TW505627B - Method for preparing purified terephthalic acid - Google Patents
Method for preparing purified terephthalic acid Download PDFInfo
- Publication number
- TW505627B TW505627B TW087118140A TW87118140A TW505627B TW 505627 B TW505627 B TW 505627B TW 087118140 A TW087118140 A TW 087118140A TW 87118140 A TW87118140 A TW 87118140A TW 505627 B TW505627 B TW 505627B
- Authority
- TW
- Taiwan
- Prior art keywords
- terephthalic acid
- solution
- solvent
- temperature
- patent application
- Prior art date
Links
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 title claims abstract description 423
- 238000000034 method Methods 0.000 title claims abstract description 96
- 239000002904 solvent Substances 0.000 claims abstract description 180
- 239000012065 filter cake Substances 0.000 claims abstract description 43
- 239000000047 product Substances 0.000 claims abstract description 38
- 238000010956 selective crystallization Methods 0.000 claims abstract description 32
- 239000007788 liquid Substances 0.000 claims abstract description 25
- 239000000463 material Substances 0.000 claims abstract description 24
- 239000012535 impurity Substances 0.000 claims abstract description 20
- 239000006185 dispersion Substances 0.000 claims abstract description 19
- 239000007858 starting material Substances 0.000 claims abstract description 15
- 238000001914 filtration Methods 0.000 claims abstract description 13
- 238000007086 side reaction Methods 0.000 claims abstract description 10
- 239000013078 crystal Substances 0.000 claims description 102
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 63
- 238000005406 washing Methods 0.000 claims description 32
- 238000000746 purification Methods 0.000 claims description 20
- 238000001704 evaporation Methods 0.000 claims description 19
- 230000008020 evaporation Effects 0.000 claims description 18
- 238000002791 soaking Methods 0.000 claims description 8
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 claims description 6
- 238000000926 separation method Methods 0.000 claims description 6
- 239000007795 chemical reaction product Substances 0.000 claims description 4
- 238000002425 crystallisation Methods 0.000 abstract description 99
- 230000008025 crystallization Effects 0.000 abstract description 80
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 abstract description 22
- 229920001225 polyester resin Polymers 0.000 abstract description 6
- 239000004645 polyester resin Substances 0.000 abstract description 6
- 230000009972 noncorrosive effect Effects 0.000 abstract description 5
- 238000012545 processing Methods 0.000 abstract description 4
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical group CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 abstract 1
- 229940113088 dimethylacetamide Drugs 0.000 abstract 1
- GOUHYARYYWKXHS-UHFFFAOYSA-N 4-formylbenzoic acid Chemical compound OC(=O)C1=CC=C(C=O)C=C1 GOUHYARYYWKXHS-UHFFFAOYSA-N 0.000 description 65
- 239000000243 solution Substances 0.000 description 45
- 239000002253 acid Substances 0.000 description 41
- 239000000203 mixture Substances 0.000 description 37
- 238000001816 cooling Methods 0.000 description 30
- 238000011084 recovery Methods 0.000 description 29
- 150000003839 salts Chemical class 0.000 description 28
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 24
- 239000007787 solid Substances 0.000 description 21
- 239000007800 oxidant agent Substances 0.000 description 20
- 239000002002 slurry Substances 0.000 description 18
- 238000004090 dissolution Methods 0.000 description 15
- 239000012452 mother liquor Substances 0.000 description 15
- 238000007254 oxidation reaction Methods 0.000 description 14
- 230000003647 oxidation Effects 0.000 description 13
- 239000013557 residual solvent Substances 0.000 description 12
- 239000008117 stearic acid Substances 0.000 description 12
- 235000021355 Stearic acid Nutrition 0.000 description 11
- 238000004519 manufacturing process Methods 0.000 description 11
