CN102532591A - Method for depolymerizing waste polyester bottle - Google Patents
Method for depolymerizing waste polyester bottle Download PDFInfo
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- CN102532591A CN102532591A CN2012100398715A CN201210039871A CN102532591A CN 102532591 A CN102532591 A CN 102532591A CN 2012100398715 A CN2012100398715 A CN 2012100398715A CN 201210039871 A CN201210039871 A CN 201210039871A CN 102532591 A CN102532591 A CN 102532591A
- Authority
- CN
- China
- Prior art keywords
- polyester bottle
- waste
- obtains
- terephthalic acid
- terepthaloyl moietie
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
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- 229920000728 polyester Polymers 0.000 title claims abstract description 43
- 238000000034 method Methods 0.000 title claims abstract description 32
- 239000002699 waste material Substances 0.000 title claims abstract description 32
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims abstract description 46
- 239000000047 product Substances 0.000 claims abstract description 23
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 18
- 238000006243 chemical reaction Methods 0.000 claims abstract description 17
- 238000001035 drying Methods 0.000 claims abstract description 10
- 238000001816 cooling Methods 0.000 claims abstract description 8
- 230000035484 reaction time Effects 0.000 claims abstract description 5
- 238000002390 rotary evaporation Methods 0.000 claims abstract description 5
- 239000007788 liquid Substances 0.000 claims description 21
- 238000000967 suction filtration Methods 0.000 claims description 17
- 239000012535 impurity Substances 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 11
- 239000000126 substance Substances 0.000 claims description 6
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 claims description 5
- 230000008021 deposition Effects 0.000 claims description 5
- 229910001415 sodium ion Inorganic materials 0.000 claims description 5
- 238000010521 absorption reaction Methods 0.000 claims description 4
- 239000003610 charcoal Substances 0.000 claims description 4
- 239000012065 filter cake Substances 0.000 claims description 4
- 239000012634 fragment Substances 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 4
- 239000007787 solid Substances 0.000 claims description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 abstract description 23
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 abstract description 10
- 238000005406 washing Methods 0.000 abstract description 6
- 229910000030 sodium bicarbonate Inorganic materials 0.000 abstract description 5
- 235000017557 sodium bicarbonate Nutrition 0.000 abstract description 5
- 238000001914 filtration Methods 0.000 abstract 2
- 229920000139 polyethylene terephthalate Polymers 0.000 abstract 2
- 239000005020 polyethylene terephthalate Substances 0.000 abstract 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract 1
- -1 Polyethylene Terephthalate Polymers 0.000 abstract 1
- 239000006227 byproduct Substances 0.000 abstract 1
- 229910052799 carbon Inorganic materials 0.000 abstract 1
- 238000004040 coloring Methods 0.000 abstract 1
- VIQSRHWJEKERKR-UHFFFAOYSA-L disodium;terephthalate Chemical compound [Na+].[Na+].[O-]C(=O)C1=CC=C(C([O-])=O)C=C1 VIQSRHWJEKERKR-UHFFFAOYSA-L 0.000 abstract 1
- 239000012153 distilled water Substances 0.000 abstract 1
- 239000005457 ice water Substances 0.000 abstract 1
- 238000004821 distillation Methods 0.000 description 7
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 7
- 238000005303 weighing Methods 0.000 description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 230000007062 hydrolysis Effects 0.000 description 4
- 238000006460 hydrolysis reaction Methods 0.000 description 4
- 238000004811 liquid chromatography Methods 0.000 description 4
- 238000011084 recovery Methods 0.000 description 4
- 206010013786 Dry skin Diseases 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- QPKOBORKPHRBPS-UHFFFAOYSA-N bis(2-hydroxyethyl) terephthalate Chemical compound OCCOC(=O)C1=CC=C(C(=O)OCCO)C=C1 QPKOBORKPHRBPS-UHFFFAOYSA-N 0.000 description 3
- 239000007795 chemical reaction product Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000002386 leaching Methods 0.000 description 3
- 239000012263 liquid product Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000007789 sealing Methods 0.000 description 3
