CN102050958A - Method for recycling waste plastics containing polybrominated diphenyls and polybrominated diphenyl ethers - Google Patents
Method for recycling waste plastics containing polybrominated diphenyls and polybrominated diphenyl ethers Download PDFInfo
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Abstract
The invention discloses a method for recycling waste plastics containing polybrominated diphenyls and polybrominated diphenyl ethers, which comprises the following steps: adding waste electronic plastics into a solvent A, dissolving the waste electronic plastics at normal temperature, screening the dissolved plastic solution by using a separating screen, centrifugalizing the screened plastic solution, complementally adding the solvent A into the centrifugalized plastic solution, applying ultrasonic waves onto the solution, adding the obtained plastic solution into a solvent B, and stirring for 30-90 minutes at the rotation speed of 1000-2000 revolutions/minute under the action of ultrasonic waves of which the frequency is 20-50 kHz and the power is 0.5-1.5 W/cm<2>; and sending the plastic precipitate into a twin screw extruder, and removing the residual solvent in the precipitate at 180-220 DEG C, thereby obtaining the recycled plastic product. The mass percent of polybrominated diphenyls and polybrominated diphenyl ethers in the plastics treated by using the method provided by the invention is reduced to lower than 0.1% without great loss of physical and mechanical properties.
Description
Technical field
Invention relates to the renovation process of waste or used plastics, particularly relates to the recycle of the fire-retardant waste or used plastics of Poly Brominated Diphenyl Ethers and Polybrominated biphenyl, and this method is applicable to the regeneration of fire-retardant waste and old electric plastics.
Background technology
The removal process of disassembling of waste and old electric electrical equipment produces a large amount of plastic refuses, generally be added with 5～20% bromide fire retardant in these plastics, wherein Polybrominated biphenyl and Poly Brominated Diphenyl Ethers have been proved to be a class to environment, the deleterious persistence organic pollutant of biology and human health, thereby European Union's clear and definite regulation in " about being limited in the electronic and electrical equipment instruction of using some objectionable constituent " (being the RoHS instruction), from July 1st, 2006 all electric equipment products and massfractions of the Polybrominated biphenyl in the parts and Poly Brominated Diphenyl Ethers thereof in European Union's market sale must not be above 0.1%.This prescribed limits waste and old electric electrical equipment plastics continue to utilize with existing renovation process.
Polybrominated biphenyl and polybromodiphenyl ether are the major causes that causes the plastic reclaimed difficulty of waste household appliances, if Polybrominated biphenyl and polybromodiphenyl ether can be separated from waste and old electric plastics, so just can resemble and handle regeneration waste household appliances plastics the common plastics.But the difficulty of separating polybrominated diphenylether is from plastics, even the plastics viscosity after the fusion is also quite high, homodisperse Polybrominated biphenyl, polybromodiphenyl ether particulate wherein is difficult to obtain to separate by general physics or chemical process.
In patent ZL00801987.8, the contriver uses dibasic alcohol system, glycol ether system or lactate series solvent contact with the plastics of solid-state or molten state, Poly Brominated Diphenyl Ethers in the dissolving plastics, reach the purpose that reduces Poly Brominated Diphenyl Ethers concentration in the reprocessed plastic(s), even but because plastics also have very high viscosity under molten state, solvent molecule and Poly Brominated Diphenyl Ethers molecule are very slow in the mass transfer velocity of diffusion of plastics inner in the dissolution process, and the solid-liquid contact area is less, therefore separating effect is not good enough, the boiling point of this kind solvent is higher in addition, the solvent that enters in the plastics also is difficult for removing totally by evaporation, causes the dissolvent residual in the reprocessed plastic(s) too high.In order to improve the contact area of solvent and plastics, the applicant has proposed innovative approach in its patent ZL02808555.8, adopt screw extrusion press to replace general stirring tank to finish extraction process, having strengthened solvent contacts with the mixing of plastic melt, thereby the higher separation efficiency of acquisition, but because the concentration of decabromodiphenyl oxide is generally higher in the plastics, and solubleness is on the low side, the massfraction that separates the decabromodiphenyl oxide in the plastics of back still can not reach and be lower than 0.1% RoHS standard, and solvent residual too high problem in plastics is not resolved yet, and influenced re-using of reprocessed plastic(s).
United States Patent (USP) (US6500872) uses with toluene, limonene, kautschin dissolving Flameproof styrenic class plastics, the solution of 20～30wt% will be formed behind the dissolving plastic, adopt centrifuge separator to isolate insoluble decabromodiphynly oxide and other additive granules, thereafter the polymers soln vaporising under vacuum can be obtained regenerating resin except that desolvating.But adopt this patented method to reclaim the fire-retardant plastics of Poly Brominated Diphenyl Ethers and have following problem: the decabromodiphenyl phenylate still has the solubleness of 0.1～0.2wt% in theory under (1) normal temperature in these solvents, the solubleness of the Poly Brominated Diphenyl Ethers that nine bromines are following is then bigger, because boiling point height, volatility is low, and major part dissolved Poly Brominated Diphenyl Ethers can not be removed with solvent in vacuum-evaporation process subsequently.Therefore can't obtain to separate to the bigger Polybrominated biphenyl of some solubleness, Poly Brominated Diphenyl Ethers (as the biphenyl ether that replaces below eight bromines).The concentration of the Poly Brominated Diphenyl Ethers in the regenerating resin that obtains thus still can exceed the standard of RoHS.(2) particle diameter of decabromodiphenyl oxide raw material is generally at 1～5 micron, experiment finds that the decabromodiphenyl oxide particle in the waste or used plastics also can be partly dissolved thereupon in dissolving plastic, particle diameter diminishes as a result, therefore in plastic solution, exist a large amount of particle diameters less than 1 micron decabromodiphenyl oxide particle, can not obtain to separate even this part finely ground particle substance adopts high speed centrifugation to separate, the result causes the concentration of decabromodiphenyl oxide in the plastic solution after the centrifugation apparently higher than its theoretical dissolution degree in solvent.