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 11
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 11
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 10
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 9
- 239000005711 Benzoic acid Substances 0.000 description 9
- -1 alkyl acids Chemical class 0.000 description 9
- 238000009826 distribution Methods 0.000 description 9
- 238000002474 experimental method Methods 0.000 description 9
- 230000008569 process Effects 0.000 description 9
- URLKBWYHVLBVBO-UHFFFAOYSA-N Para-Xylene Chemical group CC1=CC=C(C)C=C1 URLKBWYHVLBVBO-UHFFFAOYSA-N 0.000 description 8
- 238000009835 boiling Methods 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 7
- 239000003960 organic solvent Substances 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 6
- UKMSUNONTOPOIO-UHFFFAOYSA-N docosanoic acid Chemical compound CCCCCCCCCCCCCCCCCCCCCC(O)=O UKMSUNONTOPOIO-UHFFFAOYSA-N 0.000 description 6
- 238000001035 drying Methods 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- 239000002245 particle Substances 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 230000014759 maintenance of location Effects 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- 229920006395 saturated elastomer Polymers 0.000 description 5
- 238000003860 storage Methods 0.000 description 5
- XJKSTNDFUHDPQJ-UHFFFAOYSA-N 1,4-diphenylbenzene Chemical compound C1=CC=CC=C1C1=CC=C(C=2C=CC=CC=2)C=C1 XJKSTNDFUHDPQJ-UHFFFAOYSA-N 0.000 description 4
- 241000196324 Embryophyta Species 0.000 description 4
- YNAVUWVOSKDBBP-UHFFFAOYSA-N Morpholine Chemical compound C1COCCN1 YNAVUWVOSKDBBP-UHFFFAOYSA-N 0.000 description 4
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 4
- 235000010233 benzoic acid Nutrition 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 238000007654 immersion Methods 0.000 description 4
- 230000006872 improvement Effects 0.000 description 4
- WLJVXDMOQOGPHL-UHFFFAOYSA-N phenylacetic acid Chemical compound OC(=O)CC1=CC=CC=C1 WLJVXDMOQOGPHL-UHFFFAOYSA-N 0.000 description 4
- 229920000728 polyester Polymers 0.000 description 4
- 239000012047 saturated solution Substances 0.000 description 4
- 230000007704 transition Effects 0.000 description 4
- KVGZZAHHUNAVKZ-UHFFFAOYSA-N 1,4-Dioxin Chemical compound O1C=COC=C1 KVGZZAHHUNAVKZ-UHFFFAOYSA-N 0.000 description 3
- 235000021357 Behenic acid Nutrition 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 229940116226 behenic acid Drugs 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 239000006184 cosolvent Substances 0.000 description 3
- 239000003085 diluting agent Substances 0.000 description 3
- WOZVHXUHUFLZGK-UHFFFAOYSA-N dimethyl terephthalate Chemical compound COC(=O)C1=CC=C(C(=O)OC)C=C1 WOZVHXUHUFLZGK-UHFFFAOYSA-N 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 239000000543 intermediate Substances 0.000 description 3
- 239000007791 liquid phase Substances 0.000 description 3
- 231100000252 nontoxic Toxicity 0.000 description 3
- 230000003000 nontoxic effect Effects 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 2
- KXCVRJMSLWDHNJ-UHFFFAOYSA-N 1-(9H-fluoren-1-yl)pyrrolidin-2-one Chemical compound C1(=CC=CC=2C3=CC=CC=C3CC12)N1C(CCC1)=O KXCVRJMSLWDHNJ-UHFFFAOYSA-N 0.000 description 2
- ZFPGARUNNKGOBB-UHFFFAOYSA-N 1-Ethyl-2-pyrrolidinone Chemical compound CCN1CCCC1=O ZFPGARUNNKGOBB-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- CAGQYNIMOLSFJR-UHFFFAOYSA-N C1(=CC=CC=2C3=CC=CC=C3CC12)N(C(C)=O)C1=CC=CC=2C3=CC=CC=C3CC12 Chemical compound C1(=CC=CC=2C3=CC=CC=C3CC12)N(C(C)=O)C1=CC=CC=2C3=CC=CC=C3CC12 CAGQYNIMOLSFJR-UHFFFAOYSA-N 0.000 description 2
- YKFRISUTLMLERS-UHFFFAOYSA-N C1(=CC=CC=2C3=CC=CC=C3CC12)N1C(CCCC1)=O Chemical compound C1(=CC=CC=2C3=CC=CC=C3CC12)N1C(CCCC1)=O YKFRISUTLMLERS-UHFFFAOYSA-N 0.000 description 2