- 238000004587 chromatography analysis Methods 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- WOZVHXUHUFLZGK-UHFFFAOYSA-N dimethyl terephthalate Chemical compound COC(=O)C1=CC=C(C(=O)OC)C=C1 WOZVHXUHUFLZGK-UHFFFAOYSA-N 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000007380 fibre production Methods 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- OJURWUUOVGOHJZ-UHFFFAOYSA-N methyl 2-[(2-acetyloxyphenyl)methyl-[2-[(2-acetyloxyphenyl)methyl-(2-methoxy-2-oxoethyl)amino]ethyl]amino]acetate Chemical compound C=1C=CC=C(OC(C)=O)C=1CN(CC(=O)OC)CCN(CC(=O)OC)CC1=CC=CC=C1OC(C)=O OJURWUUOVGOHJZ-UHFFFAOYSA-N 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 239000012429 reaction media Substances 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- 150000003504 terephthalic acids Chemical class 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000006136 alcoholysis reaction Methods 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 235000013361 beverage Nutrition 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000012691 depolymerization reaction Methods 0.000 description 1
- 239000010791 domestic waste Substances 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- IISLNQNUYOZKNE-UHFFFAOYSA-N sodium;terephthalic acid Chemical compound [Na].OC(=O)C1=CC=C(C(O)=O)C=C1 IISLNQNUYOZKNE-UHFFFAOYSA-N 0.000 description 1
- 238000009987 spinning Methods 0.000 description 1
- 230000009967 tasteless effect Effects 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 238000003828 vacuum filtration Methods 0.000 description 1
Classifications
-
- 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
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Separation, Recovery Or Treatment Of Waste Materials Containing Plastics (AREA)
Abstract
The invention provides a method for depolymerizing a waste polyester bottle, comprising the following steps of: adding the waste polyester bottle, ethylene glycol, sodium bicarbonate and distilled water into a high-temperature and high-pressure reaction kettle according to a certain proportion and reacting at a temperature of 170-200 DEG C for 15-40 minutes to depolymerize the waste polyester bottle into sodium terephthalate, ethylene glycol and other byproducts; then, adsorbing by active carbon and de-coloring; acidifying by hydrochloric acid, and cooling and crystallizing by ice water; filtering, washing and drying to obtain terephthalic acid; and carrying out rotary evaporation on a filtering solution to obtain the ethylene glycol to be repeatedly utilized. According to the method for depolymerizing the waste polyester bottle, by utilizing a mixed reaction system, the depolymerization temperature is reduced, the reaction time is shortened, the energy source consumption is reduced, the equipment investment is reduced, the depolymerization rate of PET (Polyethylene Terephthalate) reaches to be more than 99% and the yield of the target product, namely terephthalic acid, is more than 94%.
Description
Technical field:
The present invention relates to a kind of depolymerization method of waste and old polyester bottle, under the weak basic condition of more specifically saying so, utilize the method for terepthaloyl moietie and water disaggregation of waste and old pet bottle in airtight high-temperature high-pressure reaction kettle.
Background technology:
Characteristics such as pet bottle is tasteless, nontoxic owing to having, light weight, intensity is big, resistance to air loss good, transparency is good extensively apply to fields such as beverage, food, medicine.At present, the yield of whole world waste and old polyester bottle is more than 600kt/a, and the recovery is about 18%, and the polyester after the recovery has and is used for fiber production more than 60%.And the recovery of domestic waste and old polyester bottle is merely 6%～10%, wherein has 40%～60% to be used for fiber production.
The recycle method of pet bottle mainly contains two types; One type is that physics utilizes method; Be to process regenrated slice after the waste and old polyester bottle is handled through simple physics such as direct blending, blend, granulations, can be used for spinning, membrane and engineering plastics etc., realize second stage employ as inferior shelves product; Another kind of is that chemistry utilizes method; Be that depolymerization reaction takes place under the effect of heat and chemical reagent pet bottle; Generate low-molecular-weight product, product through separate, can be again behind the purifying as the raw material of the monomer of producing polyester or synthetic other Chemicals, thereby realized the resource circulation utilization.
