CN107266664A - A kind of Reclaim of PET Scrap technique - Google Patents
A kind of Reclaim of PET Scrap technique Download PDFInfo
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- CN107266664A CN107266664A CN201710566121.6A CN201710566121A CN107266664A CN 107266664 A CN107266664 A CN 107266664A CN 201710566121 A CN201710566121 A CN 201710566121A CN 107266664 A CN107266664 A CN 107266664A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/16—Dicarboxylic acids and dihydroxy compounds
- C08G63/18—Dicarboxylic acids and dihydroxy compounds the acids or hydroxy compounds containing carbocyclic rings
- C08G63/181—Acids containing aromatic rings
- C08G63/183—Terephthalic acids
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/30—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group
- C07C67/317—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by splitting-off hydrogen or functional groups; by hydrogenolysis of functional groups
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/48—Separation; Purification; Stabilisation; Use of additives
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/78—Preparation processes
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J11/00—Recovery or working-up of waste materials
- C08J11/04—Recovery or working-up of waste materials of polymers
- C08J11/06—Recovery or working-up of waste materials of polymers without chemical reactions
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J11/00—Recovery or working-up of waste materials
- C08J11/04—Recovery or working-up of waste materials of polymers
- C08J11/10—Recovery or working-up of waste materials of polymers by chemically breaking down the molecular chains of polymers or breaking of crosslinks, e.g. devulcanisation
- C08J11/18—Recovery or working-up of waste materials of polymers by chemically breaking down the molecular chains of polymers or breaking of crosslinks, e.g. devulcanisation by treatment with organic material
- C08J11/22—Recovery or working-up of waste materials of polymers by chemically breaking down the molecular chains of polymers or breaking of crosslinks, e.g. devulcanisation by treatment with organic material by treatment with organic oxygen-containing compounds
- C08J11/24—Recovery or working-up of waste materials of polymers by chemically breaking down the molecular chains of polymers or breaking of crosslinks, e.g. devulcanisation by treatment with organic material by treatment with organic oxygen-containing compounds containing hydroxyl groups
-
- 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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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Sustainable Development (AREA)
- Separation, Recovery Or Treatment Of Waste Materials Containing Plastics (AREA)
Abstract
The invention discloses a kind of Reclaim of PET Scrap technique, it is related to resource regeneration field, solves the recovery problem of coloured polyester waste material, comprise the following steps：S1, pet waste crushed, cleans, dry；It is complete that S2, pet waste and EG, catalyst add depolymerization reaction under reactor, 170 ~ 210 DEG C of constant temperature；S3,125 ~ 145 DEG C are cooled to, heat filtering obtains first-time filtrate and unreacted PET；S4, first-time filtrate distillation obtain EG；Liquid after S5, distillation adds solvent, and heat filtering obtains secondary filtrate and BHET oligomer；Added in S6, secondary filtrate and three filtrates are obtained after decolorising agent, heat filtering；S7, three filtrate crystallisation by cooling separate out acicular crystal, are filtrated to get monomer BHET, and in 60 DEG C of dryings；Final minification gathers under precondensation under the conditions of S8, low vacuum, high vacuum condition；S9, Cast Strip, cooling, pelletizing and drying, finally obtain PET grain products.
Description
Technical field
The present invention relates to resource regeneration technical field, more particularly to a kind of Reclaim of PET Scrap technique.
Background technology
Polyethylene terephthalate（PET, abbreviation polyester）It is important industrial raw materials, its primary articles include
Beverage bottle, fiber, film, chip base, electrical apparatus insulation material and engineering plastics etc., polyethylene terephthalate are by benzene two
Formic acid glycol ester homopolymerization, or by made from terephthalic acid (TPA), ethylene glycol polymerisation.With the urgency of polyester article annual production
Play rises, and the polyester waste material brought by polyester article is also skyrocketed through, in addition, in the forming process of polyester article, often
Various scraps and tailing can be produced.Because polyethylene terephthalate has very strong chemical inertness, deposit naturally
It is difficult to degrade or be decomposed by the microorganisms to put, and not only causes the huge wasting of resources, and produce serious environmental pollution.Therefore,
By production, processing, recycle to realize that resource circulates benignly, improve environmental quality, as the important of current polyester industrial
Problem, this not only has important economic benefit, it may have great social benefit.