- QCDKDIDFDVVDLU-UHFFFAOYSA-N C1(=CC=CC=2C3=CC=CC=C3CC1=2)N1CCCCC1 Chemical compound C1(=CC=CC=2C3=CC=CC=C3CC1=2)N1CCCCC1 QCDKDIDFDVVDLU-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- IPBVNPXQWQGGJP-UHFFFAOYSA-N acetic acid phenyl ester Natural products CC(=O)OC1=CC=CC=C1 IPBVNPXQWQGGJP-UHFFFAOYSA-N 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 239000001361 adipic acid Substances 0.000 description 2
- 235000011037 adipic acid Nutrition 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000012467 final product Substances 0.000 description 2
- 239000006260 foam Substances 0.000 description 2
- BDJRBEYXGGNYIS-UHFFFAOYSA-N nonanedioic acid Chemical compound OC(=O)CCCCCCCC(O)=O BDJRBEYXGGNYIS-UHFFFAOYSA-N 0.000 description 2
- LPNBBFKOUUSUDB-UHFFFAOYSA-N p-toluic acid Chemical compound CC1=CC=C(C(O)=O)C=C1 LPNBBFKOUUSUDB-UHFFFAOYSA-N 0.000 description 2
- 229940049953 phenylacetate Drugs 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 230000008929 regeneration Effects 0.000 description 2
- 238000011069 regeneration method Methods 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 239000007790 solid phase Substances 0.000 description 2
- 230000003068 static effect Effects 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- KDYFGRWQOYBRFD-UHFFFAOYSA-N succinic acid Chemical compound OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- QWUWMCYKGHVNAV-UHFFFAOYSA-N 1,2-dihydrostilbene Chemical group C=1C=CC=CC=1CCC1=CC=CC=C1 QWUWMCYKGHVNAV-UHFFFAOYSA-N 0.000 description 1
- YJTKZCDBKVTVBY-UHFFFAOYSA-N 1,3-Diphenylbenzene Chemical compound C1=CC=CC=C1C1=CC=CC(C=2C=CC=CC=2)=C1 YJTKZCDBKVTVBY-UHFFFAOYSA-N 0.000 description 1
- WDQFELCEOPFLCZ-UHFFFAOYSA-N 1-(2-hydroxyethyl)pyrrolidin-2-one Chemical compound OCCN1CCCC1=O WDQFELCEOPFLCZ-UHFFFAOYSA-N 0.000 description 1
- JBODMFWMIWWZSF-UHFFFAOYSA-N 1-(2-sulfanylethyl)pyrrolidin-2-one Chemical compound SCCN1CCCC1=O JBODMFWMIWWZSF-UHFFFAOYSA-N 0.000 description 1
- DYNFCHNNOHNJFG-UHFFFAOYSA-N 2-formylbenzoic acid Chemical compound OC(=O)C1=CC=CC=C1C=O DYNFCHNNOHNJFG-UHFFFAOYSA-N 0.000 description 1
- RABQBOCUJIKPFY-UHFFFAOYSA-N 4-(9H-fluoren-1-yl)morpholine Chemical compound C1(=CC=CC=2C3=CC=CC=C3CC1=2)N1CCOCC1 RABQBOCUJIKPFY-UHFFFAOYSA-N 0.000 description 1
- FJKROLUGYXJWQN-UHFFFAOYSA-N 4-hydroxybenzoic acid Chemical compound OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 description 1
- 241000208140 Acer Species 0.000 description 1
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 1
- PMKKCWBIWWSSCH-UHFFFAOYSA-N C1(=CC=CC=2C3=CC=CC=C3CC12)N1C(CCC1)=S Chemical compound C1(=CC=CC=2C3=CC=CC=C3CC12)N1C(CCC1)=S PMKKCWBIWWSSCH-UHFFFAOYSA-N 0.000 description 1
- BUUJIPWMFWVIIF-UHFFFAOYSA-N C1(=CC=CC=2C3=CC=CC=C3CC12)N1CN=CC=C1 Chemical compound C1(=CC=CC=2C3=CC=CC=C3CC12)N1CN=CC=C1 BUUJIPWMFWVIIF-UHFFFAOYSA-N 0.000 description 1
- 206010061218 Inflammation Diseases 0.000 description 1
- WJJGAKCAAJOICV-UHFFFAOYSA-N N-dimethyltyrosine Natural products CN(C)C(C(O)=O)CC1=CC=C(O)C=C1 WJJGAKCAAJOICV-UHFFFAOYSA-N 0.000 description 1
- OHLUUHNLEMFGTQ-UHFFFAOYSA-N N-methylacetamide Chemical compound CNC(C)=O OHLUUHNLEMFGTQ-UHFFFAOYSA-N 0.000 description 1
- ZWXPDGCFMMFNRW-UHFFFAOYSA-N N-methylcaprolactam Chemical compound CN1CCCCCC1=O ZWXPDGCFMMFNRW-UHFFFAOYSA-N 0.000 description 1
- ZVOOGERIHVAODX-UHFFFAOYSA-N O-demycinosyltylosin Natural products O=CCC1CC(C)C(=O)C=CC(C)=CC(CO)C(CC)OC(=O)CC(O)C(C)C1OC1C(O)C(N(C)C)C(OC2OC(C)C(O)C(C)(O)C2)C(C)O1 ZVOOGERIHVAODX-UHFFFAOYSA-N 0.000 description 1
- 229910052778 Plutonium Inorganic materials 0.000 description 1
- YZCKVEUIGOORGS-NJFSPNSNSA-N Tritium Chemical compound [3H] YZCKVEUIGOORGS-NJFSPNSNSA-N 0.000 description 1
- 230000001594 aberrant effect Effects 0.000 description 1
- 238000010669 acid-base reaction Methods 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 238000005276 aerator Methods 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 150000001409 amidines Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- IYSGJCJSRBFZSZ-UHFFFAOYSA-N carbon monoxide;manganese;5-methylcyclopenta-1,3-diene Chemical compound [Mn].[O+]#[C-].[O+]#[C-].[O+]#[C-].C[C-]1C=CC=C1 IYSGJCJSRBFZSZ-UHFFFAOYSA-N 0.000 description 1