Utilize in the method at chemistry, method commonly used has hydrolysis method and alcoholysis method.Among the patent US4605762, the polyester waste material of being handled by twin-screw extruder is at 248 ℃, hydrolysis after 2 hours under the condition of 4.2MPa, product through filter, crystallisation by cooling, drying obtain the product terephthalic acid fast; Among the patent US3952053, introduced a kind of decomposing polyester and reclaimed method of terephthalic acid.Utilize massfraction to be at least 87% the vitriol oil; Hydrolysis polyester waste material under the condition of normal pressure and 37～100 ℃; Obtain the mixing solutions that terephthalic acid and sulfuric acid are formed, add proper amount of sodium hydroxide solution, through removing by filter insolubles and pigment; Add sulfuric acid then and obtain the white precipitate terephthalic acid, terepthaloyl moietie then takes out with organic solvent extracting; Among the patent CN101906218A; Polyester waste material and terepthaloyl moietie are after reacting 5～9 hours under 180～197.5 ℃ the condition; Suction filtration is removed undegradable polyester waste material while hot; Filtrating refrigerates 5～10 hours down at 5 ℃, vacuum filtration, and drying obtains product terephthalic acid-beta-hydroxy ethyl ester (BHET) and oligopolymer.Among the patent CN1571810A; PET sheet input contains in the terepthaloyl moietie of catalyzer, and at 175～190 ℃, reaction generates terephthalic acid-beta-hydroxy ethyl ester (BHET) under the condition of 0.1～0.5MPa; Remove by solid-liquid separation and not dissolve foreign matter; The classified distillation of solution, the concentrated BHET that obtains and methyl alcohol carry out transesterify and generate crude terephthalic acid dimethyl ester (DMT) and terepthaloyl moietie (EG), and refining DMT generates terephthalic acids (TA) 230～250 ℃ of following hydrolysis.Patent CN1390826A; Introduced the method for the useless polyester of a kind of pure alkali associating depolymerization, this method is reaction medium with terepthaloyl moietie, under 180 ℃ condition; Useless polyester and reaction of sodium bicarbonate generate para-phthalic sodium, with hydrochloric acid the terephthalic acid sodium reduction are obtained terephthalic acid monomers.
Above method is not all carried out detailed explanation to the yield of title product, and has weak point separately.Among the US4605762, the long reaction time of polyester waste material, and need be under the condition of HTHP, implementation cost is big; Among the US3952053, repeatedly use strong acid and strong base, corrosion reaction equipment not only, produced simultaneously waste liquor contamination environment; Among the CN101906218A, reaction times and crystallisation by cooling time all reach 5～10h, are unfavorable for large-scale production, and produce with side reaction.Among the CN1571810A, facility investment is big, whole flow process length consuming time.Among the CN1390826A, depolymerization product is coloured dope, complicated component; Be difficult for solid-liquid separation; Only, can not guarantee the purity of title product, make the complicacy of composition in spent glycol and the washings can increase the difficulty that reclaims terepthaloyl moietie in a large number with purified terepthaloyl moietie washing depolymerization product.
Summary of the invention
In order to address the above problem, the purpose of this invention is to provide a kind of fast, easy, the depolymerization method of the waste and old polyester bottle that target product yield is high.
A kind of depolymerization method of waste and old polyester bottle may further comprise the steps:
(1) the waste and old polyester bottle is cleaned, pulverized back and zero(ppm) water, terepthaloyl moietie, NaHCO
3Together putting into high-temperature high-pressure reaction kettle reacts to the depolymerization of waste and old polyester bottle and finishes; Waste and old polyester bottle fragment: zero(ppm) water: terepthaloyl moietie: NaHCO
3Mass ratio=1: 13～17: 3.7～7.5: 1～1.1;
(2) depolymerization product that obtains of suction filtration step (1) is removed insolubles impurity; The product liquid that obtains is carried out the charcoal absorption decolouring;
(3) colourless transparent liquid that obtains of heating steps (2), and the hydrochloric acid of amount of substance such as sodium ion in adding and the liquid, the adularescent deposition generates, frozen water cooling back suction filtration, wash solids filter cake;
(4) the drying solid filter cake can obtain the white product terephthalic acid, obtains terepthaloyl moietie behind the filtrating rotary evaporation.
In the step (1) the waste and old polyester bottle is ground into the big or small fragment of 1～3mm * 1～3mm.
Temperature of reaction in the step (1) is 170～200 ℃, and the reaction times is 15～40min.