Chinese invention patent ZL01116994.X discloses a kind of method of utilizing pressure fluid or supercutical fluid to remove fire retardant from flame retardant plastics, by the separated and dissolved of supercutical fluid, can obtain the polybromodiphenyl ether massfraction and meet the reprocessed plastic(s) that the RoHS of European Union requires fire retardant in the plastics.Nearest disclosed patent has also proposed the apparatus and method of fire retardant in the supercritical CO 2 extracting and separating waste or used plastics.But because CO
2Be non-polar molecule, supercritical CO
2Though to the dissolving power of polar polybromodiphenyl ether greater than common organic solvents, but the dissolving to decabromodiphynly oxide is still not ideal enough, in plastics the excessive concentration of decabromodiphynly oxide, be difficult for fully and carry out by the supercritical CO 2 dissolving, therefore the separating effect that will obtain needs under very high extracting pressure and the very high extraction temperature and the very long extraction time.Application number is 200910214489.1 Chinese invention patent application proposition employing solvent method and supercritical co bonded scheme, has solved the too high problem of dissolvent residual, and the Poly Brominated Diphenyl Ethers concentration of can regenerating simultaneously reaches the product of ROHS standard.But the supercritical extraction process exists equipment requirements height, separation condition harshness, is not suitable for problem such as scale operation.
This shows that existing technology can not solve the regeneration problem of the Plastic wastes thing that contains Polybrominated biphenyl, Poly Brominated Diphenyl Ethers preferably.
Summary of the invention
At the deficiencies in the prior art, the present invention proposes a kind of method of from flame retardant plastics, separating Polybrominated biphenyl and Poly Brominated Diphenyl Ethers, realize the physics recycle of waste and old electric electricity plastics, contain Polybrominated biphenyl, the flame retardant plastics of Poly Brominated Diphenyl Ethers is after the method that the present invention proposes is handled, the quality percentage composition of Polybrominated biphenyl in the plastics and Poly Brominated Diphenyl Ethers is reduced to below 0.1%, guarantee that simultaneously its physical and mechanical properties can not suffer big loss in the sepn process of Poly Brominated Diphenyl Ethers, can continue on for the manufacturing of various electronic and electrical equipments through the waste household appliances plastics of the present invention's processing.
Purpose of the present invention is achieved through the following technical solutions:
Contain the renovation process of the waste or used plastics of Polybrominated biphenyl and Poly Brominated Diphenyl Ethers, comprise the steps:
(1) waste and old electric plastics is added in the solvent orange 2 A, dissolving at normal temperatures, the plastic quality percentage composition is 20～30% in the control solution; Described solvent orange 2 A is toluene, dimethylbenzene, butanone, Propiophenone, pimelinketone, methyl isoamyl ketone, limonene, kautschin, butylacetate and/or ethyl acetate; Described waste and old electric plastics is the thermoplastics that has added Polybrominated biphenyl and/or Poly Brominated Diphenyl Ethers;
(2) plastic solution after the dissolving sieves by separation sieve, and the aperture of screen cloth is 1.0～0.5mm, sifts out undissolved plastics and impurity;
(3) plastic solution after sieving carries out centrifugation, and rotating speed is separated greater than 1 micron particle particle diameter in the plastic solution more than or equal to 10000 commentaries on classics/min as considering slag;
(4) add in the plastic solution that solvent orange 2 A goes out to centrifugation, control plastic quality concentration is 10-20%, and solution temperature is brought up to 50-100 ℃, and solution is applied ultrasonic wave, is that 50-100KHz, power are 0.5-1.5w/cm in frequency
2Ultrasonic wave effect stirring and dissolving 60-120min down and under the rotating speed of 500-1000 commentaries on classics/min;
(5) plastic solution with step (4) gained adds among the solvent B, is that 20-50KHz, power are 0.5-1.5w/cm in frequency
2The ultrasonic wave effect and the rotating speed agitation condition of 1000-2000 commentaries on classics/min under, stir 30-90min, the plastics of separating out are precipitated with particulate state; Then with mixed solvent and plastics precipitate and separate; The plastics precipitation is washed with solvent B; Described solvent B is a monoalcohol solvent;
(6) the plastics throw out after the washing is sent into the twin screw extruder of devolatilization type, deviates from solvent residual in the throw out under 180-220 ℃, obtains to regenerate plastic prod.
For further realizing purpose of the present invention, described monoalcohol solvent is preferably methyl alcohol, ethanol, n-propyl alcohol, Virahol, butanols, isopropylcarbinol and/or amylalcohol.
Described step (5) mixed solvent is sent into rectifying tower, steams pure solvent B from cat head, extracts solvent orange 2 A out at the bottom of tower.
The dissolving of described step (1) is to be stirring and dissolving 60～90min under 100～200 commentaries on classics/min conditions in stir speed (S.S.) preferably.
The solvent orange 2 A of described step (1) and the mass ratio of waste and old electric plastics are 100: 25～43.
Described impurity is metal, glass, gravel and/or the wood chip of insoluble solid material.
Described step (3) particle diameter is Polybrominated biphenyl, Poly Brominated Diphenyl Ethers or additive particles greater than 1 micron particle.
The consumption of described solvent B be step (1) and step (4) solvent orange 2 A quality and 1-3 doubly.