- 235000013339 cereals Nutrition 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000007810 chemical reaction solvent Substances 0.000 description 1
- 229940011182 cobalt acetate Drugs 0.000 description 1
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 239000012612 commercial material Substances 0.000 description 1
- 239000002826 coolant Substances 0.000 description 1
- 239000013058 crude material Substances 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 150000002013 dioxins Chemical class 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 238000005108 dry cleaning Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 230000007717 exclusion Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000010408 film Substances 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 150000007857 hydrazones Chemical class 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 239000012442 inert solvent Substances 0.000 description 1
- 230000004054 inflammatory process Effects 0.000 description 1
- 238000001802 infusion Methods 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 229940071125 manganese acetate Drugs 0.000 description 1
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 239000011268 mixed slurry Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- DSWNRHCOGVRDOE-UHFFFAOYSA-N n,n-dimethylmethanimidamide Chemical compound CN(C)C=N DSWNRHCOGVRDOE-UHFFFAOYSA-N 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 150000007530 organic bases Chemical group 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 238000001139 pH measurement Methods 0.000 description 1
- 150000007965 phenolic acids Chemical class 0.000 description 1
- WOHDXQQIBRMRFA-UHFFFAOYSA-N phenyl 4-methylbenzoate Chemical compound C1=CC(C)=CC=C1C(=O)OC1=CC=CC=C1 WOHDXQQIBRMRFA-UHFFFAOYSA-N 0.000 description 1
- 229960003424 phenylacetic acid Drugs 0.000 description 1
- 239000003279 phenylacetic acid Substances 0.000 description 1
- WAJUCMNAGKFHLB-UHFFFAOYSA-N phenylarsinic acid Chemical compound O[AsH](=O)C1=CC=CC=C1 WAJUCMNAGKFHLB-UHFFFAOYSA-N 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- OYEHPCDNVJXUIW-UHFFFAOYSA-N plutonium atom Chemical compound [Pu] OYEHPCDNVJXUIW-UHFFFAOYSA-N 0.000 description 1
- 239000003495 polar organic solvent Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- HNJBEVLQSNELDL-UHFFFAOYSA-N pyrrolidin-2-one Chemical compound O=C1CCCN1 HNJBEVLQSNELDL-UHFFFAOYSA-N 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 230000008521 reorganization Effects 0.000 description 1
- 238000012552 review Methods 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 239000002195 soluble material Substances 0.000 description 1
- 238000000935 solvent evaporation Methods 0.000 description 1
- 239000011877 solvent mixture Substances 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 239000001384 succinic acid Substances 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000029305 taxis Effects 0.000 description 1
- 150000003503 terephthalic acid derivatives Chemical class 0.000 description 1
- 150000003504 terephthalic acids Chemical class 0.000 description 1
- RWRDLPDLKQPQOW-UHFFFAOYSA-N tetrahydropyrrole Substances C1CCNC1 RWRDLPDLKQPQOW-UHFFFAOYSA-N 0.000 description 1
- RAOIDOHSFRTOEL-UHFFFAOYSA-N tetrahydrothiophene Chemical compound C1CCSC1 RAOIDOHSFRTOEL-UHFFFAOYSA-N 0.000 description 1
- 229910052722 tritium Inorganic materials 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 230000004580 weight loss Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/42—Separation; Purification; Stabilisation; Use of additives
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/42—Separation; Purification; Stabilisation; Use of additives
- C07C51/43—Separation; Purification; Stabilisation; Use of additives by change of the physical state, e.g. crystallisation