At present to polyester waste material（Including useless PET polyester and its useless product）Recycle mainly have physics utilize and chemistry
Utilize two major classes.Physics is using i.e. useless PET polyester and its product by the simple physical treatment such as directly blending, blending, granulation
After regenrated slice is made, can be used for spinning Ji, membrane and engineering plastics etc. as secondary shelves product, realize secondary utilization.At physics
The PET managed is not yet directly used in packaging material for food at present due to hygienic reason, the PET polyester of polycondensation again only after depolymerization
Hygienic requirements of the grocery trade to material can just be met.In addition, waste PET directly reclaims the secondary slugs that processing is produced, because of characteristic
The excessively low reason of viscosity number should not be used directly again, can only realize that it is recycled by chemical depolymerization.PET chemical cycles
Application way mainly has Hydrolyze method（Including acid water solution, alkaline water solution and neutral hydrolysis）, methanol depolymerization, ethylene glycol
Depolymerization and overcritical ethylene glycol depolymerization, it is real although these methods can obtain the brand-new chemical raw material for polymerizeing PET
The processing of existing various level polyester articles, but they there is also various defects.The weak point of acid water solution is：Reaction consumption
Substantial amounts of concentrated acid and highly basic, it is difficult to recycle, easily cause environmental pollution, and the ethylene glycol of generation also more difficult is reclaimed；Alkalescence
Hydrolyze method equally has salkali waste discharge, pollutes environment, need to carry out appropriate environmental protection treatment；Neutral hydrolysis is needed in high temperature, high pressure
It is lower to carry out, or need to contain a large amount of impurity in alkali as a catalyst, and depolymerization product, it is impossible to directly utilize, subsequent treatment ratio
It is cumbersome；Methanol depolymerization technics comparing is simple, but product purification is complicated, and final products quality is low, due under usual terms
The methanol degradation reaction time is longer, decomposes not thorough, the methanol depolymerization PET having been carried out is no more than for DMT degradation rate
90%, it is unfavorable for industrialized continuous production；Ethylene glycol depolymerization technics comparing is complicated.Overcritical ethylene glycol depolymerization reacts bar
Part is harsh, it is necessary to which high temperature, high pressure, technique realize that more difficult and cost is high.
Application publication number discloses a kind of polyester waste by normal-pressure alcoholysis for CN101906218A Chinese invention patent and reclaimed
Application way, although the purpose for recycling polyester waste material can be reached, but do not occur the step related to decolouring wherein,
Therefore the method is not suitable for the recycling of coloured polyester waste material, can not just solve the recovery problem of coloured polyester waste material yet.
The content of the invention
The technical problems to be solved by the invention are the recycling problems of coloured polyester waste material, overcome lacking for prior art
Point solves the recovery problem of coloured polyester waste material there is provided a kind of Reclaim of PET Scrap technique.
In order to solve the above technical problems, the present invention provides a kind of Reclaim of PET Scrap technique, comprise the following steps：
S1, pet waste crushed, and clean, dry；
S2, the pet waste of dry cleansing and ethylene glycol, catalyst are added in reactor in the lump, are heated to 170 ~ 210 DEG C, constant temperature
Lower stirring mixes complete to depolymerization reaction；
S3, reaction are cooled to 125 ~ 145 DEG C after terminating, and quick heat filtering, obtains first-time filtrate and coloured insoluble matter is not i.e. anti-
The PET answered；
S4, first-time filtrate is distilled, recovery obtains ethylene glycol；
S5, to the liquid after distillation solvent is added, filtered after heating, obtain the double hydroxyls of secondary filtrate and insoluble matter i.e. terephthalic acid (TPA)
The oligomer of ethyl ester；
S6, three filtrates that water white transparency is obtained after decolorising agent, heat filtering are added into secondary filtrate；
S7, three filtrate natural coolings, crystallization separate out acicular crystal, are filtrated to get the double hydroxyl ethyl esters of monomers terephthalic acid, and
Dried at 60 DEG C；
S8, with nitrogen the double hydroxyl ethyl ester materials of monomers terephthalic acid are pressed into batch condensation polymerization reactors, carried out under the conditions of low vacuum
Precondensation, then carries out final minification and gathers in high vacuum conditions；
S9, polycondensation are extruded material by nitrogen after terminating, Cast Strip, cooling, pelletizing and drying, finally obtain PET grain products.