Waste and old electric plastics at present can not recycle key reason be that Polybrominated biphenyl, the Poly Brominated Diphenyl Ethers concentration of reconstituted product can not satisfy the RoHS standard, therefore to utilize physics regeneration techniques circulation waste and old electric plastics, the most important condition is the Poly Brominated Diphenyl Ethers fire retardant of isolating wherein, and its total concn is reduced to below the 0.1wt%.
The handled object waste and old electric plastics of the present invention mainly is a styrenic polymer, as polystyrene (PS), high-impact polystyrene (HIPS), acrylonitrile-butadiene-phenylethylene multipolymer (ABS) and ABS/PC alloy etc., but be not limited to these, all can adopt the technology of the present invention to handle so long as added the thermoplastics of Polybrominated biphenyl, Poly Brominated Diphenyl Ethers.
The used solvent orange 2 A feature of the present invention is the flame retardant plastics that this solvent system can dissolve needs processing, but decabromodiphenyl or decabromodiphenyl oxide can only be slightly soluble in this solvent or be insoluble to this solvent, so-called slightly soluble is meant that the solubleness of decabromodiphenyl oxide is not more than 0.2wt%, therefore general conventional organic solvent such as toluene, dimethylbenzene, benzene, tetrahydrofuran (THF), chloroform, tetracol phenixin, ethylene dichloride,, methylene dichloride, limonene, kautschin, butylacetate, ethyl acetate etc. can be used as solvent systems of the present invention.Two of the feature of solvent orange 2 A is, the solvent that is used for dissolving flame retardant plastics can be a fresh solvent, also can be by Polybrominated biphenyl, solvent that Poly Brominated Diphenyl Ethers is saturated from solvent regeneration system.With by Polybrominated biphenyl, dissolution with solvents household electrical appliances plastics that Poly Brominated Diphenyl Ethers is saturated, do not influence its solubility property and separating effect.
The feature of the solvent B that the present invention uses is can be miscible with the A solvent, and simultaneously the B solvent is not less than solvent orange 2 A to the dissolving power of Polybrominated biphenyl, Poly Brominated Diphenyl Ethers, and at least near solvent orange 2 A, but solvent B should be the poor solvent of plastics, preferably slightly soluble or do not dissolve plastics.All can meet the demands as various monohydroxy-alcohols such as ethanol, n-propyl alcohol, Virahol, butanols, amylalcohols.The boiling point of solvent B should be lower more than 10 ℃ than solvent orange 2 A in addition, is convenient to obtain regeneration by rectifying separation.
The present invention is dissolved, and to separate plastics be to be to improve the dissolving power of solvent to the small-particle fire retardant for fear of too much dissolving Polybrominated biphenyl, Poly Brominated Diphenyl Ethers at this moment, improving temperature after the centrifugation, avoids being adsorbed by plastics in the plastics precipitation process.Improve temperature simultaneously and also can reduce carbon black, plastics precipitation surface the absorption of dissolved flame retardant molecule.
The present invention adds solvent orange 2 A in step (4), improves the residual Polybrominated biphenyl of dissolution with solvents, Poly Brominated Diphenyl Ethers particulate ability on the one hand, and the solubleness that reduces plastics on the other hand helps avoiding precipitate phase to form the tendency of floss.
At Polybrominated biphenyl, low, the insoluble characteristics of Poly Brominated Diphenyl Ethers solubleness.The present invention uses ultrasonic wave to promote the Polybrominated biphenyl, the Poly Brominated Diphenyl Ethers particulate that remain in the solution after the centrifugation to dissolve, and promotes Polybrominated biphenyl, the desorb of Poly Brominated Diphenyl Ethers molecule of being adsorbed by carbon black.In the precipitate and separate plastics stage, ultrasonic wave has and reduces that carbon black, plastics throw out improve separation efficiency to the absorption of dissolved Polybrominated biphenyl, Poly Brominated Diphenyl Ethers molecule in the precipitation process.
During the fire-retardant plastics of technical finesse Polybrominated biphenyl, the Poly Brominated Diphenyl Ethers that adopts the present invention to propose, no matter what add in the plastics is decabromodiphenyl, the decabromodiphenyl oxide of indissoluble, still Poly Brominated Diphenyl Ethers, the Polybrominated biphenyl of other low bromines replacements that solubleness is bigger; No matter be the concentration height that adds Polybrominated biphenyl, Poly Brominated Diphenyl Ethers, all can obtain to satisfy the reprocessed plastic(s) product of RoHS command request.The present invention is effective too to other additives, fire retardant in the separating plastic.
Compared with prior art, the present invention has following advantage:
(1) the present invention changes the leaching sepn process into the liquid-liquid extraction sepn process, has improved separation efficiency, has avoided prior art to cause the low problem of extraction efficiency because of liquid-solid contact interface is limited.
(2) the technology of the present invention not only can be separated decabromodiphenyl, the decabromodiphenyl oxide of low solubility, also can bigger other Polybrominated biphenyl, the Poly Brominated Diphenyl Ethers based flame retardant of separate dissolved degree.Antimonous oxide, lime carbonate in simultaneously can also separating plastic, various impurity such as mineral additives such as titanium dioxide, fiber-like strongthener and metal, plant, gravel, thereby the reconstituted product purity that obtains is very high, mechanical property is good.
(3) the technology of the present invention adopts the solvent deposition technology that high boiling solvent orange 2 A is separated with plastics, and utilize lower boiling solvent B that the solvent orange 2 A in the plastics precipitation is cemented out, therefore extrude the desolventizing stage in solvent reclamation stage and plastics, only need evaporate low boiling point solvent B, reduce treatment temp, reduced the energy consumption of sepn process.Avoided also simultaneously that polymkeric substance is degraded, crosslinked possibility in the separation regeneration process, so the reservation of the mechanical mechanics property of reconstituted product is intact.