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Crystallography & Structural Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US08/962,030 US5840968A (en) | 1995-06-07 | 1997-10-31 | Method and apparatus for preparing purified terephthalic acid |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| TW505627B true TW505627B (en) | 2002-10-11 |
Family
ID=25505339
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| TW087118140A TW505627B (en) | 1997-10-31 | 1999-02-22 | Method for preparing purified terephthalic acid |
Country Status (17)
| Country | Link |
|---|---|
| US (1) | US5840968A (https=) |
| EP (1) | EP1030829B1 (https=) |
| JP (1) | JP4381600B2 (https=) |
| KR (1) | KR100603723B1 (https=) |
| CN (1) | CN1127471C (https=) |
| AR (1) | AR017765A1 (https=) |
| AU (1) | AU1286899A (https=) |
| BR (1) | BR9813349B1 (https=) |
| CA (1) | CA2307783C (https=) |
| DE (1) | DE69835229T2 (https=) |
| ES (1) | ES2263227T3 (https=) |
| ID (1) | ID21201A (https=) |
| MY (1) | MY119529A (https=) |
| RU (1) | RU2213725C2 (https=) |
| TR (1) | TR200001138T2 (https=) |
| TW (1) | TW505627B (https=) |
| WO (1) | WO1999023055A1 (https=) |
Families Citing this family (83)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| AU4002199A (en) * | 1998-05-29 | 1999-12-20 | Hfm International, Inc. | Method for preparing purified terephthalic acid and isophthalic acid from mixed xylenes |
| KR100642625B1 (ko) * | 1998-11-24 | 2006-11-10 | 티. 디. 빈센트 린 | 고순도 방향족 폴리카르복실산 및 이것의 유도체를 정제및 생성하는 방법 |
| US6291707B1 (en) * | 1999-03-12 | 2001-09-18 | Tsong-Dar Vincent Lin | Process of purifying and producing high purity aromatic polycarboxylic acids and derivatives thereof |
| US6392091B2 (en) * | 1998-11-24 | 2002-05-21 | Tsong-Dar Vincent Lin | Process of purifying and producing high purity aromatic polycarboxylic acids |
| AU7055500A (en) | 1999-08-30 | 2001-03-26 | Mossi & Ghisolfi Overseas S.A. | An integrated process for the production of 2,6-naphthalene dicarboxylic acid |
| US6649263B2 (en) | 2001-11-16 | 2003-11-18 | Honeywell International Inc. | Polyester resin and industrial yarn process |
| DE10206168A1 (de) * | 2002-02-14 | 2003-08-21 | Guehring Joerg | Kupplung für mudular aufgebaute Werkzeughalterarme |
| US7276625B2 (en) * | 2002-10-15 | 2007-10-02 | Eastman Chemical Company | Process for production of a carboxylic acid/diol mixture suitable for use in polyester production |
| US7161027B2 (en) | 2002-12-09 | 2007-01-09 | Eastman Chemical Company | Process for the oxidative purification of terephthalic acid |
| US7074954B2 (en) * | 2002-12-09 | 2006-07-11 | Eastman Chemical Company | Process for the oxidative purification of terephthalic acid |
| US7132566B2 (en) * | 2003-09-22 | 2006-11-07 | Eastman Chemical Company | Process for the purification of a crude carboxylic acid slurry |
| BR0316462A (pt) * | 2002-12-09 | 2005-10-11 | Eastman Chem Co | Processos para reduzir uma suspensão de ácido carboxìlico purificado, para purificar um produto de oxidação em estágios, para produzir um produto de ácido carboxìlico purificado, e, suspensão de ácido carboxìlico purificado |
| CN100453517C (zh) * | 2003-01-10 | 2009-01-21 | 三菱化学株式会社 | 芳香羧酸的制备方法和对苯二甲酸的制备方法 |
| US7193109B2 (en) * | 2003-03-06 | 2007-03-20 | Eastman Chemical Company | Process for production of a carboxylic acid/diol mixture suitable for use in polyester production |
| US20050059709A1 (en) * | 2003-09-15 | 2005-03-17 | Meythaler Jay M. | Treatment of a neuropathy with rapid release aminopyridine |
| US7214760B2 (en) * | 2004-01-15 | 2007-05-08 | Eastman Chemical Company | Process for production of a carboxylic acid/diol mixture suitable for use in polyester production |
| WO2006088470A2 (en) * | 2004-04-09 | 2006-08-24 | Gtc Technology Inc. | Purification of carboxylic acids by complexation with selective solvents |
| US20050288527A1 (en) * | 2004-06-28 | 2005-12-29 | Cook William L | Method for preparing free-flowing crystalline material |
| US7741515B2 (en) | 2004-09-02 | 2010-06-22 | Eastman Chemical Company | Optimized liquid-phase oxidation |