Technique effect：Glycolysis alcoholysis method is industrial prospect most a kind of prominent method in Reclaim of PET Scrap method,
The present invention uses glycolysis alcoholysis method, and increases decolorization process for coloured polyester waste material in the process, through glycolysis alcoholysis
After obtain the double hydroxyl ethyl esters of monomers terephthalic acid, then purified aftercondensated forms the PET particles of white, solves coloured discarded poly-
The recycle of ester material because color be restricted the problem of, so as to reach the purpose recycled to polyester waste material.This method
It is simple and easy to apply, the alcoholysis high conversion rate of polyester waste material, therefore recovery utilization rate is high；The ethylene glycol used in production process is recyclable
Reuse, environmental protection reduces cost again；The technique is adapted to industrialization, with preferable Social benefit and economic benefit.
The technical scheme that further limits of the present invention is：
Further, in step S2, depolymerization reaction carries out 2.5 ~ 3.5h under 195 ~ 197 DEG C of constant temperature.
In a kind of preceding described Reclaim of PET Scrap technique, step S2, the quality of ethylene glycol is 2 times of pet waste quality.
In a kind of preceding described Reclaim of PET Scrap technique, step S2, the catalyst of depolymerization reaction uses zinc oxide or vinegar
Sour zinc, and the quality of catalyst is the 0.45 ~ 0.55% of pet waste quality.
In a kind of preceding described Reclaim of PET Scrap technique, step S4, using air-distillation absorption method：By first-time filtrate plus
Enter into reactor, be passed through nitrogen and condensed water, be heated to boiling point i.e. 197 DEG C of ethylene glycol, the second two being distilled to recover under normal pressure
Alcohol.
In a kind of preceding described Reclaim of PET Scrap technique, step S4, using revolving absorption method：First-time filtrate is cooled to
85 ~ 95 DEG C, the deionized water of a small amount of 85 ~ 95 DEG C of addition stirs suction filtration, obtains filtrate afterwards twice repeatedly；Pass through rotary evaporator
Moisture in filtrate is steamed；A small amount of calcium chloride is added into remaining solution again, 12 ~ 14h, the second two being recycled is stood
Alcohol.
In a kind of preceding described Reclaim of PET Scrap technique, step S4, using vacuum distillation absorption method：By first-time filtrate plus
Enter into reactor, be passed through condensed water, open multiplex vavuum pump of circulating water type, using magnetic stirrer, be slowly heated to
Liquid is oozed；Heating-up temperature is adjusted, the speed let the liquid out is per second to be no more than 1 drop；Stop heating after having distilled, be recycled
Ethylene glycol.
In a kind of preceding described Reclaim of PET Scrap technique, step S5, solvent can be used in toluene, dimethylbenzene or acetone
Any one.
In a kind of preceding described Reclaim of PET Scrap technique, step S6, decolorising agent is hydrogen peroxide or activated carbon.
In a kind of preceding described Reclaim of PET Scrap technique, step S6, decolorising agent is activated carbon, and bleaching temperature be 80 ~
85 DEG C, bleaching time is 1 ~ 1.5h, and the quality of activated carbon is the 10% of secondary filtrate quality.
The beneficial effects of the invention are as follows：
（1）In the present invention, the alcoholysis reaction of polyester waste material is endothermic process, therefore is conducive to reaction to carry out with the rise of temperature,
But temperature is too high, the volatilization loss of ethylene glycol is not only resulted in, energy consumption of reaction increases, and reaction speed slows down, and can cause second
Shunk between glycol molecules side reaction, therefore temperature selection, in 196 DEG C or so of the boiling point of ethylene glycol, reaction depolymerization rate is close to most
It is high；
（2）In the present invention, with the increase in reaction time, reaction depolymerization rate increases, but when the alcoholysis time continuing to increase, due to
Alcoholysis product polymerize again, and the reaction depolymerization rate reaction time on a declining curve therefore appropriate is 2.5 ~ 3h or so；
（3）In the present invention, increase with the amount ratio of ethylene glycol and pet waste, depolymerization rate also increases, when ethylene glycol and PET are useless
When the mass ratio of material reaches 2, it is held essentially constant to the later stage, therefore appropriate ethylene glycol consumption is twice of PET mass；
（4）In the present invention, revolving method recovery ethylene glycol technique power consumption is minimum, and does not influence the quality of PET catabolites, the rate of recovery
Height, therefore revolving recovery process is more excellent；
（5）In the present invention, hydrogen peroxide and activated carbon decolorizing can obtain qualified products, and hydrogen peroxide for decoloration effect is preferable, but product
Loss is larger, and the loss of activated carbon decolorizing product is less, therefore can select active carbon adsorption；
（6）In the present invention, the product that being passed through nitrogen can play after reduction depolymerization reaction is aoxidized again, so as to improve percent alcoholysis.
