WO2022154224A1 - 폴리에스테르의 해중합 방법 - Google Patents
폴리에스테르의 해중합 방법 Download PDFInfo
- Publication number
- WO2022154224A1 WO2022154224A1 PCT/KR2021/015822 KR2021015822W WO2022154224A1 WO 2022154224 A1 WO2022154224 A1 WO 2022154224A1 KR 2021015822 W KR2021015822 W KR 2021015822W WO 2022154224 A1 WO2022154224 A1 WO 2022154224A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- polyester
- depolymerization
- acid
- glycol
- dibasic acid
- Prior art date
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- 229920000728 polyester Polymers 0.000 title claims abstract description 137
- 238000000034 method Methods 0.000 title claims abstract description 77
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 105
- -1 polypropylene Polymers 0.000 claims description 72
- 239000002253 acid Substances 0.000 claims description 63
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 48
- 239000000203 mixture Substances 0.000 claims description 31
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 30
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 29
- 239000003795 chemical substances by application Substances 0.000 claims description 26
- 150000003839 salts Chemical class 0.000 claims description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 22
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 19
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 18
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims description 15
- 239000013078 crystal Substances 0.000 claims description 14
- DNIAPMSPPWPWGF-UHFFFAOYSA-N propylene glycol Substances CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 14
- 238000006116 polymerization reaction Methods 0.000 claims description 13
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 12
- 239000012535 impurity Substances 0.000 claims description 12
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 10
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 10
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 claims description 9
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 9
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 9
- 238000000354 decomposition reaction Methods 0.000 claims description 9
- 239000007788 liquid Substances 0.000 claims description 9
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 8
- 239000007864 aqueous solution Substances 0.000 claims description 8
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 claims description 8
- 238000000926 separation method Methods 0.000 claims description 8
- 239000007787 solid Substances 0.000 claims description 8
- 150000005846 sugar alcohols Polymers 0.000 claims description 8
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 6
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 6
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 6
- 239000003513 alkali Substances 0.000 claims description 6
- WQYVRQLZKVEZGA-UHFFFAOYSA-N hypochlorite Chemical compound Cl[O-] WQYVRQLZKVEZGA-UHFFFAOYSA-N 0.000 claims description 6
- QWPPOHNGKGFGJK-UHFFFAOYSA-N hypochlorous acid Chemical compound ClO QWPPOHNGKGFGJK-UHFFFAOYSA-N 0.000 claims description 6
- 239000002202 Polyethylene glycol Substances 0.000 claims description 5
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 5
- 229920001223 polyethylene glycol Polymers 0.000 claims description 5
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 claims description 5
- 229910019142 PO4 Inorganic materials 0.000 claims description 4
- SZXQTJUDPRGNJN-UHFFFAOYSA-N dipropylene glycol Chemical compound OCCCOCCCO SZXQTJUDPRGNJN-UHFFFAOYSA-N 0.000 claims description 4
- 235000011187 glycerol Nutrition 0.000 claims description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 4
- 239000010452 phosphate Substances 0.000 claims description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 claims description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-K Citrate Chemical compound [O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O KRKNYBCHXYNGOX-UHFFFAOYSA-K 0.000 claims description 3
- BDAGIHXWWSANSR-UHFFFAOYSA-M Formate Chemical compound [O-]C=O BDAGIHXWWSANSR-UHFFFAOYSA-M 0.000 claims description 3
- 229910002651 NO3 Inorganic materials 0.000 claims description 3
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 3
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims description 3
- 239000004743 Polypropylene Substances 0.000 claims description 3
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 3
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 claims description 3
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 claims description 3
- 229910021529 ammonia Inorganic materials 0.000 claims description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 claims description 3
- 229910017604 nitric acid Inorganic materials 0.000 claims description 3
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 claims description 3
- WVDDGKGOMKODPV-ZQBYOMGUSA-N phenyl(114C)methanol Chemical compound O[14CH2]C1=CC=CC=C1 WVDDGKGOMKODPV-ZQBYOMGUSA-N 0.000 claims description 3
- 229920001155 polypropylene Polymers 0.000 claims description 3
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 3
- 230000003472 neutralizing effect Effects 0.000 claims description 2
- 239000007921 spray Substances 0.000 claims description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 62
- 229920000139 polyethylene terephthalate Polymers 0.000 description 39
- 239000005020 polyethylene terephthalate Substances 0.000 description 39
- 239000002699 waste material Substances 0.000 description 22
- WOZVHXUHUFLZGK-UHFFFAOYSA-N dimethyl terephthalate Chemical compound COC(=O)C1=CC=C(C(=O)OC)C=C1 WOZVHXUHUFLZGK-UHFFFAOYSA-N 0.000 description 16
- 238000012691 depolymerization reaction Methods 0.000 description 15
- 239000000975 dye Substances 0.000 description 15
- 239000000047 product Substances 0.000 description 15
- 239000000835 fiber Substances 0.000 description 14
- 239000002904 solvent Substances 0.000 description 14
- 238000006243 chemical reaction Methods 0.000 description 13
- 239000000178 monomer Substances 0.000 description 13
- 230000008569 process Effects 0.000 description 12
- 239000003054 catalyst Substances 0.000 description 11
- 238000005406 washing Methods 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 10
- 239000004744 fabric Substances 0.000 description 9
- 239000002994 raw material Substances 0.000 description 8
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 description 6
- 229910052783 alkali metal Inorganic materials 0.000 description 6
- 150000001340 alkali metals Chemical class 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 6
- 238000004821 distillation Methods 0.000 description 6
- 230000034659 glycolysis Effects 0.000 description 6
- 238000012545 processing Methods 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 238000005809 transesterification reaction Methods 0.000 description 6
- 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 5
- 238000002845 discoloration Methods 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- 238000004042 decolorization Methods 0.000 description 4
- 238000006068 polycondensation reaction Methods 0.000 description 4
- 229920001225 polyester resin Polymers 0.000 description 4
- 239000004645 polyester resin Substances 0.000 description 4
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- 239000003381 stabilizer Substances 0.000 description 4
- LWIHDJKSTIGBAC-UHFFFAOYSA-K tripotassium phosphate Chemical compound [K+].[K+].[K+].[O-]P([O-])([O-])=O LWIHDJKSTIGBAC-UHFFFAOYSA-K 0.000 description 4