| US7563926B2 (en) | 2004-09-02 | 2009-07-21 | Eastman Chemical Company | Optimized liquid-phase oxidation |
| US7568361B2 (en) | 2004-09-02 | 2009-08-04 | Eastman Chemical Company | Optimized liquid-phase oxidation |
| US7361784B2 (en) | 2004-09-02 | 2008-04-22 | Eastman Chemical Company | Optimized liquid-phase oxidation |
| US7371894B2 (en) | 2004-09-02 | 2008-05-13 | Eastman Chemical Company | Optimized liquid-phase oxidation |
| US7608732B2 (en) | 2005-03-08 | 2009-10-27 | Eastman Chemical Company | Optimized liquid-phase oxidation |
| US7692036B2 (en) | 2004-11-29 | 2010-04-06 | Eastman Chemical Company | Optimized liquid-phase oxidation |
| US7692037B2 (en) | 2004-09-02 | 2010-04-06 | Eastman Chemical Company | Optimized liquid-phase oxidation |
| US7399882B2 (en) | 2004-09-02 | 2008-07-15 | Eastman Chemical Company | Optimized liquid-phase oxidation |
| US7572932B2 (en) | 2004-09-02 | 2009-08-11 | Eastman Chemical Company | Optimized liquid-phase oxidation |
| US7572936B2 (en) | 2004-09-02 | 2009-08-11 | Eastman Chemical Company | Optimized liquid-phase oxidation |
| US7608733B2 (en) | 2004-09-02 | 2009-10-27 | Eastman Chemical Company | Optimized liquid-phase oxidation |
| US7586000B2 (en) | 2004-09-02 | 2009-09-08 | Eastman Chemical Company | Optimized liquid-phase oxidation |
| US7390921B2 (en) | 2004-09-02 | 2008-06-24 | Eastman Chemical Company | Optimized liquid-phase oxidation |
| US7482482B2 (en) | 2004-09-02 | 2009-01-27 | Eastman Chemical Company | Optimized liquid-phase oxidation |
| US7910769B2 (en) | 2004-09-02 | 2011-03-22 | Eastman Chemical Company | Optimized liquid-phase oxidation |
| US7381836B2 (en) | 2004-09-02 | 2008-06-03 | Eastman Chemical Company | Optimized liquid-phase oxidation |
| US7507857B2 (en) | 2004-09-02 | 2009-03-24 | Eastman Chemical Company | Optimized liquid-phase oxidation |
| US7589231B2 (en) | 2004-09-02 | 2009-09-15 | Eastman Chemical Company | Optimized liquid-phase oxidation |
| US7683210B2 (en) | 2004-09-02 | 2010-03-23 | Eastman Chemical Company | Optimized liquid-phase oxidation |
| US7495125B2 (en) | 2004-09-02 | 2009-02-24 | Eastman Chemical Company | Optimized liquid-phase oxidation |
| US7504535B2 (en) | 2004-09-02 | 2009-03-17 | Eastman Chemical Company | Optimized liquid-phase oxidation |
| US7582793B2 (en) | 2004-09-02 | 2009-09-01 | Eastman Chemical Company | Optimized liquid-phase oxidation |
| US7304178B2 (en) * | 2005-05-19 | 2007-12-04 | Eastman Chemical Company | Enriched isophthalic acid composition |
| US7834208B2 (en) * | 2005-05-19 | 2010-11-16 | Eastman Chemical Company | Process to produce a post catalyst removal composition |
| US7557243B2 (en) * | 2005-05-19 | 2009-07-07 | Eastman Chemical Company | Enriched terephthalic acid composition |
| US7741516B2 (en) | 2005-05-19 | 2010-06-22 | Eastman Chemical Company | Process to enrich a carboxylic acid composition |
| US20060264664A1 (en) * | 2005-05-19 | 2006-11-23 | Parker Kenny R | Esterification of an exchange solvent enriched composition |
| US7880031B2 (en) * | 2005-05-19 | 2011-02-01 | Eastman Chemical Company | Process to produce an enrichment feed |
| US20060264662A1 (en) * | 2005-05-19 | 2006-11-23 | Gibson Philip E | Esterification of an enriched composition |
| US7919652B2 (en) * | 2005-05-19 | 2011-04-05 | Eastman Chemical Company | Process to produce an enriched composition through the use of a catalyst removal zone and an enrichment zone |
| US7884231B2 (en) * | 2005-05-19 | 2011-02-08 | Eastman Chemical Company | Process to produce an enriched composition |
| US7897809B2 (en) * | 2005-05-19 | 2011-03-01 | Eastman Chemical Company | Process to produce an enrichment feed |
| US7432395B2 (en) * | 2005-05-19 | 2008-10-07 | Eastman Chemical Company | Enriched carboxylic acid composition |
| US20060264656A1 (en) * | 2005-05-19 | 2006-11-23 | Fujitsu Limited | Enrichment process using compounds useful in a polyester process |