(4) Polybrominated biphenyl, the Poly Brominated Diphenyl Ethers that adopts the present invention to separate the flame-resistant electronic plastics, the regenerated plastic prod can satisfy the requirement of RoHS instruction, dissolvent residual concentration can be reduced to below the 0.1wt% simultaneously.
(5) adopt Polybrominated biphenyl, the Poly Brominated Diphenyl Ethers of technical point of the present invention in waste and old electric plastics, not only the concentration of the Polybrominated biphenyl in the reprocessed plastic(s) product, Poly Brominated Diphenyl Ethers can satisfy the requirement of RoHS instruction.Adopt technology of the present invention can also improve the purity of reprocessed plastic(s) product, mechanical mechanics property is retained.Thereby realize efficient, the safe recycle of waste and old electric plastics.
Specific implementation method
The present invention is further illustrated below in conjunction with embodiment, but embodiment does not constitute the restriction to the claimed scope of the present invention.
Embodiment 1
Contain in the waste and old HIPS of 1kg (high anti-the fill polystyrene) particle of decabromodiphenyl oxide 5% (weight) and the stirring tank that 4kg toluene joins one 10 liters, stirring and dissolving 60min under the normal temperature, solution is separated with separation sieve (aperture is 0.5mm), obtain impurity such as 4.9kg plastic solution and the insoluble plastic grain of 0.1kg and screw, glass, gravel.Plastic solution is passed through a high speed tubular-bowl centrifuge, the worry slag and the 4.72kg that isolate 0.18kg mud shape under the rotating speed of 10000 commentaries on classics/min consider liquid, add 4kg toluene again in considering liquid the concentration of HIPS is reduced to about 10%, be heated to 50 ℃, inserting frequency is that 100kHz, power are 0.5W/cm
2The ultrasonic wave effect under, and with the speed stirring and dissolving 60min of 500 commentaries on classics/min, join in the 8kg Virahol stirring tank that is preheating to 50 ℃ with the speed of 100ml/min then and precipitate, the stirring velocity of Virahol is 1000 commentaries on classics/min in the adition process, plastic solution adds the back to be continued to stir 30min under action of ultrasonic waves, and frequency of ultrasonic is that 20KHz, power are 1.5W/cm
2Filter down at 50 ℃ then, the plastics throw out washs 2 times with 2.0kg Virahol (50 ℃), filtration obtains the plastics precipitation, through devolatilization type twin screw extruder extruding under 180-220 ℃ remove solvent after, sampling analysis, the weight concentration that records the decabromodiphenyl oxide in the regenerated plastic sample is 0.075%, the weight concentration of residual toluene is 0.02% in the plastics, the weight concentration of Virahol is 0.05%, the tensile strength that records reprocessed plastic(s) according to plastic tensile standard of performance test method (GB/T1042-92) is 26.8MPa, and the notched Izod impact strength that records reprocessed plastic(s) according to plastics socle girder normal of impact test method (GB/T1843-1996) is 7.11KJ/m
2, with tensile strength and the 6.21KJ/m of 27.5MPa before the regeneration
2Notched Izod impact strength approaching.(the relevant performance test methods of following embodiment is with embodiment 1)
The mixture of toluene and Virahol can be extracted toluene out at the recovered overhead Virahol by rectifying at the bottom of the tower, cold filtration is removed the decabromodiphenyl oxide crystal of separating out, and obtains being can be recycled by the saturated toluene of decabromodiphenyl oxide.
Embodiment 2
The 1kg waste and old polystyrol (PS) that contains decabromodiphenyl oxide 5%, decabromodiphenyl 3% and 2.3kg limonene join in one 10 liters the stirring tank, stirring and dissolving 60min under the normal temperature, solution by separation sieve (aperture is 1mm), is obtained impurity such as 3.19kg polymers soln and about insoluble plastic grain of 0.11kg and screw, glass, gravel.Polymers soln is passed through a high speed tubular-bowl centrifuge, the worry slag and the 2.94kg that isolate 0.25kg mud shape under the rotating speed of 15000 commentaries on classics/min consider liquid, control plastics concentration is about 20% in the liquid to considering to add the 1kg limonene again, being heated to 60 ℃, is 0.5w/cm at frequency 100kHz/, power simultaneously
2The ultrasonic wave effect under with the speed stirring and dissolving 120min of 1000 commentaries on classics/min, join in the 8kg n-propyl alcohol stirring tank that is preheating to 60 ℃ with the speed of 100ml/min then and precipitate, the stirring velocity of n-propyl alcohol is 2000 commentaries on classics/min in the adition process, continue to stir 60min under action of ultrasonic waves after adding plastic solution, frequency of ultrasonic is that 50KHz, power are 1.5w/cm
2Filter then, the plastics throw out washs 2 times with 2.0kg n-propyl alcohol (60 ℃), filtration obtains the plastics precipitation, through devolatilization type twin screw extruder extruding under 180-220 ℃ remove solvent after, sampling analysis, record the regenerated plastic sample, the concentration that sampling analysis records the decabromodiphenyl oxide in the plastics is 0.058%, the concentration of decabromodiphenyl is 0.018%, total Poly Brominated Diphenyl Ethers, the concentration of Polybrominated biphenyl are 0.076%, the concentration of residual limonene is 0.04% in the plastics, and the concentration of residual n-propyl alcohol is 0.06%.The tensile strength of reprocessed plastic(s) sample is 35.2MPa, and notched Izod impact strength is 3.93KJ/m
2, with tensile strength and the 3.21KJ/m of 37.5MPa before the regeneration
2Notched Izod impact strength approaching.