Stir when reacting in the step (1), stirring velocity is for being no more than 100r/min.
The add-on of step (2) gac and the ratio of liquid volume are pressed m/v=0.3%;
Step (2) charcoal absorption condition is 50 ℃ of following water-baths.
Colourless transparent liquid to 30～60 that heating steps (2) obtains in the step (3) ℃.
Step (3) the frozen water refrigerative time is 1 hour.
The temperature of the dry terephthalic acid of step (4) is 80～105 ℃.
Compare with other technologies, the invention has the advantages that:
(1) the present invention utilizes mixed system that the waste and old polyester bottle is decomposed, under 170～200 ℃, and reaction 15～40min, the depolymerization rate of polyester (PET) reaches more than 99%.Simultaneously low temperature fast reaction process reduced the possibility of side reaction, improved the yield of title product.
(2) adding of water not only can reduce the consumption of terepthaloyl moietie in the mixed system, and helps the carrying out of the subsequent operations such as removal of impurities, decolouring of product;
(3) need not to add catalyzer in the reaction process of waste and old polyester bottle, reduced the link that catalyst recovery is utilized.
(4) terepthaloyl moietie of one of reaction medium also is resultant of reaction simultaneously, can recycle and reuse through rotary evaporation.
Embodiment
The present invention will further specify through following embodiment, and these instances only are used to illustrate, rather than limits scope of the present invention.
Embodiment 1:
(1) the waste and old polyester bottle that in reaction kettle, adds the about 3mm of 3g * 3mm size is pulverized material, 3.3g sodium hydrogencarbonate, 40ml zero(ppm) water; 10ml terepthaloyl moietie, the sealing kettle cover is heated to 180 ℃ under the stirring velocity of 40r/min; Under this temperature, react 30min, obtain weak yellow liquid product and insolubles impurity, the suction filtration reaction product; Taking by weighing insolubles impurity quality is 0.008g, and the depolymerization rate of PET is 99.73%.
(2) add the 0.15g gac and put into filtrating decolouring, 50 ℃ of following water-bath half a hour, suction filtration adds the 0.15g gac once more and puts into filtrating, and 50 ℃ of following water-bath half a hour, suction filtration obtains colourless transparent liquid.
(3) beaker that fills product liquid is as for being heated to 30 ℃ on the battery stove, add gradually in constantly stirring with liquid in the hydrochloric acid (the hydrochloric acid mass concentration is 18～19%) of amount of substance such as sodium ion, the adularescent deposition occurs.Beaker was put into the frozen water cooling after 1 hour, suction filtration.Washing leaching cake gets terephthalic acid 2.444g after 85 ℃ of dryings, yield is 94.22%; Through efficient liquid phase chromatographic analysis; The content of measuring terephthalic acid is 98.14%, obtains terepthaloyl moietie 10.80ml behind the filtrating rotary distillation, and the iodometric determination glycol content is 96.34%.
The comparative example 1:
Except becoming the add-on of zero(ppm) water the 60ml all the other parameters and operation steps reference implementation example 1.Taking by weighing insolubles impurity quality is 0.198g; The depolymerization rate of PET is 93.40%, gets terephthalic acid 2.272g after the drying, and yield is 87.59%; Through efficient liquid phase chromatographic analysis; The content of measuring terephthalic acid is 98.38%, obtains terepthaloyl moietie 10.93ml behind the filtrating rotary distillation, and the iodometric determination glycol content is 96.05%.
Embodiment 2:
(1) the waste and old polyester bottle that in reaction kettle, adds the about 3mm of 3g * 3mm size is pulverized material, 3.3g sodium hydrogencarbonate, 50ml zero(ppm) water; 15ml terepthaloyl moietie, the sealing kettle cover is heated to 170 ℃ under the stirring velocity of 40r/min; Under this temperature, react 30min, obtain weak yellow liquid product and insolubles impurity, the suction filtration reaction product; Taking by weighing insolubles impurity quality is 0.010g, and the depolymerization rate of PET is 99.67%.
(2) add the 0.195g gac and put into filtrating decolouring, 50 ℃ of following water-bath half a hour, suction filtration adds the 0.195g gac once more and puts into filtrating, and 50 ℃ of following water-bath half a hour, suction filtration obtains colourless transparent liquid.