| US7884232B2 (en) | 2005-06-16 | 2011-02-08 | Eastman Chemical Company | Optimized liquid-phase oxidation |
| US7358389B2 (en) | 2006-01-04 | 2008-04-15 | Eastman Chemical Company | Oxidation system employing internal structure for enhanced hydrodynamics |
| US7355068B2 (en) * | 2006-01-04 | 2008-04-08 | Eastman Chemical Company | Oxidation system with internal secondary reactor |
| US20070179312A1 (en) * | 2006-02-02 | 2007-08-02 | O'meadhra Ruairi Seosamh | Process for the purification of a crude carboxylic axid slurry |
| US8173835B2 (en) * | 2006-03-01 | 2012-05-08 | Grupo Petrotemex, S.A. De C.V. | Method and apparatus for drying carboxylic acid |
| US7888529B2 (en) | 2006-03-01 | 2011-02-15 | Eastman Chemical Company | Process to produce a post catalyst removal composition |
| US8697906B2 (en) * | 2006-03-01 | 2014-04-15 | Grupo Petrotemex, S.A. De C.V. | Methods and apparatus for producing a low-moisture carboxylic acid wet cake |
| US8455680B2 (en) | 2008-01-15 | 2013-06-04 | Eastman Chemical Company | Carboxylic acid production process employing solvent from esterification of lignocellulosic material |
| US8614350B2 (en) | 2008-01-15 | 2013-12-24 | Eastman Chemical Company | Carboxylic acid production process employing solvent from esterification of lignocellulosic material |
| CN102421741B (zh) * | 2009-04-24 | 2014-03-26 | 英威达技术有限公司 | 用于处理、纯化粗对苯二甲酸及相关过程流的方法、步骤及系统 |
| WO2012026333A1 (ja) * | 2010-08-23 | 2012-03-01 | ソニー株式会社 | 有機薄膜の形成方法および形成装置、ならびに有機デバイスの製造方法 |
| CN102234226A (zh) * | 2010-09-02 | 2011-11-09 | 华东理工大学 | 一种从碱减量废液中回收提纯对苯二甲酸的方法 |
| CN102179063A (zh) * | 2011-03-23 | 2011-09-14 | 苏州汇通色谱分离纯化有限公司 | 高压液-液萃取方法 |
| CN103030554B (zh) * | 2011-09-30 | 2015-04-08 | 中国石油化工股份有限公司 | 溶剂置换粗对苯二甲酸氧化浆料的方法 |
| CN103121943B (zh) * | 2011-11-18 | 2015-08-12 | 中国石油化工股份有限公司 | 提纯粗间苯二甲酸氧化浆料的方法 |
| RU2475475C1 (ru) * | 2011-12-26 | 2013-02-20 | Открытое акционерное общество "Каустик" (ОАО "Каустик") | Способ получения диамида терефталевой кислоты |
| US8927764B2 (en) | 2011-12-29 | 2015-01-06 | Uop Llc | Process for producing terephthalic acid |
| US9150484B2 (en) | 2011-12-29 | 2015-10-06 | Uop Llc | Process for producing terephthalic acid |
| US8759571B2 (en) | 2011-12-29 | 2014-06-24 | Uop Llc | Process for oxidizing alkyl-aromatic compounds |
| US9156765B2 (en) | 2011-12-29 | 2015-10-13 | Uop Llc | Process for oxidizing alkyl-aromatic compounds |
| US9045408B2 (en) | 2011-12-29 | 2015-06-02 | Uop Llc | Process for oxidizing alkyl-aromatic compounds |
| US8697905B2 (en) | 2011-12-29 | 2014-04-15 | Uop Llc | Process for producing terephthalic acid |
| US9024059B2 (en) | 2011-12-29 | 2015-05-05 | Uop Llc | Process for producing terephthalic acid |
| US9085522B2 (en) | 2011-12-29 | 2015-07-21 | Uop Llc | Process for producing terephthalic acid |
| CN108623065B (zh) | 2017-03-22 | 2020-08-25 | 天华化工机械及自动化研究设计院有限公司 | Pta精制单元母液的回收利用方法 |
| AU2022277645A1 (en) | 2021-05-20 | 2023-11-30 | Carbios | Process for degrading a plastic product comprising at least one polyester |
| CN117413007A (zh) | 2021-05-20 | 2024-01-16 | 卡比奥斯公司 | 降解包含至少一种聚酯的塑料产品的方法 |
| EP4206270A4 (en) * | 2021-07-19 | 2025-04-09 | Lg Chem, Ltd. | Monomer composition for synthesizing recycled plastic, method for preparing same, and recycled plastic, molded article, and plasticizer composition using same |
| TW202332768A (zh) | 2021-11-16 | 2023-08-16 | 法商卡爾畢歐斯公司 | 酯酶之新穎用途 |
| CN120864981B (zh) * | 2025-09-22 | 2026-04-21 | 浙江工业大学 | 一种印染白泥绿色资源化利用的工艺 |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB818211A (en) * | 1955-11-08 | 1959-08-12 | Hoechst Ag | Manufacture of pure terephthalic acid |
| US3931305A (en) * | 1973-08-20 | 1976-01-06 | Standard Oil Company | Terephthalic acid recovery by continuous flash crystallization |
| US4380662A (en) * | 1981-03-16 | 1983-04-19 | Labofina, S.A. | Process for the purification of terephthalic acid |
| US5159109A (en) * | 1990-06-25 | 1992-10-27 | Amoco Corporation | Purification of organic polycarboxylic acids |