- 238000006136 alcoholysis reaction Methods 0.000 description 3
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- 230000008025 crystallization Effects 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
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- YIWUKEYIRIRTPP-UHFFFAOYSA-N 2-ethylhexan-1-ol Chemical compound CCCCC(CC)CO YIWUKEYIRIRTPP-UHFFFAOYSA-N 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 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 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- 238000003916 acid precipitation Methods 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 2
- 150000001342 alkaline earth metals Chemical class 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 235000019445 benzyl alcohol Nutrition 0.000 description 2
- 235000013361 beverage Nutrition 0.000 description 2
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- KZTYYGOKRVBIMI-UHFFFAOYSA-N diphenyl sulfone Chemical compound C=1C=CC=CC=1S(=O)(=O)C1=CC=CC=C1 KZTYYGOKRVBIMI-UHFFFAOYSA-N 0.000 description 2
- 239000007884 disintegrant Substances 0.000 description 2
- 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 description 2
- 230000000694 effects Effects 0.000 description 2
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- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 2
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- BDJRBEYXGGNYIS-UHFFFAOYSA-N nonanedioic acid Chemical compound OC(=O)CCCCCCCC(O)=O BDJRBEYXGGNYIS-UHFFFAOYSA-N 0.000 description 2
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical class OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 description 2
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- 229910052698 phosphorus Inorganic materials 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- WLJVNTCWHIRURA-UHFFFAOYSA-N pimelic acid Chemical compound OC(=O)CCCCCC(O)=O WLJVNTCWHIRURA-UHFFFAOYSA-N 0.000 description 2
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- 229910052700 potassium Inorganic materials 0.000 description 2
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- 238000011084 recovery Methods 0.000 description 2
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- ARWQHTZTOWMAEQ-UHFFFAOYSA-N (2-carboxyoxyphenyl) hydrogen carbonate Chemical compound OC(=O)OC1=CC=CC=C1OC(O)=O ARWQHTZTOWMAEQ-UHFFFAOYSA-N 0.000 description 1
- PXGZQGDTEZPERC-UHFFFAOYSA-N 1,4-cyclohexanedicarboxylic acid Chemical compound OC(=O)C1CCC(C(O)=O)CC1 PXGZQGDTEZPERC-UHFFFAOYSA-N 0.000 description 1
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- RTBFRGCFXZNCOE-UHFFFAOYSA-N 1-methylsulfonylpiperidin-4-one Chemical compound CS(=O)(=O)N1CCC(=O)CC1 RTBFRGCFXZNCOE-UHFFFAOYSA-N 0.000 description 1
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- SXFJDZNJHVPHPH-UHFFFAOYSA-N 3-methylpentane-1,5-diol Chemical compound OCCC(C)CCO SXFJDZNJHVPHPH-UHFFFAOYSA-N 0.000 description 1
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- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
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- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
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- 239000005708 Sodium hypochlorite Substances 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 1
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- XSTXAVWGXDQKEL-UHFFFAOYSA-N Trichloroethylene Chemical compound ClC=C(Cl)Cl XSTXAVWGXDQKEL-UHFFFAOYSA-N 0.000 description 1
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- 150000007824 aliphatic compounds Chemical class 0.000 description 1
- 150000001339 alkali metal compounds Chemical class 0.000 description 1
- 150000001341 alkaline earth metal compounds Chemical class 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 239000000908 ammonium hydroxide Substances 0.000 description 1
- JFCQEDHGNNZCLN-UHFFFAOYSA-N anhydrous glutaric acid Natural products OC(=O)CCCC(O)=O JFCQEDHGNNZCLN-UHFFFAOYSA-N 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- 229910052790 beryllium Inorganic materials 0.000 description 1
- ATBAMAFKBVZNFJ-UHFFFAOYSA-N beryllium atom Chemical compound [Be] ATBAMAFKBVZNFJ-UHFFFAOYSA-N 0.000 description 1
- GKVWVSJEEYWABA-UHFFFAOYSA-N bis(4-hydroxy-2-methylbutan-2-yl) benzene-1,4-dicarboxylate Chemical compound OCCC(C)(C)OC(=O)C1=CC=C(C(=O)OC(C)(C)CCO)C=C1 GKVWVSJEEYWABA-UHFFFAOYSA-N 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 1
- BNMJSBUIDQYHIN-UHFFFAOYSA-N butyl dihydrogen phosphate Chemical compound CCCCOP(O)(O)=O BNMJSBUIDQYHIN-UHFFFAOYSA-N 0.000 description 1
- 229910052792 caesium Inorganic materials 0.000 description 1
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- PMMYEEVYMWASQN-IMJSIDKUSA-N cis-4-Hydroxy-L-proline Chemical compound O[C@@H]1CN[C@H](C(O)=O)C1 PMMYEEVYMWASQN-IMJSIDKUSA-N 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 238000001944 continuous distillation Methods 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- XBZSBBLNHFMTEB-UHFFFAOYSA-N cyclohexane-1,3-dicarboxylic acid Chemical compound OC(=O)C1CCCC(C(O)=O)C1 XBZSBBLNHFMTEB-UHFFFAOYSA-N 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 150000001991 dicarboxylic acids Chemical class 0.000 description 1
- 150000002009 diols Chemical class 0.000 description 1
- VVTXSHLLIKXMPY-UHFFFAOYSA-L disodium;2-sulfobenzene-1,3-dicarboxylate Chemical compound [Na+].[Na+].OS(=O)(=O)C1=C(C([O-])=O)C=CC=C1C([O-])=O VVTXSHLLIKXMPY-UHFFFAOYSA-L 0.000 description 1
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- 239000012634 fragment Substances 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- 229910052732 germanium Inorganic materials 0.000 description 1
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 description 1
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 1
- 238000004128 high performance liquid chromatography Methods 0.000 description 1
- 229960004337 hydroquinone Drugs 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 150000002484 inorganic compounds Chemical class 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
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- 230000008018 melting Effects 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 150000004702 methyl esters Chemical class 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
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- RXOHFPCZGPKIRD-UHFFFAOYSA-N naphthalene-2,6-dicarboxylic acid Chemical compound C1=C(C(O)=O)C=CC2=CC(C(=O)O)=CC=C21 RXOHFPCZGPKIRD-UHFFFAOYSA-N 0.000 description 1
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 238000005502 peroxidation Methods 0.000 description 1
- ACVYVLVWPXVTIT-UHFFFAOYSA-N phosphinic acid Chemical compound O[PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-N 0.000 description 1
- 150000003014 phosphoric acid esters Chemical class 0.000 description 1
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- 230000000704 physical effect Effects 0.000 description 1
- 229920003207 poly(ethylene-2,6-naphthalate) Polymers 0.000 description 1
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- 229920000570 polyether Polymers 0.000 description 1
- 239000011112 polyethylene naphthalate Substances 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920000137 polyphosphoric acid Polymers 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 239000011736 potassium bicarbonate Substances 0.000 description 1
- 235000015497 potassium bicarbonate Nutrition 0.000 description 1
- 229910000028 potassium bicarbonate Inorganic materials 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 235000011181 potassium carbonates Nutrition 0.000 description 1