Embodiment
Embodiment 1
A kind of Reclaim of PET Scrap technique that the present embodiment is provided, including the following raw material：
Pet waste（The green beverage bottle of recovery）-100kg；
Ethylene glycol（AR grades）- 200kg- Nanjing chemical reagent limited company；
Zinc acetate -0.5kg- Nanjing chemical reagent limited company；
Calcium chloride -2kg- Nanjing chemical reagent limited company；
Acetone -5kg- Nanjing chemical reagent limited company；
Activated carbon -10kg- Nanjing chemical reagent limited company；
Comprise the following steps that：
S1, pet waste crushed, and clean, dry；
S2, dry cleansing pet waste and ethylene glycol（EG）, zinc acetate add in the lump in reactor, be heated to 196 DEG C, constant temperature
Lower stirring mixing 3h or so is complete to depolymerization reaction；
S3, reaction are cooled to 135 DEG C after terminating, and quick heat filtering, obtains first-time filtrate and coloured insoluble matter is i.e. unreacted
PET；
S4, first-time filtrate is cooled to 90 DEG C, adds a small amount of 90 DEG C of deionized water, stir suction filtration, filtered afterwards twice repeatedly
Liquid；The moisture in filtrate is steamed by RE-201C rotary evaporators；Calcium chloride is added into remaining solution again, 12h is stood,
The EG being recycled；
S5, to the liquid after distillation acetone is added, filtered after heating, obtain the double hydroxyl second of secondary filtrate and insoluble matter i.e. phthalic acid
Ester（BHET）Oligomer；
S6, three filtrates that water white transparency is obtained after the 1h that decolourized at activated carbon, 80 DEG C, heat filtering are added into secondary filtrate；
S7, three filtrate natural coolings, crystallization separate out acicular crystal, are filtrated to get monomer BHET, and dried at 60 DEG C；
S8, with nitrogen by monomer BHET materials be pressed into batch condensation polymerization reactor in, in low vacuum（40mmHg）Under the conditions of carry out precondensation,
Then in high vacuum（＜ 3mmHg）Under the conditions of carry out final minification gather；
S9, polycondensation are extruded material by nitrogen after terminating, Cast Strip, cooling, pelletizing and drying, finally obtain PET grain products.
Embodiment 2
A kind of Reclaim of PET Scrap technique that the present embodiment is provided, including the following raw material：
Pet waste（The green beverage bottle of recovery）-150kg；
EG（AR grades）- 300kg- Nanjing chemical reagent limited company；
Zinc acetate -0.75kg- Nanjing chemical reagent limited company；
Calcium chloride -3kg- Nanjing chemical reagent limited company；
Acetone -7.5kg- Nanjing chemical reagent limited company；
Activated carbon -15kg- Nanjing chemical reagent limited company；
Comprise the following steps that：
S1, pet waste crushed, and clean, dry；
S2, the pet waste of dry cleansing and EG, zinc acetate are added in reactor in the lump, are heated to 196 DEG C, stir mixed under constant temperature
2.5h or so is closed, it is complete to depolymerization reaction；
S3, reaction are cooled to 125 DEG C after terminating, and quick heat filtering, obtains first-time filtrate and coloured insoluble matter is i.e. unreacted
PET；
S4, first-time filtrate is cooled to 85 DEG C, adds a small amount of 85 DEG C of deionized water, stir suction filtration, filtered afterwards twice repeatedly
Liquid；The moisture in filtrate is steamed by RE-201C rotary evaporators；Calcium chloride is added into remaining solution again, 13h is stood,
The EG being recycled；
S5, to after distillation liquid add acetone, after heating filter, obtain secondary filtrate and insoluble matter i.e. BHET oligomer；
S6, three filtrates that water white transparency is obtained after the 1h that decolourized at activated carbon, 83 DEG C, heat filtering are added into secondary filtrate；
S7, three filtrate natural coolings, crystallization separate out acicular crystal, are filtrated to get monomer BHET, and dried at 60 DEG C；
S8, with nitrogen by monomer BHET materials be pressed into batch condensation polymerization reactor in, in low vacuum（40mmHg）Under the conditions of carry out precondensation,
Then in high vacuum（＜ 3mmHg）Under the conditions of carry out final minification gather；
S9, polycondensation are extruded material by nitrogen after terminating, Cast Strip, cooling, pelletizing and drying, finally obtain PET grain products.
