CN118420453A - Method for preparing bio-based terephthalic acid from furfuryl alcohol - Google Patents
Method for preparing bio-based terephthalic acid from furfuryl alcohol Download PDFInfo
- Publication number
- CN118420453A CN118420453A CN202410514470.3A CN202410514470A CN118420453A CN 118420453 A CN118420453 A CN 118420453A CN 202410514470 A CN202410514470 A CN 202410514470A CN 118420453 A CN118420453 A CN 118420453A
- Authority
- CN
- China
- Prior art keywords
- catalyst
- reaction
- dimethylfuran
- furandimethanol
- furfuryl alcohol
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- XPFVYQJUAUNWIW-UHFFFAOYSA-N furfuryl alcohol Chemical compound OCC1=CC=CO1 XPFVYQJUAUNWIW-UHFFFAOYSA-N 0.000 title claims abstract description 99
- 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 80
- 238000000034 method Methods 0.000 title claims abstract description 20
- URLKBWYHVLBVBO-UHFFFAOYSA-N Para-Xylene Chemical group CC1=CC=C(C)C=C1 URLKBWYHVLBVBO-UHFFFAOYSA-N 0.000 claims abstract description 86
- 238000006243 chemical reaction Methods 0.000 claims abstract description 84
- GSNUFIFRDBKVIE-UHFFFAOYSA-N 2,5-dimethylfuran Chemical compound CC1=CC=C(C)O1 GSNUFIFRDBKVIE-UHFFFAOYSA-N 0.000 claims abstract description 82
- DSLRVRBSNLHVBH-UHFFFAOYSA-N 2,5-furandimethanol Chemical compound OCC1=CC=C(CO)O1 DSLRVRBSNLHVBH-UHFFFAOYSA-N 0.000 claims abstract description 78
- 239000003054 catalyst Substances 0.000 claims abstract description 50
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims abstract description 48
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 17
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000005977 Ethylene Substances 0.000 claims abstract description 14
- 229910052751 metal Inorganic materials 0.000 claims abstract description 9
- 239000002184 metal Substances 0.000 claims abstract description 9
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 18
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 16
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 12
- 239000002808 molecular sieve Substances 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 11
- 239000002904 solvent Substances 0.000 claims description 11
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 10
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 10
- 238000001914 filtration Methods 0.000 claims description 10
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 9
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 9
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 8
- 229910052739 hydrogen Inorganic materials 0.000 claims description 8
- 239000001257 hydrogen Substances 0.000 claims description 8
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 7
- 229940011182 cobalt acetate Drugs 0.000 claims description 7
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 claims description 7
- 229940071125 manganese acetate Drugs 0.000 claims description 7
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 claims description 7
- 229910052760 oxygen Inorganic materials 0.000 claims description 7
- 239000001301 oxygen Substances 0.000 claims description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical group OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 6
- 229910052799 carbon Inorganic materials 0.000 claims description 6
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 6
- 230000035484 reaction time Effects 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- 239000000395 magnesium oxide Substances 0.000 claims description 5
- IYDGMDWEHDFVQI-UHFFFAOYSA-N phosphoric acid;trioxotungsten Chemical compound O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.OP(O)(O)=O IYDGMDWEHDFVQI-UHFFFAOYSA-N 0.000 claims description 5
- 239000000377 silicon dioxide Substances 0.000 claims description 5
- 235000012239 silicon dioxide Nutrition 0.000 claims description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical group Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical group OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 4
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- IOLCXVTUBQKXJR-UHFFFAOYSA-M potassium bromide Chemical compound [K+].[Br-] IOLCXVTUBQKXJR-UHFFFAOYSA-M 0.000 claims description 4
- 239000004408 titanium dioxide Substances 0.000 claims description 4
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 3
- 238000011068 loading method Methods 0.000 claims description 3
- CNHRNMLCYGFITG-UHFFFAOYSA-A niobium(5+);pentaphosphate Chemical compound [Nb+5].[Nb+5].[Nb+5].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O CNHRNMLCYGFITG-UHFFFAOYSA-A 0.000 claims description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical group O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 2
- ILRRQNADMUWWFW-UHFFFAOYSA-K aluminium phosphate Chemical compound O1[Al]2OP1(=O)O2 ILRRQNADMUWWFW-UHFFFAOYSA-K 0.000 claims description 2
- 150000001450 anions Chemical class 0.000 claims description 2