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 description 1
- 229940086066 potassium hydrogencarbonate Drugs 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000003908 quality control method Methods 0.000 description 1
- 229910052705 radium Inorganic materials 0.000 description 1
- HCWPIIXVSYCSAN-UHFFFAOYSA-N radium atom Chemical compound [Ra] HCWPIIXVSYCSAN-UHFFFAOYSA-N 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
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- 229910052701 rubidium Inorganic materials 0.000 description 1
- IGLNJRXAVVLDKE-UHFFFAOYSA-N rubidium atom Chemical compound [Rb] IGLNJRXAVVLDKE-UHFFFAOYSA-N 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 150000003385 sodium Chemical class 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 238000000638 solvent extraction Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 1
- KKEYFWRCBNTPAC-UHFFFAOYSA-L terephthalate(2-) Chemical compound [O-]C(=O)C1=CC=C(C([O-])=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-L 0.000 description 1
- 150000003503 terephthalic acid derivatives Chemical class 0.000 description 1
- ISIJQEHRDSCQIU-UHFFFAOYSA-N tert-butyl 2,7-diazaspiro[4.5]decane-7-carboxylate Chemical compound C1N(C(=O)OC(C)(C)C)CCCC11CNCC1 ISIJQEHRDSCQIU-UHFFFAOYSA-N 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- DQWPFSLDHJDLRL-UHFFFAOYSA-N triethyl phosphate Chemical compound CCOP(=O)(OCC)OCC DQWPFSLDHJDLRL-UHFFFAOYSA-N 0.000 description 1
- GGUBFICZYGKNTD-UHFFFAOYSA-N triethyl phosphonoacetate Chemical compound CCOC(=O)CP(=O)(OCC)OCC GGUBFICZYGKNTD-UHFFFAOYSA-N 0.000 description 1
- WVLBCYQITXONBZ-UHFFFAOYSA-N trimethyl phosphate Chemical compound COP(=O)(OC)OC WVLBCYQITXONBZ-UHFFFAOYSA-N 0.000 description 1
- XZZNDPSIHUTMOC-UHFFFAOYSA-N triphenyl phosphate Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)(=O)OC1=CC=CC=C1 XZZNDPSIHUTMOC-UHFFFAOYSA-N 0.000 description 1
- 238000007666 vacuum forming Methods 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
Images
Classifications
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- 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
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- 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
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- C08G63/18—Dicarboxylic acids and dihydroxy compounds the acids or hydroxy compounds containing carbocyclic rings
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C08J11/14—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 steam or water
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- C08J11/16—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 inorganic material
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- 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
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- C—CHEMISTRY; METALLURGY
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- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
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- 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
- C08J11/26—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 carboxylic acid groups, their anhydrides or esters
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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
- C08J11/28—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 compounds containing nitrogen, sulfur or phosphorus
-
- 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
- C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
-
- 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
- C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
- C08J2367/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
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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
- C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
- C08J2367/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
- C08J2367/03—Polyesters derived from dicarboxylic acids and dihydroxy compounds the dicarboxylic acids and dihydroxy compounds having the hydroxy and the carboxyl groups directly linked to aromatic rings
-
- 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
Definitions
- the present invention relates to a process for the rapid depolymerization of polyesters.
- Polyester represented by polyethylene terephthalate (PET) has excellent chemical stability and is used in textiles, fabrics, clothes, films, sheets, beverage bottles, and the like.
- This chemical recycling is expected as a means to realize the reuse of resources because impurities can be separated and the quality as a raw material is not significantly different from that of virgin.
- the three major methods for depolymerization of polyester to monomers are the hydrolysis method using water as the solvent, the alcoholysis method using alcohol as the solvent, and the glycolysis method using glycol as the solvent.
- the hydrolysis method includes, for example, a method in which a polyethylene terephthalate melt is reacted with water and then reacted with ammonium hydroxide to decompose into terephthalic acid and ethylene glycol (see Patent Document 1).
- This method has the advantage of not using glycol or alcohol for the reaction, but requires a special high-pressure reactor because the reaction takes place under high-pressure conditions.
- the alcoholysis method is a method of depolymerizing polyester, for example, by heating in an alcohol solvent (adding a catalyst if necessary) (see Patent Document 2 and Patent Document 3).
- an alcohol solvent for example, when polyethylene terephthalate is depolymerized using methanol as a solvent, dimethyl terephthalate (DMT), a useful and easy-to-handle monomer, is directly produced by the depolymerization reaction, and the depolymerization reaction is also relatively fast.
- DMT dimethyl terephthalate
- alcohol used as a solvent has a low boiling point and requires pressurization to proceed with the reaction (for example, it is reacted in methanol in a supercritical or subcritical state), and a special high-pressure reactor is required.
- the glycolysis method is a method of depolymerizing polyester by heating it together with a depolymerization catalyst such as sodium carbonate in an excess alkylene glycol solvent to produce bis( ⁇ -hydroxyalkyl) terephthalate and ethylene glycol (Patent Document 4, and See Patent Document 5).
- a depolymerization catalyst such as sodium carbonate
- an excess alkylene glycol solvent to produce bis( ⁇ -hydroxyalkyl) terephthalate and ethylene glycol
- Patent Document 4 ethylene glycol
- BHET bis( ⁇ -hydroxyethyl) terephthalate
- methanol is added in the presence of a transesterification catalyst to carry out transesterification, whereby dimethyl Terephthalate (DMT) can be recovered.
- the glycolysis method can be reacted under normal pressure, but the reaction time is relatively long, so it is required to shorten the reaction time, and there is a problem in that the glycol in the solvent is heated for a long time and deteriorates.
- polyester raw materials are not transparent like beverage bottles.
- the color removal of the dye injected during processing is the final step. It greatly affects the quality of the product.
- the amount of dye input also rapidly increases according to the color and fineness of the fibers. Accordingly, the use of colored polyester feedstock is limited, and in order to create added value, it is the most rational and eco-friendly method to decompose it into a raw material through depolymerization and then repolymerize it, but it is not economical due to the high process cost.