Embodiment 3
A kind of Reclaim of PET Scrap technique that the present embodiment is provided, including the following raw material：
Pet waste（The green beverage bottle of recovery）-200kg；
EG（AR grades）- 400kg- Nanjing chemical reagent limited company；
Zinc acetate -2kg- Nanjing chemical reagent limited company；
Calcium chloride -4kg- Nanjing chemical reagent limited company；
Acetone -10kg- Nanjing chemical reagent limited company；
Activated carbon -20kg- Nanjing chemical reagent limited company；
Comprise the following steps that：
S1, pet waste crushed, and clean, dry；
S2, the pet waste of dry cleansing and EG, zinc acetate are added in reactor in the lump, are heated to 196 DEG C, stir mixed under constant temperature
3.5h or so is closed, it is complete to depolymerization reaction；
S3, reaction are cooled to 145 DEG C after terminating, and quick heat filtering, obtains first-time filtrate and coloured insoluble matter is i.e. unreacted
PET；
S4, first-time filtrate is cooled to 95 DEG C, adds a small amount of 95 DEG C of deionized water, stir suction filtration, filtered afterwards twice repeatedly
Liquid；The moisture in filtrate is steamed by RE-201C rotary evaporators；Calcium chloride is added into remaining solution again, 14h is stood,
The EG being recycled；
S5, to after distillation liquid add acetone, after heating filter, obtain secondary filtrate and insoluble matter i.e. BHET oligomer；
S6, three filtrates that water white transparency is obtained after the 1.5h that decolourized at activated carbon, 85 DEG C, heat filtering are added into secondary filtrate；
S7, three filtrate natural coolings, crystallization separate out acicular crystal, are filtrated to get monomer BHET, and dried at 60 DEG C；
S8, with nitrogen by monomer BHET materials be pressed into batch condensation polymerization reactor in, in low vacuum（40mmHg）Under the conditions of carry out precondensation,
Then in high vacuum（＜ 3mmHg）Under the conditions of carry out final minification gather；
S9, polycondensation are extruded material by nitrogen after terminating, Cast Strip, cooling, pelletizing and drying, finally obtain PET grain products.
Using differential scanning calorimetric（DSC）Analysis, infrared spectrum analysis, efficient liquid phase chromatographic analysis, nuclear magnetic resonance H spectrums point
Analysis is analyzed product, consistent with content described in above-described embodiment.
Formula one：；
Formula two：；
The percent alcoholysis and the rate of recovery of pet waste are calculated by formula one, formula two, wherein：M1 is the quality of pet waste in step S1, m2
For the quality of unreacted pet waste in step S3, m3 monomer BHET obtained by after being dried in step S7 quality；
In addition, the EG rate of recovery is calculated by formula two, wherein：The quality that m1 is EG in step S2, m3 is recovery EG in step S4
Quality.
As seen from the above table, the recovery process for the polyester waste material that the present invention is provided, the average percent alcoholysis of pet waste reaches
99.4%, the average recovery rate of pet waste reaches that 99.0%, EG average recovery rate reaches 97.5%.The technique not only causes polyester
Waste material has obtained good recycling, while the ethylene glycol recovery utilization rate in processing procedure is also very high, furthermore achieved that
The purpose of environmental protection recycling production；The recycling problem of coloured polyester waste material is solved well, and colourless, coloured polyester is given up
Material is all suitable for, and practicality is high, have a wide range of application；Polyester waste material is ultimately converted to PET grain products, in the pin of enterprise's production and application
It is strong to property.
In addition to the implementation, the present invention can also have other embodiment.All use equivalent substitution or equivalent transformation shape
Into technical scheme, all fall within the protection domain of application claims.