(3) beaker that fills product liquid is as for being heated to 45 ℃ on the battery stove, add gradually in constantly stirring with liquid in the hydrochloric acid (the hydrochloric acid mass concentration is 18～19%) of amount of substance such as sodium ion, the adularescent deposition occurs.Beaker was put into the frozen water cooling after 1 hour, suction filtration.Washing leaching cake; After 95 ℃ of dryings terephthalic acid 2.478g, yield is 95.52%, is 98.64% through the content of high effective liquid chromatography for measuring terephthalic acid; Obtain terepthaloyl moietie 15.94ml behind the filtrating rotary distillation, the iodometric determination glycol content is 97.04%.
The comparative example 2:
Except becoming stirring velocity the 300r/min all the other parameters and operation steps reference implementation example 2.Taking by weighing insolubles impurity quality is 0.773g; The depolymerization rate of PET is 74.23%; After the drying terephthalic acid 1.808g, yield is 69.70%, is 97.68% through the content of high effective liquid chromatography for measuring terephthalic acid; Obtain terepthaloyl moietie 15.66ml behind the filtrating rotary distillation, the iodometric determination glycol content is 96.42%.
Embodiment 3:
(1) the waste and old polyester bottle that in reaction kettle, adds the about 3mm of 3g * 3mm size is pulverized material, 3g sodium hydrogencarbonate, 50ml zero(ppm) water; 10ml terepthaloyl moietie, the sealing kettle cover does not have and stirs; Be heated to 180 ℃, under this temperature, react 30min, obtain weak yellow liquid product and insolubles impurity; The suction filtration reaction product, taking by weighing insolubles impurity quality is 0.030g, the depolymerization rate of PET is 99.00%.
(2) add the 0.18g gac and put into filtrating decolouring, 50 ℃ of following water-bath half a hour, suction filtration adds the 0.18g gac once more and puts into filtrating, and 50 ℃ of following water-bath half a hour, suction filtration obtains colourless transparent liquid.
(3) beaker that fills product liquid is as for being heated to 60 ℃ on the battery stove, add gradually in constantly stirring with liquid in the hydrochloric acid (the hydrochloric acid mass concentration is 18～19%) of amount of substance such as sodium ion, the adularescent deposition occurs.Beaker was put into the frozen water cooling after 1 hour, suction filtration.Washing leaching cake; After 105 ℃ of dryings terephthalic acid 2.439g, yield is 94.02%, is 98.79% through the content of high effective liquid chromatography for measuring terephthalic acid; Obtain terepthaloyl moietie 10.84ml behind the filtrating rotary distillation, the iodometric determination glycol content is 96.87%.
The comparative example 3:
Except not adding the terepthaloyl moietie all the other parameters and operation steps reference implementation example 3.Taking by weighing insolubles impurity quality is 0.328g, and the depolymerization rate of PET is 89.07%, gets terephthalic acid 2.264g after the drying, and yield is 87.28%.Content through the high effective liquid chromatography for measuring terephthalic acid is 97.62%, obtains terepthaloyl moietie 0.72ml behind the filtrating rotary distillation, and the iodometric determination glycol content is 95.68%.
Claims (10)
1. the method for a disaggregation of waste and old pet bottle is characterized in that, this method may further comprise the steps:
(1) the waste and old polyester bottle is cleaned, pulverized back and zero(ppm) water, terepthaloyl moietie, NaHCO
3Together putting into high-temperature high-pressure reaction kettle reacts to the depolymerization of waste and old polyester bottle and finishes; Waste and old polyester bottle fragment: zero(ppm) water: terepthaloyl moietie: NaHCO
3Mass ratio=1: 13～17: 3.7～7.5: 1～1.1;
(2) depolymerization product that obtains of suction filtration step (1) is removed insolubles impurity; The product liquid that obtains is carried out the charcoal absorption decolouring;
(3) colourless transparent liquid that obtains of heating steps (2), and the hydrochloric acid of amount of substance such as sodium ion in adding and the liquid, the adularescent deposition generates, frozen water cooling back suction filtration, wash solids filter cake;
(4) the drying solid filter cake can obtain the white product terephthalic acid, obtains terepthaloyl moietie behind the filtrating rotary evaporation.