The mixture of limonene and n-propyl alcohol is by rectifying, can extract limonene at the bottom of the tower out at the recovered overhead n-propyl alcohol, and cold filtration is removed decabromodiphenyl, the decabromodiphenyl oxide crystal of separating out, and obtains being can be recycled by decabromodiphenyl, limonene that decabromodiphynly oxide is saturated.
Embodiment 3
Contain in the waste and old HIPS of 1kg of decabromodiphenyl oxide 10% and the stirring tank that the 4kg butylacetate joins one 10 liters, stirring and dissolving 90min under the normal temperature, solution by separation sieve (aperture is 0.5mm), is obtained impurity such as 4.92kg polymers soln and the insoluble plastic grain of 0.08kg and screw, glass, gravel.Polymers soln is passed through a high speed tubular-bowl centrifuge, the worry slag and the 4.59kg that isolate 0.33kg mud shape under the rotating speed of 10000 commentaries on classics/min consider liquid, adding the 4.5kg butylacetate in considering liquid again is reduced to the concentration of plastics about 10%, be heated to 50 ℃ then, insert frequency 50kHz, power is 1.5w/cm
2The ultrasonic wave effect under with the speed stirring and dissolving 60min of 500 commentaries on classics/min.Join in the 9.5kg ethanol stirring tank that is preheating to 50 ℃ with the speed of 100ml/min then and precipitate, the alcoholic acid stirring velocity is 1000 commentaries on classics/min in the adition process, plastic solution adds the back to be continued to stir 90min under action of ultrasonic waves, and frequency of ultrasonic is that 50KHz, power are 0.5W/cm
2Filter down at 50 ℃ again, the plastics throw out washs 2 times with 2.0kg ethanol (50 ℃), filtration obtains the HIPS precipitation, through devolatilization type twin screw extruder extruding under 180-220 ℃ remove solvent after, sampling analysis, the concentration that records the decabromodiphenyl oxide in the regenerated HIPS sample is 0.085%, the concentration of residual butylacetate is 0.03% in the plastics, concentration of ethanol is 0.05%, and the tensile strength of sample is 27.4MPa, and notched Izod impact strength is 7.31KJ/m
2, with tensile strength and the 6.21KJ/m of 27.5MPa before the regeneration
2Notched Izod impact strength approaching.
Butylacetate and alcoholic acid mixture can be extracted butylacetate out at recovered overhead ethanol by rectifying at the bottom of the tower, cold filtration is removed the decabromodiphenyl oxide crystal of separating out, and obtains being can be recycled by the saturated butylacetate of decabromodiphynly oxide.
Embodiment 4
Contain in the waste and old ABS of 1kg (acrylonitrile-butadiene-phenylethylene multipolymer) particle of octa-BDE 10% and the stirring tank that the 3.3kg butanone joins one 10 liters, stirring and dissolving 90min under the normal temperature, solution is separated with separation sieve (aperture is 1mm), obtain impurity such as 4.17kg polymers soln and the insoluble plastic grain of 0.13kg and metal, glass, gravel.Polymers soln is passed through a high speed tubular-bowl centrifuge, the worry slag and the 4.07kg that isolate 0.10kg mud shape under the rotating speed of 15000 commentaries on classics/min consider liquid, in considering liquid, add the 1.5kg butanone again the concentration of plastics is reduced to about 15%, be heated to 50 ℃, insert 50kHz, 1.5w/cm
2The ultrasonic wave effect under with the speed stirring and dissolving 60min of 500 commentaries on classics/min, join in the 5kg methyl alcohol stirring tank that is preheating to 50 ℃ with the speed of 100ml/min then and precipitate, stirring velocity is 1500 commentaries on classics/min in the adition process, plastic solution adds the back to be continued to stir 60min under action of ultrasonic waves, and frequency of ultrasonic is that 20KHz, power are 0.5W/cm
2Filter down at 50 ℃ then, the plastics throw out filters and to obtain the plastics precipitation with 2kg methyl alcohol (50 ℃) washing 2 times, through devolatilization type twin screw extruder extruding under 180-220 ℃ remove solvent after, sampling analysis, the concentration that records the octa-BDE in the regenerated plastic sample is 0.067%, and the concentration of residual butanone is 0.03% in the plastics, and the concentration of methyl alcohol is 0.04%, the tensile strength of reprocessed plastic(s) sample is 44.34MPa, and notched Izod impact strength is 15.31KJ/m
2, with tensile strength and the 14.61KJ/m of 45.5MPa before the regeneration
2Notched Izod impact strength approaching.
Butanone and methanol mixture can be extracted butanone out at recovered overhead methyl alcohol by rectifying at the bottom of the tower, cold filtration is removed the octa-BDE crystal of separating out, and obtains being can be recycled by the saturated butanone of octa-BDE.
Embodiment 5
Contain in the waste and old HIPS particle of 1kg of decabromodiphenyl oxide 10% and the stirring tank that the 4kg kautschin joins one 10 liters, stirring and dissolving 90min under the normal temperature, solution with separation sieve (aperture is 1.00mm), is obtained impurity such as 4.88kg polymers soln and about insoluble plastic grain of 0.12kg and metal, glass, gravel.Polymers soln is passed through a high speed tubular-bowl centrifuge, the worry slag and the 4.6kg that isolate 0.28kg mud shape under the rotating speed of 15000 commentaries on classics/min consider liquid, adding 5kg kautschin control plastics concentration in considering liquid again is about 10%, is heated to 60 ℃, simultaneously at 100kHz, 0.5w/cm
2The ultrasonic wave effect under with the speed stirring and dissolving 120min of 500 commentaries on classics/min, join in the 27kg n-propyl alcohol stirring tank that is preheating to 60 ℃ with the speed of 100ml/min then and precipitate, the stirring velocity of n-propyl alcohol is 1000 commentaries on classics/min in the adition process, and frequency of ultrasonic is that 50KHz, power are 1w/cm
2Plastic solution adds the back and continue to stir 90min under action of ultrasonic waves, filter then, the plastics throw out filters and to obtain the plastics precipitation with 2.0kg n-propyl alcohol (60 ℃) washing 2 times, through devolatilization type twin screw extruder extruding under 180-220 ℃ remove solvent after, sampling analysis, the concentration that records the decabromodiphenyl oxide in the regenerated plastic sample is 0.088%, and the concentration of residual kautschin is 0.07% in the plastics, and the concentration of residual n-propyl alcohol is 0.04%.The tensile strength of reprocessed plastic(s) sample is 24.2MPa, and notched Izod impact strength is 6.93KJ/m
2, with tensile strength and the 6.21KJ/m of 27.5MPa before the regeneration
2Notched Izod impact strength approaching.