- 229910000420 cerium oxide Inorganic materials 0.000 claims description 2
- 229910052802 copper Inorganic materials 0.000 claims description 2
- 150000002191 fatty alcohols Chemical class 0.000 claims description 2
- 229910052737 gold Inorganic materials 0.000 claims description 2
- 239000002815 homogeneous catalyst Substances 0.000 claims description 2
- GPRLSGONYQIRFK-UHFFFAOYSA-N hydron Chemical group [H+] GPRLSGONYQIRFK-UHFFFAOYSA-N 0.000 claims description 2
- 239000003456 ion exchange resin Substances 0.000 claims description 2
- 229920003303 ion-exchange polymer Polymers 0.000 claims description 2
- 229910052742 iron Inorganic materials 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 229910017604 nitric acid Inorganic materials 0.000 claims description 2
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 claims description 2
- 229910052698 phosphorus Inorganic materials 0.000 claims description 2
- 229940094035 potassium bromide Drugs 0.000 claims description 2
- 229910052717 sulfur Inorganic materials 0.000 claims description 2
- 229910052718 tin Inorganic materials 0.000 claims description 2
- QUBMWJKTLKIJNN-UHFFFAOYSA-B tin(4+);tetraphosphate Chemical compound [Sn+4].[Sn+4].[Sn+4].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QUBMWJKTLKIJNN-UHFFFAOYSA-B 0.000 claims description 2
- JUWGUJSXVOBPHP-UHFFFAOYSA-B titanium(4+);tetraphosphate Chemical compound [Ti+4].[Ti+4].[Ti+4].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O JUWGUJSXVOBPHP-UHFFFAOYSA-B 0.000 claims description 2
- 229910000166 zirconium phosphate Inorganic materials 0.000 claims description 2
- LEHFSLREWWMLPU-UHFFFAOYSA-B zirconium(4+);tetraphosphate Chemical compound [Zr+4].[Zr+4].[Zr+4].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O LEHFSLREWWMLPU-UHFFFAOYSA-B 0.000 claims description 2
- 239000002994 raw material Substances 0.000 abstract description 26
- 238000006555 catalytic reaction Methods 0.000 abstract description 2
- 230000001590 oxidative effect Effects 0.000 abstract description 2
- 238000001308 synthesis method Methods 0.000 abstract description 2
- 239000003377 acid catalyst Substances 0.000 abstract 1
- 239000011973 solid acid Substances 0.000 abstract 1
- 238000003786 synthesis reaction Methods 0.000 description 21
- 230000015572 biosynthetic process Effects 0.000 description 20
- 238000004458 analytical method Methods 0.000 description 15
- 238000004817 gas chromatography Methods 0.000 description 15
- 239000007788 liquid Substances 0.000 description 15
- 238000007254 oxidation reaction Methods 0.000 description 11
- 239000000047 product Substances 0.000 description 11
- JHJLBTNAGRQEKS-UHFFFAOYSA-M sodium bromide Chemical compound [Na+].[Br-] JHJLBTNAGRQEKS-UHFFFAOYSA-M 0.000 description 10
- 230000003647 oxidation Effects 0.000 description 9
- 238000004128 high performance liquid chromatography Methods 0.000 description 5
- 239000002028 Biomass Substances 0.000 description 4
- NOEGNKMFWQHSLB-UHFFFAOYSA-N 5-hydroxymethylfurfural Chemical compound OCC1=CC=C(C=O)O1 NOEGNKMFWQHSLB-UHFFFAOYSA-N 0.000 description 3
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 2
- JOOXCMJARBKPKM-UHFFFAOYSA-N 4-oxopentanoic acid Chemical compound CC(=O)CCC(O)=O JOOXCMJARBKPKM-UHFFFAOYSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- 238000006117 Diels-Alder cycloaddition reaction Methods 0.000 description 2
- 229930091371 Fructose Natural products 0.000 description 2
- 239000005715 Fructose Substances 0.000 description 2
- RFSUNEUAIZKAJO-ARQDHWQXSA-N Fructose Chemical compound OC[C@H]1O[C@](O)(CO)[C@@H](O)[C@@H]1O RFSUNEUAIZKAJO-ARQDHWQXSA-N 0.000 description 2
- 229920002488 Hemicellulose Polymers 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- IAQRGUVFOMOMEM-UHFFFAOYSA-N but-2-ene Chemical compound CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 description 2
- 230000018044 dehydration Effects 0.000 description 2
- 238000006297 dehydration reaction Methods 0.000 description 2
- RJGBSYZFOCAGQY-UHFFFAOYSA-N hydroxymethylfurfural Natural products COC1=CC=C(C=O)O1 RJGBSYZFOCAGQY-UHFFFAOYSA-N 0.000 description 2
- XMGQYMWWDOXHJM-UHFFFAOYSA-N limonene Chemical compound CC(=C)C1CCC(C)=CC1 XMGQYMWWDOXHJM-UHFFFAOYSA-N 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- FXLOVSHXALFLKQ-UHFFFAOYSA-N p-tolualdehyde Chemical compound CC1=CC=C(C=O)C=C1 FXLOVSHXALFLKQ-UHFFFAOYSA-N 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- -1 polyethylene terephthalate Polymers 0.000 description 2
- 229920000139 polyethylene terephthalate Polymers 0.000 description 2
- 239000005020 polyethylene terephthalate Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- 239000001431 2-methylbenzaldehyde Substances 0.000 description 1
- FEYLYTBPPCYZLO-UHFFFAOYSA-N 4,5-dimethylcyclohexene Chemical compound CC1CC=CCC1C FEYLYTBPPCYZLO-UHFFFAOYSA-N 0.000 description 1
- 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
- 241000219495 Betulaceae Species 0.000 description 1