- the dyes of these colored polyesters are removed through solvent treatment and adsorption process (activated carbon) for decolorization during the depolymerization process. This is rapidly reduced, and the overall process cost is high, which is practically not economical. For this reason, it is common to use polyester bottle flakes with high recovery purity for polyester depolymerization.
- Patent Document 1 Japanese Patent Laid-Open No. 2003-527363 (published date: September 16, 2003)
- Patent Document 2 Japanese Patent Laid-Open No. 1999-100336 (published on: April 13, 1999)
- Patent Document 3 Japanese Patent Laid-Open No. 2003-300916 (published date: October 21, 2003)
- Patent Document 4 Japanese Patent Laid-Open No. 2002-167468 (published on: June 11, 2002)
- Patent Document 5 Japanese Patent Laid-Open No. 2004-300115 (published on October 28, 2004)
- the dye of the colored polyester can be removed inexpensively and with high efficiency, and the colored polyester can be depolymerized in a short time, the depolymerization efficiency is high, and there is no need to increase the depolymerization temperature of the entire depolymerization composition to the depolymerization temperature, which is economical.
- a method for depolymerizing phosphorus polyester is provided.
- composition for polymerization of recycled polyester prepared by a method of depolymerization of polyester.
- a recycled polyester prepared using a composition for polymerization of recycled polyester.
- a depolymerization step of contacting the polyester with superheated steam It provides a method of depolymerization of polyester comprising a.
- the temperature of the superheated steam may be 250 °C to 450 °C.
- Superheated steam may be applied at an injection pressure of 0.1 bar to 2 bar.
- the depolymerization step may be performed for 1 minute to 120 minutes.
- the alkali may include sodium hydroxide, potassium hydroxide, lithium hydroxide, ammonia, or mixtures thereof.
- the acid may include hydrochloric acid, nitric acid, sulfuric acid, carbonic acid, phosphoric acid, acetic acid, hypochlorous acid (HClO), or mixtures thereof.
- Salts may include carbonate, hydrogen carbonate, phosphate, sulfate, sulfite, nitrate, silicate, hypochlorite, formate, acetate, citrate, oxalate, or mixtures thereof.
- the mono alcohol may include methanol, ethanol, propanol, butanol, or mixtures thereof.
- Polyhydric alcohols include ethylene glycol, n-propylene glycol, isopropylene glycol, diethylene glycol, polyethylene glycol, triethylene glycol, dipropylene glycol, 1,3-butanediol, 1,4-butanediol, glycerin, benzyl alcohol, polypropylene glycol , pentaerythritol, trimethylolpropane, or mixtures thereof.
- the decomposing agent may be added in an amount of 0.75 mol to 3.0 mol based on 1.0 mol of the dibasic acid contained in the polyester.
- the depolymerization method of polyester comprises the steps of solid-liquid separation of a liquid alkylene glycol and a solid dibasic acid salt from the depolymerization product obtained in the depolymerization step, dissolving the solid dibasic acid salt in water, and acidifying an aqueous solution of the dibasic acid salt. It may further include the step of precipitating the dibasic acid crystals by neutralizing with the , and the step of solid-liquid separation of the dibasic acid crystals from the precipitated product.
- the method of depolymerizing the polyester may further include removing impurities from the aqueous solution of the dibasic acid salt.
- the method for depolymerizing polyester may further include recrystallizing dibasic acid crystals.
- composition for polymerization of recycled polyester comprising a dibasic acid and an alkylene glycol, obtained by the method of depolymerizing polyester according to an embodiment.
- a recycled polyester prepared using the polyester polymerization composition according to an embodiment.
- the color of the recycled polyester may have an L value of 60 or more.
- the method of depolymerizing polyester according to an embodiment can remove the dye of colored polyester with low cost and high efficiency, and at the same time can depolymerize the colored polyester within a short time, and the depolymerization efficiency is high, and the entire depolymerization composition is raised to the depolymerization temperature. It is economical as there is no need to
- 1 is a photograph showing colored polyethylene terephthalate.
- 3 is a photograph of removing impurities by washing the depolymerized product with water.
- 5 is a photograph of colored polyethylene terephthalate fibers and recovered terephthalic acid before and after depolymerization.
- FIG. 6 is a comparative photograph of a polyester chip and a virgin polyester chip obtained by re-polymerizing recovered terephthalic acid as a raw material.
- the depolymerization method of polyester according to an embodiment includes a depolymerization step of adding a decomposing agent to the polyester and then contacting the polyester with superheated steam.
- the polyester may be a polyester formed by polymerization of a dibasic acid and an alkylene glycol, for example, polyethylene terephthalate (PET), polybutylene terephthalate, or polyethylene naphthalate, or polycaprolactone formed by polymerization of caprolactone.
- PET polyethylene terephthalate
- PBT polybutylene terephthalate
- polyethylene naphthalate polyethylene naphthalate
- polycaprolactone formed by polymerization of caprolactone.
- Alkylene glycols obtainable by depolymerizing polyester include, for example, ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, 1,3-butanediol, 1,4-butanediol, 3 -Methyl-1,5-pentanediol, 1,6-hexanediol, 1,9-nonanediol, neopentyl glycol, polytetramethylene glycol, 1,4-cyclohexanediol, 1,4-benzenediol, etc. are mentioned.
- ethylene glycol can be recovered as alkylene glycol
- butylene glycol can be recovered as a monomer when the polyester is polybutylene terephthalate.
- dibasic acid obtainable by depolymerizing polyester examples include terephthalic acid, phthalic acid (ortho), isophthalic acid, dibromoisophthalic acid, sodium sulfoisophthalate, phenylenedioxydicarboxylic acid, 4,4' -diphenyldicarboxylic acid, 4,4'-diphenyletherdicarboxylic acid, 4,4'-diphenylketone dicarboxylic acid, 4,4'-diphenoxyethanedicarboxylic acid, 4,4'- and aromatic dicarboxylic acids such as diphenyl sulfone dicarboxylic acid, 2,6-naphthalene dicarboxylic acid, trimellitic acid and pyromellitic acid.
- dicarboxylic acids for example, alicyclic dicarboxylic acids such as hexahydro terephthalic acid, hexahydroisophthalic acid, and succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid , aliphatic dicarboxylic acids such as undecadicarboxylic acid and dodecadicarboxylic acid.