The mixture of kautschin and n-propyl alcohol can be extracted kautschin out at the recovered overhead n-propyl alcohol by rectifying at the bottom of the tower, cold filtration is removed the decabromodiphenyl oxide crystal of separating out, and obtains being can be recycled by the saturated kautschin of decabromodiphynly oxide.
Embodiment 6
Contain in 1kg waste and old polystyrol (PS) particle of decabromodiphenyl oxide 10% and the stirring tank that the 4kg kautschin joins one 10 liters, stirring and dissolving 90min under the normal temperature, solution with separation sieve (aperture is 1.00mm), is obtained impurity such as 4.85kg polymers soln and about insoluble plastic grain of 0.15kg and metal, glass, gravel.Plastic solution is passed through a high speed tubular-bowl centrifuge, the worry slag and the 4.59kg that isolate 0.26kg mud shape under the rotating speed of 15000 commentaries on classics/min consider liquid, in considering liquid, add the 4kg kautschin again, the concentration of polystyrene is reduced to about 10%, reheat to 100 ℃ is simultaneously at 100kHz/, 1.5w/cm
2The ultrasonic wave effect under with the speed stirring and dissolving 120min of 500 commentaries on classics/min, join in the 8kg Pentyl alcohol stirring tank that is preheating to 100 ℃ with the speed of 100ml/min then and precipitate, the stirring velocity of Pentyl alcohol is 2000 commentaries on classics/min in the adition process, plastic solution adds the back to be continued to stir 90min under action of ultrasonic waves, and frequency of ultrasonic is that 50KHz, power are 0.5w/cm
2Filter then, the plastics throw out washs 2 times with 2kg Pentyl alcohol (100 ℃), filtration obtains the plastics precipitation, through devolatilization type twin screw extruder extruding under 180-220 ℃ remove solvent after, sampling analysis, the concentration that records the decabromodiphenyl oxide of regenerated plastic sample is 0.088%, and the concentration of residual kautschin is 0.04% in the plastics, and the concentration of residual Pentyl alcohol is 0.06%.The tensile strength of reprocessed plastic(s) sample is 35.2MPa, and notched Izod impact strength is 3.43KJ/m
2, approaching with the notched Izod impact strength of the tensile strength of 37.5MPa and 3.21KJ/m before the regeneration.
The mixture of kautschin and Pentyl alcohol can be extracted kautschin out at the recovered overhead Pentyl alcohol by rectifying at the bottom of the tower, cold filtration is removed the decabromodiphenyl oxide crystal of separating out, and obtains being can be recycled by the saturated kautschin of decabromodiphynly oxide.
Embodiment 7
The waste and old housing of TV set shredded plastic of the 1kg particle (mainly being high-impact polystyrene and polystyrene) that contains decabromodiphenyl 5% and 4kg dimethylbenzene join in one 10 liters the stirring tank, stirring and dissolving 90min under the normal temperature, solution with separation sieve (aperture is 0.5mm), is obtained impurity such as 4.90kg polymers soln and about insoluble plastic grain of 0.10kg and metal, glass, gravel.By a high speed tubular-bowl centrifuge, the worry slag and the 4.72kg that isolate 0.18kg mud shape under the rotating speed of 15000 commentaries on classics/min consider liquid with polymers soln, and it is about 10% that additional 4kg dimethylbenzene makes plastics concentration, is heated to 60 ℃, simultaneously at 100kHz/, 1.5w/cm
2The ultrasonic wave effect under with the speed stirring and dissolving 120min of 500 commentaries on classics/min, join in the 24kg n-propyl alcohol stirring tank that is preheating to 60 ℃ with the speed of 100ml/min then and precipitate, the stirring velocity of n-propyl alcohol is 1000 commentaries on classics/min in the adition process, plastic solution adds the back to be continued to stir 90min under action of ultrasonic waves, and frequency of ultrasonic is that 50KHz, power are 0.5w/cm
2Filter then, the plastics throw out washs 2 times with 2kg n-propyl alcohol (60 ℃), filtration obtains the plastics precipitation, through devolatilization type twin screw extruder extruding under 180-220 ℃ remove solvent after, sampling analysis, the concentration that records the decabromodiphenyl in the reprocessed plastic(s) is 0.053%, and the concentration of residual dimethylbenzene is 0.03% in the plastics, and the concentration of residual n-propyl alcohol is 0.05%.The tensile strength of reprocessed plastic(s) sample is 29.3MPa, and notched Izod impact strength is 6.03KJ/m
2, with the tensile strength of 28.5MPa before the regeneration, 5.21KJ/m
2Notched Izod impact strength approaching.
The mixture of dimethylbenzene and n-propyl alcohol can be extracted dimethylbenzene out at the recovered overhead n-propyl alcohol by rectifying at the bottom of the tower, cold filtration is removed the decabromodiphenyl crystal of separating out, and obtains being can be recycled by the saturated dimethylbenzene of decabromodiphenyl.