Claims (10)
1. a kind of Reclaim of PET Scrap technique, it is characterised in that：Comprise the following steps：
S1, pet waste crushed, and clean, dry；
S2, the pet waste of dry cleansing and ethylene glycol, catalyst are added in reactor in the lump, are heated to 170 ~ 210 DEG C, constant temperature
Lower stirring mixes complete to depolymerization reaction；
S3, reaction are cooled to 125 ~ 145 DEG C after terminating, and quick heat filtering, obtains first-time filtrate and coloured insoluble matter is not i.e. anti-
The PET answered；
S4, first-time filtrate is distilled, recovery obtains ethylene glycol；
S5, to the liquid after distillation solvent is added, filtered after heating, obtain the double hydroxyls of secondary filtrate and insoluble matter i.e. terephthalic acid (TPA)
The oligomer of ethyl ester；
S6, three filtrates that water white transparency is obtained after decolorising agent, heat filtering are added into secondary filtrate；
S7, three filtrate natural coolings, crystallization separate out acicular crystal, are filtrated to get the double hydroxyl ethyl esters of monomers terephthalic acid, and
Dried at 60 DEG C；
S8, with nitrogen the double hydroxyl ethyl ester materials of monomers terephthalic acid are pressed into batch condensation polymerization reactors, carried out under the conditions of low vacuum
Precondensation, then carries out final minification and gathers in high vacuum conditions；
S9, polycondensation are extruded material by nitrogen after terminating, Cast Strip, cooling, pelletizing and drying, finally obtain PET grain products.
2. a kind of Reclaim of PET Scrap technique according to claim 1, it is characterised in that：In the step S2, depolymerization is anti-
2.5 ~ 3.5h should be carried out under 195 ~ 197 DEG C of constant temperature.
3. a kind of Reclaim of PET Scrap technique according to claim 2, it is characterised in that：In the step S2, ethylene glycol
Quality be 2 times of pet waste quality.
4. a kind of Reclaim of PET Scrap technique according to claim 3, it is characterised in that：In the step S2, depolymerization is anti-
The catalyst answered uses zinc oxide or zinc acetate, and the quality of catalyst is the 0.45 ~ 0.55% of pet waste quality.
5. a kind of Reclaim of PET Scrap technique according to claim 1, it is characterised in that：In the step S4, using normal
Press distillation recovery method：First-time filtrate is added in reactor, nitrogen and condensed water is passed through, the boiling point of ethylene glycol is heated to i.e.
197 DEG C, the ethylene glycol being distilled to recover under normal pressure.
6. a kind of Reclaim of PET Scrap technique according to claim 1, it is characterised in that：In the step S4, using rotation
Steam absorption method：First-time filtrate is cooled to 85 ~ 95 DEG C, a small amount of 85 ~ 95 DEG C of deionized water is added, suction filtration is stirred, repeatedly twice
After obtain filtrate；The moisture in filtrate is steamed by rotary evaporator；A small amount of calcium chloride is added into remaining solution again, it is quiet
12 ~ 14h is put, the ethylene glycol being recycled.
7. a kind of Reclaim of PET Scrap technique according to claim 1, it is characterised in that：In the step S4, using subtracting
Press distillation recovery method：First-time filtrate is added in reactor, condensed water is passed through, multiplex vavuum pump of circulating water type is opened, used
Magnetic stirrer, is slowly heated to liquid and oozes；Heating-up temperature is adjusted, the speed let the liquid out is per second to be no more than 1 drop；
Stop heating, the ethylene glycol being recycled after having distilled.
8. a kind of Reclaim of PET Scrap technique according to claim 1, it is characterised in that：In the step S5, solvent can
Using any one in toluene, dimethylbenzene or acetone.
9. a kind of Reclaim of PET Scrap technique according to claim 1, it is characterised in that：In the step S6, decolorising agent
For hydrogen peroxide or activated carbon.