- alicyclic dicarboxylic acids such as hexahydro terephthalic acid, hexahydroisophthalic acid, and succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid
- aliphatic dicarboxylic acids such as undecadicarboxylic acid and dodecadicarboxylic acid.
- Wastes may be residues, defective products, etc. generated during the manufacture of molded products in addition to wastes generated after using a molded article containing polyester.
- it may be a used PET bottle, cup, string, packaging pack, etc., or a burr or sprue when molding these, a sheet after cutting the cup after vacuum forming, fiber, fabric, clothing, film, sheet, or the like.
- the method of depolymerizing polyester according to an embodiment can economically and efficiently depolymerize colored polyester such as fibers, fabrics, and clothes containing a large amount of dye, as will be described later.
- the content of polyester in the polyester waste may be 60% to 100% by weight based on the total weight of the polyester waste. If the content of the polyester is less than 60% by weight, the amount of side-reactants and non-recyclable separation and purification wastes compared to the raw materials obtained through the depolymerization process is too large, so it may not be practically economical.
- polyester waste When polyester waste is used as a feedstock for depolymerization, it may optionally be subjected to a pretreatment step of washing the waste and removing contaminants attached to the waste, such as dyes, contents, or soil, before the depolymerization step.
- the polyester depolymerization method according to the embodiment has a fast reaction rate, the recovered polyester waste can be provided to the depolymerization reaction as a relatively large fragment, but the waste is mechanically cut in order to proceed with the reaction more efficiently.
- pulverization and processing may be performed using a known suitable means, for example, the polyester waste may be pulverized into pieces having a size of 2 mm to 8 mm by pulverization using a hammer mill or the like, and then used for depolymerization.
- the pulverized chip can be immersed in a solvent to extract and remove dyes, or components lighter than the solvent can be separated, and only a certain size can be recovered by blowing the pulverized product with the wind or using a sieve. It can also be used for a depolymerization reaction.
- the polyester is directly contacted with superheated steam to depolymerize in a dry manner.
- the depolymerization efficiency is high because superheated steam directly reacts with the polyester, and it is economical because there is no need to increase the temperature of the depolymerization composition including the solvent to the depolymerization temperature.
- it is advantageous for depolymerization of colored polyester containing dye because decolorization occurs simultaneously with depolymerization by adding superheated water vapor to the polyester.
- the depolymerization reaction is performed by directly adding superheated steam to the polyester, a high-pressure reactor is not required, and the apparatus can be configured as a batch or continuous reactor.
- the contact between the polyester and the superheated steam may be achieved by directly spraying the superheated steam of 250 ° C to 450 ° C to the polyester at a spray pressure of 0.1 bar to 2 bar, for example, the temperature of the superheated steam is It may be 280 °C to 380 °C.
- the depolymerization time of the polyester may be too long, resulting in lower economic feasibility.
- the pressure of the superheated steam is less than 0.1 bar, the actual decomposition time may not have a great effect compared to the general wet reaction due to the lack of contact effectiveness of the direct reaction steam.
- melting is preceded rather than decomposition, and a large mass is formed, so the time to decompose in stages from the surface to the inner surface may be long.
- the depolymerization reaction may be carried out for 1 minute to 120 minutes, or may be carried out for 10 minutes to 60 minutes.
- the depolymerization reaction time may be increased within 120 minutes as the concentration of impurities including dyes of the polyester increases, the processing amount of the polyester increases, and the temperature of the superheated steam decreases.
- a decomposing agent may be added to the polyester prior to contacting the polyester with superheated steam.
- high-temperature superheated steam is treated alone, the polyester, a thermoplastic resin, is dissolved before the polyester is decomposed into monomers. If treated first, the polyester can be allowed to decompose into monomers before dissolving.
- the disintegrant may include an alkali, an acid, a salt thereof, a mono alcohol, a polyhydric alcohol, or a mixture thereof.
- the alkali may include a hydroxide of an alkali metal or alkaline earth metal, ammonia, or a mixture thereof.
- the alkali metal may be a monovalent metal such as lithium, sodium, potassium, rubidium, or cesium, among which sodium or potassium, which is relatively inexpensive, may be used.
- the alkaline earth metal may be beryllium, magnesium, calcium, strontium, barium, radium, or the like.
- the hydroxide of an alkali metal include sodium hydroxide, potassium hydroxide, or lithium hydroxide. Among them, when sodium hydroxide is used in combination with ethylene glycol, etc., the reaction rate and reaction rate are excellent.
- the acid may be an organic or inorganic acid and may include, for example, hydrochloric acid, nitric acid, sulfuric acid, carbonic acid, phosphoric acid, acetic acid, hypochlorous acid (HClO), or mixtures thereof.
- Salts may include inorganic acid salts such as carbonate, hydrogen carbonate, phosphate, sulfate, sulfite, nitrate, silicate, hypochlorite, and organic acid salt such as formate, acetate, citrate, oxalate, or mixtures thereof, for example,
- it may include sodium carbonate, sodium hydrogen carbonate, potassium carbonate, potassium hydrogen carbonate, tripotassium phosphate (hydrate), sodium hypochlorite, or a mixture thereof.
- Polyhydric alcohols include ethylene glycol, n-propylene glycol, isopropylene glycol, diethylene glycol, polyethylene glycol, triethylene glycol, dipropylene glycol, 1,3-butanediol, 1,4-butanediol, glycerin, benzyl alcohol, polypropylene glycol , pentaerythritol, trimethylolpropane, or mixtures thereof.
- ethylene glycol, n-propylene glycol, isopropylene glycol, diethylene glycol, polyethylene glycol, triethylene glycol, and glycerin having a high boiling point and relatively high reactivity can be used.
- the mono-alcohol may include methanol, ethanol, propanol, butanol, or a mixture thereof, and an alkyl ether compound of a polyhydric alcohol such as diol or triol exemplified above, for example, diethylene glycol monomethyl ether or benzyl alcohol; 2-ethyl hexanol and the like.
- a polyhydric alcohol such as diol or triol exemplified above, for example, diethylene glycol monomethyl ether or benzyl alcohol; 2-ethyl hexanol and the like.
- the amount of the decomposing agent may be added in an amount of 0.75 mol to 3.0 mol based on 1.0 mol of the dibasic acid contained in the polyester, for example, a monovalent decomposing agent (eg, hydroxylated sodium) is suitably added in an amount of 1.5 to 3.0 mol, and in the case of a divalent decomposing agent (eg, calcium carbonate), it is suitably added in an amount of 0.75 to 1.5 mol.