Embodiment 8
The 1kg waste and old polystyrol (PS) that contains decabromodiphenyl oxide 8%, octa-BDE 2% and 4kg limonene join in one 10 liters the stirring tank, stirring and dissolving 60min under the normal temperature, solution by separation sieve (aperture is 1mm), is obtained impurity such as 4.89kg polymers soln and about insoluble plastic grain of 0.11kg and screw, glass, gravel.Polymers soln is passed through a high speed tubular-bowl centrifuge, the worry slag and the 4.57kg that isolate 0.32kg mud shape under the rotating speed of 15000 commentaries on classics/min consider liquid, adding 4.5kg limonene control plastics concentration again at worry liquid is about 10%, is heated to 50 ℃, simultaneously at 100kHz/, 0.5w/cm
2The ultrasonic wave effect under with the speed stirring and dissolving 120min of 1000 commentaries on classics/min, join in the 9kg isopropylcarbinol stirring tank that is preheating to 50 ℃ with the speed of 100ml/min then and precipitate, the stirring velocity of isopropylcarbinol is 2000 commentaries on classics/min in the adition process, plastic solution adds the back to be continued to stir 60min under action of ultrasonic waves, and frequency of ultrasonic is that 50KHz, power are 1.5w/cm
2Filter then, the plastics throw out washs 2 times with 2.0kg isopropylcarbinol (50 ℃), filtration obtains the plastics precipitation, through devolatilization type twin screw extruder extruding under 180-220 ℃ remove solvent after, sampling analysis, record the regenerated plastic sample, the concentration that sampling analysis records the decabromodiphenyl oxide in the plastics is 0.048%, the concentration of octa-BDE is 0.018%, total Poly Brominated Diphenyl Ethers, the concentration of Polybrominated biphenyl are 0.066%, the concentration of residual limonene is 0.03% in the plastics, and the concentration of residual isopropylcarbinol is 0.05%.The tensile strength of reprocessed plastic(s) sample is 36.2MPa, and notched Izod impact strength is 3.39KJ/m
2, with tensile strength and the 3.21KJ/m of 37.5MPa before the regeneration
2Notched Izod impact strength approaching.
The mixture of limonene and isopropylcarbinol is by rectifying, can extract limonene at the bottom of the tower out at the recovered overhead isopropylcarbinol, cold filtration is removed decabromodiphenyl oxide, the octa-BDE crystal of separating out, obtain being can be recycled by decabromodiphenyl oxide, toluene that octa-BDE is saturated.
Embodiment 9
Contain in the 1kg waste and old ABS/PC alloy plastic particle of octa-BDE 10% and the stirring tank that the 4kg butanone joins one 10 liters, stirring and dissolving 90min under the normal temperature, solution with separation sieve (aperture is 0.5mm), is obtained impurity such as 4.89kg polymers soln and about insoluble plastic grain of 0.11kg and metal, glass, gravel.By a high speed tubular-bowl centrifuge, the worry slag and the 4.67kg that isolate 0.22kg mud shape under the rotating speed of 10000 commentaries on classics/min consider liquid with polymers soln, and it is about 10% that additional 4kg butanone makes plastics concentration, is heated to 50 ℃, simultaneously at 100kHz/, 0.5w/cm
2The ultrasonic wave effect under with the speed stirring and dissolving 60min of 500 commentaries on classics/min, join in the 8kg methyl alcohol stirring tank that is preheating to 50 ℃ with the speed of 100ml/min then and precipitate, the stirring velocity of methyl alcohol is 1000 commentaries on classics/min in the adition process, and frequency of ultrasonic is that 50KHz, power are 0.5w/cm
2Plastic solution adds the back and continue to stir 90min under action of ultrasonic waves, filter then, the plastics throw out filters and to obtain the plastics precipitation with 2kg methyl alcohol (50 ℃) washing 2 times, through devolatilization type twin screw extruder extruding under 180-220 ℃ remove solvent after, sampling analysis, the concentration that records the octa-BDE in the reprocessed plastic(s) is 0.063%, and the concentration of residual butanone is 0.05% in the plastics, and the concentration of residual methanol is 0.03%.The tensile strength of reprocessed plastic(s) sample is 49.3MPa, and notched Izod impact strength is 10.03KJ/m
2, with tensile strength (50.5MPa) and the notched Izod impact strength (9.21KJ/m before the regeneration
2) approaching.
Butanone and methanol mixture can be extracted butanone out at recovered overhead methyl alcohol by rectifying at the bottom of the tower, cold filtration is removed the octa-BDE crystal of separating out, and obtains being can be recycled by the saturated butanone of octabromo-diphenyl.
