尔股份有限公司 | FPC inserts recycling techniques |
| CN108160683A (en) * | 2018-02-06 | 2018-06-15 | 湖南科技大学 | A kind of method that waste and old tin plating copper-clad plate resource utilization utilizes |
| CN109365487A (en) * | 2018-11-30 | 2019-02-22 | 清远市进田企业有限公司 | The energy-efficient cleaning process of epoxy coating in a kind of waste and old circuit board |
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