| DE69210790T2 (de) * | 1991-12-03 | 1996-10-10 | Mitsubishi Chem Corp | Verfahren zur Herstellung von Naphthalendicarbonsäure |
| US5767311A (en) * | 1995-06-07 | 1998-06-16 | Glitsch International, Inc. | Method and apparatus for preparing purified terephtalic acid |
-
1997
- 1997-10-31 US US08/962,030 patent/US5840968A/en not_active Expired - Lifetime
-
1998
- 1998-10-29 BR BRPI9813349-7A patent/BR9813349B1/pt not_active IP Right Cessation
- 1998-10-29 EP EP98956315A patent/EP1030829B1/en not_active Expired - Lifetime
- 1998-10-29 AU AU12868/99A patent/AU1286899A/en not_active Abandoned
- 1998-10-29 ID IDP981421A patent/ID21201A/id unknown
- 1998-10-29 CN CN98810798A patent/CN1127471C/zh not_active Expired - Fee Related
- 1998-10-29 ES ES98956315T patent/ES2263227T3/es not_active Expired - Lifetime
- 1998-10-29 KR KR1020007004687A patent/KR100603723B1/ko not_active Expired - Fee Related
- 1998-10-29 JP JP2000518932A patent/JP4381600B2/ja not_active Expired - Fee Related
- 1998-10-29 DE DE69835229T patent/DE69835229T2/de not_active Expired - Lifetime
- 1998-10-29 RU RU2000113847/04A patent/RU2213725C2/ru not_active IP Right Cessation
- 1998-10-29 WO PCT/US1998/022942 patent/WO1999023055A1/en not_active Ceased
- 1998-10-29 TR TR2000/01138T patent/TR200001138T2/xx unknown
- 1998-10-29 CA CA002307783A patent/CA2307783C/en not_active Expired - Fee Related
- 1998-10-30 MY MYPI98004967A patent/MY119529A/en unknown
- 1998-10-30 AR ARP980105476A patent/AR017765A1/es not_active Application Discontinuation
-
1999
- 1999-02-22 TW TW087118140A patent/TW505627B/zh not_active IP Right Cessation
Also Published As
| Publication number | Publication date |
|---|---|
| CN1278239A (zh) | 2000-12-27 |
| DE69835229T2 (de) | 2006-11-23 |
| ES2263227T3 (es) | 2006-12-01 |
| CN1127471C (zh) | 2003-11-12 |
| BR9813349A (pt) | 2000-08-22 |
| JP2001521917A (ja) | 2001-11-13 |
| WO1999023055A1 (en) | 1999-05-14 |
| TR200001138T2 (tr) | 2000-09-21 |
| EP1030829B1 (en) | 2006-07-12 |
| AU1286899A (en) | 1999-05-24 |
| RU2213725C2 (ru) | 2003-10-10 |
| BR9813349B1 (pt) | 2010-08-24 |
| EP1030829A1 (en) | 2000-08-30 |
| JP4381600B2 (ja) | 2009-12-09 |
| EP1030829A4 (en) | 2003-01-02 |
| MY119529A (en) | 2005-06-30 |
| CA2307783C (en) | 2008-12-30 |
| DE69835229D1 (de) | 2006-08-24 |
| ID21201A (id) | 1999-05-06 |
| KR20010031634A (ko) | 2001-04-16 |
| AR017765A1 (es) | 2001-10-24 |
| CA2307783A1 (en) | 1999-05-14 |
| KR100603723B1 (ko) | 2006-07-26 |
| US5840968A (en) | 1998-11-24 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| TW505627B (en) | Method for preparing purified terephthalic acid | |
| US6113866A (en) | Apparatus for preparing purified terephthalic acid | |
| JP4272704B2 (ja) | 精製テレフタル酸の製造法および装置 | |
| US6054610A (en) | Method and apparatus for preparing purified terephthalic acid and isophthalic acid from mixed xylenes | |
| EP1082286B1 (en) | Method for preparing purified terephthalic acid and isophthalic acid from mixed xylenes | |
| JP5095390B2 (ja) | 選択的溶媒を用いた複合体形成によるカルボン酸の精製 | |
| RU2208606C2 (ru) | Способ очистки изофталевой кислоты путем кристаллизации | |
| JP4817496B2 (ja) | 精製テレフタル酸及びイソフタル酸を混合キシレンから製造する方法 | |
| JPH07118200A (ja) | ナフタレンジカルボン酸の製造方法 | |
| JP4032186B2 (ja) | 高純度２，６−ナフタレンジカルボン酸ジメチルの製造法 | |
| JPH07238051A (ja) | 高純度ナフタレンジカルボン酸の製造方法 | |
| JP4729173B2 (ja) | 結晶化によるイソフタル酸の精製方法 | |
| TW487700B (en) | Method for purifying crude terephthalic acid from a liquid dispersion produced from the oxidation of mixed xylenes | |
| JP2002069073A (ja) | 高純度無水ピロメリット酸の製造方法 | |
| MXPA00010846A (en) | Process for purifying isophthalic acid by crystallization | |
| HK1105628A (en) | Purification of carboxylic acids by complexation with selective solvents | |
| MXPA00011782A (en) | Method for preparing purified terephthalic acid and isophthalic acid from mixed xylenes |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| GD4A | Issue of patent certificate for granted invention patent | ||
| MM4A | Annulment or lapse of patent due to non-payment of fees |