2. method according to claim 1 is characterized in that, in the step (1) the waste and old polyester bottle is ground into the big or small fragment of 1～3mm * 1～3mm.
3. method according to claim 1 is characterized in that, the temperature of reaction in the step (1) is 170～200 ℃, and the reaction times is 15～40min.
4. method according to claim 1 is characterized in that, stirs when reacting in the step (1), and stirring velocity is no more than 100r/min.
5. method according to claim 1 is characterized in that, the add-on of step (2) gac and the ratio of liquid volume are pressed m/v=0.3%.
6. method according to claim 1 is characterized in that, step (2) charcoal absorption condition is 50 ℃ of following water-baths.
7. method according to claim 1 is characterized in that, colourless transparent liquid to 30～60 that heating steps (2) obtains in the step (3) ℃.
8. method according to claim 1 is characterized in that, step (3) the frozen water refrigerative time is 1 hour.
9. method according to claim 1 is characterized in that, the temperature of the dry terephthalic acid of step (4) is 80～105 ℃.
10. method according to claim 1 is characterized in that, the terepthaloyl moietie that obtains behind step (4) the filtrating rotary evaporation returns step (1) and recycles.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2012100398715A CN102532591B (en) | 2012-02-22 | 2012-02-22 | Method for depolymerizing waste polyester bottle |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2012100398715A CN102532591B (en) | 2012-02-22 | 2012-02-22 | Method for depolymerizing waste polyester bottle |
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| CN102532591A true CN102532591A (en) | 2012-07-04 |
| CN102532591B CN102532591B (en) | 2013-12-04 |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104479168A (en) * | 2014-11-18 | 2015-04-01 | 广东树业环保科技股份有限公司 | Waste PET (polyethylene terephthalate) decolorization recovery method, product and application |
| US10604634B1 (en) | 2018-09-26 | 2020-03-31 | Far Eastern New Century Corporation | Method for manufacturing terephthalic acid and system thereof |
| CN113149825A (en) * | 2021-04-02 | 2021-07-23 | 华中科技大学 | Method for catalytic degradation of polyethylene glycol terephthalate |
| WO2023231628A1 (en) * | 2022-05-31 | 2023-12-07 | 科泽新材料股份有限公司 | Process and system for implementing continuous preparation of high-purity bhet monomer from waste polyester |
| CN118002600A (en) * | 2024-04-08 | 2024-05-10 | 国高材高分子材料产业创新中心有限公司 | Recovery method of solar cell backboard |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1390826A (en) * | 2002-07-24 | 2003-01-15 | 重庆大学 | Process for depolymerizing waste polyester |
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Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1390826A (en) * | 2002-07-24 | 2003-01-15 | 重庆大学 | Process for depolymerizing waste polyester |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104479168A (en) * | 2014-11-18 | 2015-04-01 | 广东树业环保科技股份有限公司 | Waste PET (polyethylene terephthalate) decolorization recovery method, product and application |
| US10604634B1 (en) | 2018-09-26 | 2020-03-31 | Far Eastern New Century Corporation | Method for manufacturing terephthalic acid and system thereof |
| CN110950751A (en) * | 2018-09-26 | 2020-04-03 | 远东新世纪股份有限公司 | Method and system for producing terephthalic acid |
| TWI694064B (en) * | 2018-09-26 | 2020-05-21 | 遠東新世紀股份有限公司 | Method for manufacturing terephthalic acid and system thereof |
| CN113149825A (en) * | 2021-04-02 | 2021-07-23 | 华中科技大学 | Method for catalytic degradation of polyethylene glycol terephthalate |
| CN113149825B (en) * | 2021-04-02 | 2023-02-14 | 华中科技大学 | Method for catalytic degradation of polyethylene glycol terephthalate |
| WO2023231628A1 (en) * | 2022-05-31 | 2023-12-07 | 科泽新材料股份有限公司 | Process and system for implementing continuous preparation of high-purity bhet monomer from waste polyester |
| CN118002600A (en) * | 2024-04-08 | 2024-05-10 | 国高材高分子材料产业创新中心有限公司 | Recovery method of solar cell backboard |
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| CN102532591B (en) | 2013-12-04 |
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