- a monovalent decomposing agent eg, hydroxylated sodium
- a divalent decomposing agent eg, calcium carbonate
- the reaction formula is PET (polyethylene terephthalate) + 2NaOH ⁇ TPA salt (disodium terephthalate) + EG (ethylene glycol), so 1 kg of PET Decomposition requires 2 moles of NaOH (420 g) per mole of TPA.
- the amount of dye added during processing varies from 0.5% to 20% by weight of the weight of the polyester fiber (based on on the weight of fabric (o.w.f.)), so the input amount of the decomposing agent is It is preferably 2.0 moles or more with respect to 1.0 moles of the dibasic acid contained in the polyester so that both the dye decomposition and the polyester fibers can be decomposed.
- the alkylene glycol and the dibasic acid salt are separated and recovered from the depolymerization product obtained in the depolymerization step.
- alkylene glycol which is a component of polyester, and other alcohols are used as the decomposing agent
- the alkylene glycol produced by depolymerization and the decomposing agent are once mixed, but the alkylene glycol produced by depolymerization by separating them Rene glycol can be recovered.
- a method for separating the alkylene glycol and the decomposing agent produced by the depolymerization reaction is not particularly limited in the present invention, and an appropriate method may be selected according to the target compound, and may be separated by, for example, distillation and concentration method.
- a conventional distillation concentration apparatus for example, a reduced pressure continuous distillation apparatus, a reduced pressure batch type distillation apparatus, and the like may be used.
- alkylene glycol produced by the depolymerization reaction is of the same type as the decomposing agent, it is not necessary to separate the produced alkylene glycol.
- a hydrolysis method using water, an alcoholysis method using alcohol, and a glycolysis method using glycol may be selectively applied depending on the type of the decomposing agent, and the type of dibasic acid obtained accordingly is different
- the obtained dibasic acid salt may change depending on the kind of the decomposing agent used in the depolymerization reaction.
- the decomposing agent used in the depolymerization reaction.
- BHET bis( ⁇ -hydroxyethyl) terephthalate
- propylene glycol As a monomer, mainly bis( ⁇ -hydroxyethyl isopropyl)terephthalate (BHEPT) can be obtained.
- the obtained oligomer ester compound has very good solubility in chloroform and the like, and thus can be efficiently recovered by solvent extraction.
- the ester compound of a dibasic acid or an oligomer can also be collect
- ester compound of a dibasic acid or oligomer eg BHET
- DMT methyl ester of a dibasic acid or oligomer
- the depolymerization reaction concentrate and methanol are transesterified in the presence of a transesterification catalyst (alkali metal compound, etc.) at 65° C. to 85° C. for 0.5 hours to 5 hours.
- a transesterification catalyst alkali metal compound, etc.
- purified DMT can be collect
- polyester when polyester is depolymerized using the glycolysis method, a dibasic acid salt such as a dibasic acid or a dialkali metal salt of an oligomer may be produced, and this product varies depending on the type of alkali metal used in the depolymerization reaction.
- a dibasic acid salt such as a dibasic acid or a dialkali metal salt of an oligomer
- this product varies depending on the type of alkali metal used in the depolymerization reaction.
- sodium hydroxide sodium hydroxide
- dibasic acid salts eg, sodium terephthalate
- filtration such as solid-liquid separation
- alcohol adhering to the obtained powdery crystal can be removed by washing with alcohol, such as methanol or ethanol.
- a dibasic acid eg, terephthalic acid
- a dibasic acid salt can be obtained by dissolving the crystals of the dibasic acid salt in water, followed by a neutralization reaction by mixing an acid. Since the dibasic acid also precipitates as crystals in water, it can be recovered by solid-liquid separation from water by a method such as centrifugation treatment.
- the amount of water added during the recovery process may be 3 to 10 weights based on 1 weight of the dibasic acid salt.
- the content of the acid supplied to separate the dibasic acid may be equimolar or more with the alkali metal contained in the dibasic acid salt, and the type of acid used in this case is an inorganic acid such as hydrochloric acid, sulfuric acid, phosphoric acid, etc., which are strong acids of pH 2, or formic acid. , acetic acid, oxalic acid and the like can be used, and among them, inorganic acids, especially hydrochloric acid or sulfuric acid, are suitable because impurities in the produced monomer can be reduced.
- the neutralization reaction temperature may be 65° C. to 85° C., and the neutralization reaction can usually be completed within 0.5 hours to 5 hours.
- the polyester depolymerization method may further include selectively removing impurities contained in the polyester molded article or waste in the aqueous solution of the dibasic acid salt.
- a means for removing impurities is not particularly limited, and any suitable technique, apparatus, or the like may be used.
- solid content such as resins other than polyester (polyethylene, polypropylene, polyvinyl chloride, etc.) remaining unreacted and decomposing agents such as insoluble alkali metals can be removed using a mesh or the like.
- dyes, fillers, and the like cannot be removed from a mesh or the like, they can be removed by centrifugation, filtration treatment with an adsorbent such as activated carbon, or the like.
- the method may further include recrystallizing the dibasic acid crystals to a commercially available particle size (100 ⁇ m or more) by selectively recrystallizing the dibasic acid crystals.
- the recrystallization method is not particularly limited, and for example, after mixing the dibasic acid crystal with water, it may be made under high temperature and high pressure conditions.
- the dibasic acid and alkylene glycol obtained by the depolymerization method of polyester can be recycled as monomers for polymerizing recycled polyester.
- the regenerated polyester may be prepared by esterifying and polycondensing a composition for polymerization of a regenerated polyester comprising a dibasic acid and an alkylene glycol obtained by the depolymerization method of the polyester.
- Esterification is a reaction between a recovered monomer, dibasic acid, and alkylene glycol, for example, terephthalic acid and ethylene glycol. Although this reaction may proceed without a catalyst, it may be carried out in the presence of a catalyst such as alkaline earth metal compounds such as magnesium and calcium, and metal compounds such as titanium, zinc, and manganese, which are well known as transesterification catalysts.
- a catalyst such as alkaline earth metal compounds such as magnesium and calcium, and metal compounds such as titanium, zinc, and manganese, which are well known as transesterification catalysts.
- the product of the esterification process may be polycondensed to prepare a recycled polyester resin.
- both solution polymerization and solid-state polymerization may be used.
- a compound for promoting water treatment and/or crystallization may be added as needed, and a polycondensation catalyst or stabilizer may be added at the beginning or during the polycondensation process.