10. a kind of Reclaim of PET Scrap technique according to claim 9, it is characterised in that：In the step S6, decolorising agent
For activated carbon, and bleaching temperature is 80 ~ 85 DEG C, and bleaching time is 1 ~ 1.5h, and the quality of activated carbon is secondary filtrate quality
10%。
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710566121.6A CN107266664A (en) | 2017-07-12 | 2017-07-12 | A kind of Reclaim of PET Scrap technique |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710566121.6A CN107266664A (en) | 2017-07-12 | 2017-07-12 | A kind of Reclaim of PET Scrap technique |
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| Publication Number | Publication Date |
|---|---|
| CN107266664A true CN107266664A (en) | 2017-10-20 |
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Cited By (11)
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| CN108018709A (en) * | 2017-12-21 | 2018-05-11 | 福建荔枝新材料有限公司 | A kind of polyester material recycles and utilizes plasma to carry out surface treatment method |
| CN110128271A (en) * | 2019-06-10 | 2019-08-16 | 东莞博斯环保科技有限公司 | A method of dimethyl terephthalate (DMT) is prepared using waste PET polyester |
| CN110229062A (en) * | 2019-06-10 | 2019-09-13 | 东莞博斯环保科技有限公司 | A kind of recovery method of waste PET polyester |
| CN110272608A (en) * | 2019-06-04 | 2019-09-24 | 中塑联新材料科技湖北有限公司 | The modified method of PET filling modeling ABS is aggregated into terylene waste spinning depolymerization purification |
| CN112759746A (en) * | 2019-10-21 | 2021-05-07 | 中国石油化工股份有限公司 | Preparation method of high-cleanness food grade recycled bottle flakes |
| IT201900025039A1 (en) * | 2019-12-20 | 2021-06-20 | Garbo S R L | PROCESS TO PURIFY BIS (2-HYDROXYETHYL) TEREPHTHALATE. |
| CN113603584A (en) * | 2021-08-16 | 2021-11-05 | 苏州大学 | Method for photo-thermal degradation of polyester |
| CN114367512A (en) * | 2021-12-06 | 2022-04-19 | 界首市双特新材料科技有限公司 | Polyethylene terephthalate bottle recovery processing technology |
| CN114989400A (en) * | 2022-07-05 | 2022-09-02 | 河南源宏高分子新材料有限公司 | Preparation method of chemically regenerated PETG polyester |
| WO2023060768A1 (en) | 2021-10-13 | 2023-04-20 | 国高材高分子材料产业创新中心有限公司 | Method for preparing regenerated polyester by means of closed-loop recovery of waste polyester with typical green and low-carbon characteristics |
| US11858891B2 (en) | 2021-11-08 | 2024-01-02 | Nan Ya Plastics Corporation | Decolorization and purification method of BHET material |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108018709A (en) * | 2017-12-21 | 2018-05-11 | 福建荔枝新材料有限公司 | A kind of polyester material recycles and utilizes plasma to carry out surface treatment method |
| CN110272608A (en) * | 2019-06-04 | 2019-09-24 | 中塑联新材料科技湖北有限公司 | The modified method of PET filling modeling ABS is aggregated into terylene waste spinning depolymerization purification |
| CN110128271A (en) * | 2019-06-10 | 2019-08-16 | 东莞博斯环保科技有限公司 | A method of dimethyl terephthalate (DMT) is prepared using waste PET polyester |
| CN110229062A (en) * | 2019-06-10 | 2019-09-13 | 东莞博斯环保科技有限公司 | A kind of recovery method of waste PET polyester |
| CN112759746A (en) * | 2019-10-21 | 2021-05-07 | 中国石油化工股份有限公司 | Preparation method of high-cleanness food grade recycled bottle flakes |
| WO2021124149A1 (en) * | 2019-12-20 | 2021-06-24 | Garbo S.R.L. | Process for purifying bis(2-hydroxyethyl)terephthalate |
| IT201900025039A1 (en) * | 2019-12-20 | 2021-06-20 | Garbo S R L | PROCESS TO PURIFY BIS (2-HYDROXYETHYL) TEREPHTHALATE. |
| CN114746391A (en) * | 2019-12-20 | 2022-07-12 | 嘉尔宝有限责任公司 | Process for purifying bis (2-hydroxyethyl) terephthalate |
| CN113603584A (en) * | 2021-08-16 | 2021-11-05 | 苏州大学 | Method for photo-thermal degradation of polyester |
| WO2023060768A1 (en) | 2021-10-13 | 2023-04-20 | 国高材高分子材料产业创新中心有限公司 | Method for preparing regenerated polyester by means of closed-loop recovery of waste polyester with typical green and low-carbon characteristics |
| US11858891B2 (en) | 2021-11-08 | 2024-01-02 | Nan Ya Plastics Corporation | Decolorization and purification method of BHET material |
| CN114367512A (en) * | 2021-12-06 | 2022-04-19 | 界首市双特新材料科技有限公司 | Polyethylene terephthalate bottle recovery processing technology |
| CN114989400A (en) * | 2022-07-05 | 2022-09-02 | 河南源宏高分子新材料有限公司 | Preparation method of chemically regenerated PETG polyester |
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Application publication date: 20171020 |