Embodiment 10
Contain in the waste and old HIPS of 1kg (high-impact polystyrene) particle of decabromodiphenyl oxide 10% and the stirring tank that 4kg regenerated toluene joins one 10 liters, stirring and dissolving 60min under the normal temperature, solution is separated with separation sieve (aperture is 0.5mm), obtain impurity such as 4.88kg plastic solution and the insoluble plastic grain of 0.12kg and screw, glass, gravel.Plastic solution is passed through a high speed tubular-bowl centrifuge, the worry slag and the 4.52kg that isolate 0.35kg mud shape under the rotating speed of 10000 commentaries on classics/min consider liquid, in considering liquid, add 4kg regeneration toluene again the concentration of HIPS is reduced to about 10%, be heated to 50 ℃, insert 100kHz, 0.5W/em
2The ultrasonic wave effect under with the speed stirring and dissolving 60min of 500 commentaries on classics/min, join in the 8kg regenerated Virahol stirring tank that is preheating to 50 ℃ with the speed of 100ml/min then and precipitate, the stirring velocity of Virahol is 1000 commentaries on classics/min in the adition process, and frequency of ultrasonic is that 20KHz, power are 1.5W/cm
2Plastic solution adds the back and continue to stir 30min under action of ultrasonic waves, filter down at 50 ℃ then, the plastics throw out washs 2 times with 2.0kg regenerated Virahol (50 ℃), filtration obtains the plastics precipitation, through devolatilization type twin screw extruder extruding under 180-220 ℃ remove solvent after, sampling analysis, the concentration that records the decabromodiphenyl oxide in the regenerated plastic sample is 0.079%, the concentration of residual toluene is 0.03% in the plastics, the concentration of Virahol is 0.04%, and the tensile strength of reprocessed plastic(s) sample is 26.6MPa, and notched Izod impact strength is 7.71KJ/m
2, with the 27.5MPa tensile strength before the regeneration, 6.21KJ/m
2Notched Izod impact strength approaching.
The mixture of toluene and Virahol can be extracted toluene out at the recovered overhead Virahol by rectifying at the bottom of the tower, cold filtration is removed the decabromodiphenyl oxide crystal of separating out, and obtains being can be recycled by the saturated toluene of decabromodiphenyl oxide.
Claims (8)
1. the renovation process that contains the waste or used plastics of Polybrominated biphenyl and Poly Brominated Diphenyl Ethers is characterized in that comprising the steps:
(1) waste and old electric plastics is added in the solvent orange 2 A, dissolving at normal temperatures, the plastic quality percentage composition is 20～30% in the control solution; Described solvent orange 2 A is toluene, dimethylbenzene, butanone, Propiophenone, pimelinketone, methyl isoamyl ketone, limonene, kautschin, butylacetate and/or ethyl acetate; Described waste and old electric plastics is the thermoplastics that has added Polybrominated biphenyl and/or Poly Brominated Diphenyl Ethers;
(2) plastic solution after the dissolving sieves by separation sieve, and the aperture of screen cloth is 1.0～0.5mm, sifts out undissolved plastics and impurity;
(3) plastic solution after sieving carries out centrifugation, and rotating speed is separated greater than 1 micron particle particle diameter in the plastic solution more than or equal to 10000 commentaries on classics/min as considering slag;
(4) add in the plastic solution that solvent orange 2 A goes out to centrifugation, control plastic quality concentration is 10-20%, and solution temperature is brought up to 50-100 ℃, and solution is applied ultrasonic wave, is that 50-100KHz, power are 0.5-1.5w/cm in frequency
2Ultrasonic wave effect stirring and dissolving 60-120min down and under the rotating speed of 500-1000 commentaries on classics/min;
(5) plastic solution with step (4) gained adds among the solvent B, is that 20-50KHz, power are 0.5-1.5w/cm in frequency
2The ultrasonic wave effect and the rotating speed agitation condition of 1000-2000 commentaries on classics/min under, stir 30-90min, the plastics of separating out are precipitated with particulate state; Then with mixed solvent and plastics precipitate and separate; The plastics precipitation is washed with solvent B; Described solvent B is a monoalcohol solvent;
(6) the plastics throw out after the washing is sent into the twin screw extruder of devolatilization type, deviates from solvent residual in the throw out under 180-220 ℃, obtains to regenerate plastic prod.
2. the renovation process that contains the waste or used plastics of Polybrominated biphenyl and Poly Brominated Diphenyl Ethers according to claim 1 is characterized in that: described monoalcohol solvent is methyl alcohol, ethanol, n-propyl alcohol, Virahol, butanols, isopropylcarbinol and/or amylalcohol.
3. the renovation process that contains the waste or used plastics of Polybrominated biphenyl and Poly Brominated Diphenyl Ethers according to claim 1 is characterized in that: described step (5) mixed solvent is sent into rectifying tower, steams pure solvent B from cat head, extracts solvent orange 2 A out at the bottom of tower.
4. the renovation process that contains the waste or used plastics of Polybrominated biphenyl and Poly Brominated Diphenyl Ethers according to claim 1 is characterized in that: the dissolving of described step (1) is to be stirring and dissolving 60～90min under 100～200 commentaries on classics/min conditions in stir speed (S.S.).
5. the renovation process that contains the waste or used plastics of Polybrominated biphenyl and Poly Brominated Diphenyl Ethers according to claim 1 is characterized in that: the solvent orange 2 A of described step (1) and the mass ratio of waste and old electric plastics are 100: 25～43.
6. the renovation process that contains the waste or used plastics of Polybrominated biphenyl and Poly Brominated Diphenyl Ethers according to claim 1 is characterized in that: described impurity is metal, glass, gravel and/or the wood chip of insoluble solid material.
7. the renovation process that contains the waste or used plastics of Polybrominated biphenyl and Poly Brominated Diphenyl Ethers according to claim 1 is characterized in that: described step (3) particle diameter is Polybrominated biphenyl, Poly Brominated Diphenyl Ethers or additive particles greater than 1 micron particle.
8. the renovation process that contains the waste or used plastics of Polybrominated biphenyl and Poly Brominated Diphenyl Ethers according to claim 1 is characterized in that: the consumption of described solvent B be step (1) and step (4) solvent orange 2 A quality and 1-3 doubly.
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| CN105237799A (en) * | 2015-11-05 | 2016-01-13 | 广东石油化工学院 | Regeneration method of waste plastic containing polybrominated biphenyls and poly brominated diphenyl ethers |
| CN113144667A (en) * | 2021-04-01 | 2021-07-23 | 深圳市通产丽星科技集团有限公司 | Purification method and purification system for post-consumer recycled plastic |
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