- the water treatment may be performed by contacting the recycled polyester resin prepared in the form of solid particles, for example, with water, water vapor, an inert gas containing water vapor, air containing water vapor, or the like.
- the compound that promotes crystallization include polyolefin-based thermoplastic resins such as polyhexamethylene terephthalate, inorganic compounds, higher aliphatic compounds, polyether-based compounds, polypropylene, and polyethylene, and these compounds are recycled polyester resins It may be added in an amount of 1 ppm to 100 ppm.
- the addition amount of the polycondensation catalyst may be 2 ppm to 800 ppm, for example, 4 ppm to 500 ppm as the weight of the catalyst metal element based on the total weight of the dibasic acid component.
- the regenerated polyester is a stabilizer, such as phosphoric acid esters such as trimethyl phosphate, triethyl phosphate, triphenyl phosphate, and triethyl phosphonoacetate; phosphorous acid esters such as triphenyl phosphite and trisdodecyl phosphite; and phosphorus compounds such as phosphate, monobutyl phosphate, phosphoric acid, phosphorous acid, hypophosphorous acid, and polyphosphoric acid.
- the amount of the stabilizer added may be 1000 ppm or less, for example, 500 ppm or less, or 300 ppm or less as the weight of elemental phosphorus in the stabilizer based on the total weight of the regenerated polyester.
- the color of the regenerated polyester prepared using the dibasic acid and alkylene glycol obtained thereby may have an L value of 60 or more, for example, from 65 to may be 95.
- the L, a, and b color systems are commonly used internationally as standards for color evaluation of polyester.
- This color numerical value is one of the color systems for standardizing color measurements, and describes recognizable colors and color differences.
- L is the lightness factor and a and b are the color measures.
- the L value means a numerical factor indicating brightness, and is a very important number in the manufacture of textiles, fabrics or clothes.
- a positive b value means yellow discoloration
- a negative value means blue discoloration
- a positive a value means red discoloration
- a negative value means green discoloration.
- L, a, and b values are defined in KS A 0061, 0063, 0064, 0065, 0066, 0067, 0084, 0085, 0089, 0114, etc. in the Korean Industrial Standards (KS) related to color measurement.
- KS Korean Industrial Standards
- L, a The , and b values can be measured by measuring the color 10 times by putting 50 g of the polyester resin to be measured in a calorimeter model SA-2000 after removing moisture from the air, and setting the average value as a standard value.
- the L value of the recycled polyester is related to the purity of the recycled dibasic acid and alkylene glycol. For example, as the amount of the matting agent such as impurities or titanium dioxide (TiO 2 ) inside increases, the L value decreases. If the L value is less than 60, the amount of impurities is too large, and the color after polymerization and fiberization may be colored or it may not be used as a high value-added material due to many side reactions during polymerization. So it may not be meaningful. On the other hand, when the L value exceeds 95, it is a physical property that is difficult to reach even with existing virgin materials. The cost increase can lead to lower economic feasibility.
- the matting agent such as impurities or titanium dioxide (TiO 2 ) inside
- TiO 2 titanium dioxide
- the content of sodium hydroxide impregnated in polyethylene terephthalate is 2.1 mol, 2.4 mol, and 3.0 mol, respectively, based on 1 mol of terephthalic acid.
- the content of sodium hydroxide impregnated in polyethylene terephthalate is 1.0 mol and 3.3 mol, respectively, based on 1 mol of terephthalic acid.
- the content of sodium hydroxide impregnated in polyethylene terephthalate is 2.1 moles, respectively, based on 1 mole of terephthalic acid.
- Example 1 The depolymerization process of Example 1 was observed, and pictures at each stage are shown in FIGS. 1 to 6 .
- FIG. 1 is a photograph showing colored polyethylene terephthalate
- FIG. 2 is a photograph showing decolorized polyethylene terephthalate
- FIG. 3 is a photograph of removing impurities by washing the depolymerized product with water
- FIG. 4 is a photograph of terephthalic acid recovered after washing with water and acid precipitation.
- 5 is a photograph of colored polyethylene terephthalate fibers and recovered terephthalic acid before and after depolymerization
- FIG. 6 is a comparative photograph of a polyester chip and a virgin polyester chip obtained by repolymerizing the recovered terephthalic acid as a raw material.
- the decomposition rate of the PET feedstock was measured by checking the residual amount of undecomposed polyethylene terephthalate (PET), and the yield of terephthalic acid (TPA) was obtained through NMR and HPLC analysis, and the result was Table 1 shows.
- the remainder except for terephthalic acid was determined as a side reactant, an unreacted substance, and an impurity.
- Example 1 93.8 93.1 90.8 -0.9 0.0
- Example 2 96.4 92.8 89.3 -1.2 -1.3
- Example 3 98 or higher 88.6 84.7 0.0 0.1
- Example 4 78.2 70.56 76.5 1.5 0.8
- Example 5 98 or higher 80.43 82.1 0.6
- Comparative Example 1 81.2 64.67 64.6 4.3 1.2 Comparative Example 2 72.4 53.56 58.5 2.2 4.1
- Examples 1 to 5 have superior PET degradation rate and TPA yield compared to Comparative Examples 1 and 2. It can be seen that in Comparative Example 1, since no decomposing agent was used, the neutral aqueous depolymerization process resulted in a decrease in the yield of terephthalic acid due to a large number of unreacted and side-reacted substances, and in Comparative Example 2, ordinary steam was used instead of superheated steam Accordingly, it can be seen that the PET decomposition rate and TPA yield are low even when the depolymerization treatment time is increased by 6 times or more.
- Example 4 since the content of the disintegrant is 1.0 mol, which does not reach the substantially required 2.0 mol, it is expected that PET will not be completely decomposed. However, the reason that the decomposition rate is higher than the expected decomposition rate according to the equivalent ratio is because the thermal decomposition was concurrently performed at a high temperature of 350 °C. Compared to this, it can be seen that the yield of TPA is lowered as expected due to unreacted materials and side reactants.
- Example 5 as the content of the decomposing agent was 3.3 moles, the amount of side reactants produced increased beyond the depolymerization step of an appropriate level, and the yield and purity of the recovered terephthalic acid decreased. Based on this, after purification through crystallization, the L value decreased due to side reactions during the final polyester repolymerization.
- the present invention relates to a method for rapid depolymerization of polyester, which removes dyes from colored polyester with low cost and high efficiency, can depolymerize colored polyester within a short time, has high depolymerization efficiency, and reduces the total depolymerization temperature of the depolymerization composition. It is economical as there is no need to increase it to
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Abstract
Description
PET 분해율 (%) |
TPA 수율 (%) |
색상 | |||
L | a | b | |||
실시예 1 | 93.8 | 93.1 | 90.8 | -0.9 | 0.0 |
실시예 2 | 96.4 | 92.8 | 89.3 | -1.2 | -1.3 |
실시예 3 | 98 이상 | 88.6 | 84.7 | 0.0 | 0.1 |
실시예 4 | 78.2 | 70.56 | 76.5 | 1.5 | 0.8 |
실시예 5 | 98 이상 | 80.43 | 82.1 | 0.6 | 0.5 |
비교예 1 | 81.2 | 64.67 | 64.6 | 4.3 | 1.2 |
비교예 2 | 72.4 | 53.56 | 58.5 | 2.2 | 4.1 |
Claims (16)
- 알칼리, 산, 이들의 염(salt), 모노 알코올, 다가 알코올, 또는 이들의 혼합물을 포함하는 분해제를 폴리에스테르에 첨가한 후,상기 폴리에스테르에 과열 수증기를 접촉시키는 해중합 단계를 포함하는, 폴리에스테르의 해중합 방법.
- 제1항에서,상기 과열 수증기의 온도는 250 ℃ 내지 450 ℃인, 폴리에스테르의 해중합 방법.
- 제1항에서,상기 과열 수증기는 0.1 bar 내지 2 bar의 분사 압력으로 가해지는, 폴리에스테르의 해중합 방법.
- 제1항에서,상기 해중합 단계는 1 분 내지 120 분 동안 이루어지는, 폴리에스테르의 해중합 방법.
- 제1항에서,상기 알칼리는 수산화나트륨, 수산화칼륨, 수산화리튬, 암모니아, 또는 이들의 혼합물을 포함하는, 폴리에스테르의 해중합 방법.
- 제1항에서,상기 산은 염산, 질산, 황산, 탄산, 인산, 아세트산, 차아염소산(HClO), 또는 이들의 혼합물을 포함하는, 폴리에스테르의 해중합 방법.
- 제1항에서,상기 염은 탄산염, 탄산수소염, 인산염, 황산염, 아황산염, 질산염, 규산염, 차아염소산염, 포름산염, 아세트산염, 구연산염, 옥살산염, 또는 이들의 혼합물을 포함하는, 폴리에스테르의 해중합 방법.
- 제1항에서,상기 모노 알코올은 메탄올, 에탄올, 프로판올, 부탄올, 또는 이들의 혼합물을 포함하는, 폴리에스테르의 해중합 방법.
- 제1항에서,상기 다가 알코올은 에틸렌 글리콜, n-프로필렌 글리콜, 이소프로필렌 글리콜, 디에틸렌 글리콜, 폴리에틸렌 글리콜, 트리에틸렌 글리콜, 디프로필렌 글리콜, 1,3-부탄디올, 1,4-부탄디올, 글리세린, 벤질 알코올, 폴리프로필렌 글리콜, 펜타에리트리톨, 트리메티롤프로판, 또는 이들의 혼합물을 포함하는, 폴리에스테르의 해중합 방법.
- 제1항에서,상기 분해제는 상기 폴리에스테르가 포함하는 이염기산 1.0 몰에 대하여 0.75 몰 내지 3.0 몰로 첨가되는, 폴리에스테르의 해중합 방법.
- 제1항에서,상기 폴리에스테르의 해중합 방법은,상기 해중합 단계에서 얻어진 해중합 생성물로부터 액상의 알킬렌 글리콜과 고상의 이염기산염을 고액분리하는 단계,상기 고상의 이염기산염을 물에 용해시키는 단계,상기 이염기산염의 수용액을 산으로 중화하여 이염기산 결정을 석출시키는 단계, 및상기 석출 생성물로부터 이염기산 결정을 고액분리하는 단계를 더 포함하는 폴리에스테르의 해중합 방법.
- 제1항에서,상기 폴리에스테르의 해중합 방법은, 상기 이염기산염의 수용액에서 불순물을 제거하는 단계를 더 포함하는, 폴리에스테르의 해중합 방법.
- 제1항에서,상기 폴리에스테르의 해중합 방법은, 상기 이염기산 결정을 재결정시키는 단계를 더 포함하는, 폴리에스테르의 해중합 방법.
- 제1항에 따른 폴리에스테르의 해중합 방법에 의하여 얻어진, 이염기산 및 알킬렌 글리콜을 포함하는, 재생 폴리에스테르 중합용 조성물.
- 제14항에 따른 폴리에스테르 중합용 조성물을 이용하여 제조된, 재생 폴리에스테르.
- 제15항에서,상기 재생 폴리에스테르의 색상은 L값이 60 이상인, 재생 폴리에스테르.
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EP21919848.8A EP4257636A1 (en) | 2021-01-14 | 2021-11-03 | Method for depolymerising polyester |
JP2023542546A JP2024502864A (ja) | 2021-01-14 | 2021-11-03 | ポリエステルの解重合方法 |
US18/260,792 US20240052131A1 (en) | 2021-01-14 | 2021-11-03 | Method for depolymerising polyester |
CN202180090826.XA CN116745349A (zh) | 2021-01-14 | 2021-11-03 | 使聚酯解聚的方法 |
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KR1020210005356A KR20220102882A (ko) | 2021-01-14 | 2021-01-14 | 폴리에스테르의 해중합 방법 |
KR10-2021-0005356 | 2021-01-14 |
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EP (1) | EP4257636A1 (ko) |
JP (1) | JP2024502864A (ko) |
KR (1) | KR20220102882A (ko) |
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2021
- 2021-01-14 KR KR1020210005356A patent/KR20220102882A/ko not_active Application Discontinuation
- 2021-11-03 CN CN202180090826.XA patent/CN116745349A/zh active Pending
- 2021-11-03 US US18/260,792 patent/US20240052131A1/en active Pending
- 2021-11-03 EP EP21919848.8A patent/EP4257636A1/en active Pending
- 2021-11-03 JP JP2023542546A patent/JP2024502864A/ja active Pending
- 2021-11-03 WO PCT/KR2021/015822 patent/WO2022154224A1/ko active Application Filing
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JP2024502864A (ja) | 2024-01-23 |
CN116745349A (zh) | 2023-09-12 |
US20240052131A1 (en) | 2024-02-15 |
KR20220102882A (ko) | 2022-07-21 |
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