- WSWCOQWTEOXDQX-MQQKCMAXSA-N E-Sorbic acid Chemical compound C\C=C\C=C\C(O)=O WSWCOQWTEOXDQX-MQQKCMAXSA-N 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000031018 biological processes and functions Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000004523 catalytic cracking Methods 0.000 description 1
- 238000001833 catalytic reforming Methods 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- IHLIVAHFDOAPFC-UHFFFAOYSA-N cyclohex-2-ene-1,4-dicarboxylic acid Chemical compound OC(=O)C1CCC(C(O)=O)C=C1 IHLIVAHFDOAPFC-UHFFFAOYSA-N 0.000 description 1
- XNMQEEKYCVKGBD-UHFFFAOYSA-N dimethylacetylene Natural products CC#CC XNMQEEKYCVKGBD-UHFFFAOYSA-N 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 description 1
- 239000002663 humin Substances 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 125000004029 hydroxymethyl group Chemical group [H]OC([H])([H])* 0.000 description 1
- 238000006317 isomerization reaction Methods 0.000 description 1
- 229940040102 levulinic acid Drugs 0.000 description 1
- 239000002029 lignocellulosic biomass Substances 0.000 description 1
- 229940087305 limonene Drugs 0.000 description 1
- 235000001510 limonene Nutrition 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 125000001805 pentosyl group Chemical group 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000007363 ring formation reaction Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The application provides a method for preparing bio-based terephthalic acid from furfuryl alcohol, which comprises the following steps of carrying out a methylolation reaction on furfuryl alcohol and formaldehyde under the action of an acid catalyst to generate 2, 5-furandimethanol, carrying out selective hydrodeoxygenation on the 2, 5-furandimethanol on a metal catalyst to generate 2, 5-dimethylfuran, carrying out a third step of carrying out a reaction on the 2, 5-dimethylfuran and bio-based ethanol or ethylene under the action of a solid acid catalyst to generate paraxylene, and carrying out a fourth step of oxidizing the paraxylene into terephthalic acid under the catalysis. The synthesis method provided by the application synthesizes the bio-based terephthalic acid by taking the cheap and renewable furfuryl alcohol as the raw material, and has wide application prospect.
Description
Technical Field
The invention relates to the technical field of chemical synthesis of bio-based da Zong chemicals, in particular to a synthesis process of bio-based terephthalic acid.
Background
Terephthalic acid (TPA), a key bulk compound, is widely used in various national economic fields such as chemical fiber, light industry, electronic industry, and construction. In particular, the use of TPA has focused mainly on the production of polyethylene terephthalate (PET), accounting for more than 90% of the total consumption of TPA. Traditionally, TPA has been synthesized by the oxidation reaction of para-xylene, which itself is obtained from petroleum feedstocks by catalytic reforming processes. However, recent feed lightening trends in cracker units have had a significant impact on the production of heavy products such as para-xylene; and petroleum resources are gradually depleted, and an alternative TPA preparation method is urgently needed to be found under the background of double carbon, so that the method has important significance for ensuring sustainable supply of the key raw materials.
Currently, processes for synthesizing terephthalic acid from biomass are disclosed from a number of patents. Patent CN106467461a proposes that trans, trans-hexadienoic acid obtained by bio-enzyme catalysis and ethylene undergo Diels-Alder cycloaddition reaction to construct a 2-cyclohexen-1, 4-dicarboxylic acid molecule with six-membered cyclic structure, and then hydrogen of the two molecules is removed to prepare bio-terephthalic acid. Patent CN108164386a proposes the conversion of bioethanol to 2-butene and 1, 3-butadiene, respectively, followed by Diels-Alder cycloaddition of the two products to give 4, 5-dimethylcyclohex-1-ene, followed by dehydrocyclization, isomerization and oxidation of the latter products to give bio-terephthalic acid. Patent CN117337332a discloses a synthesis method of bio-based terephthalic acid, namely, edible and non-edible biomass is converted into 4-methylbenzaldehyde by microorganism, and the product is subjected to biological oxidation to prepare terephthalic acid. Patent CN102325822B proposes the preparation of bio-based terephthalic acid by the first dehydrogenation-then oxidation of limonene. Patent CN113354533B discloses a process for producing terephthalic acid from lignocellulosic biomass, i.e. lignocellulose is catalytically cracked in a protective atmosphere to produce an intermediate rich in para-xylene, which is then oxidized to obtain terephthalic acid. Although these methods can produce bio-based terephthalic acid, they still suffer from disadvantages such as a low source of raw materials, low efficiency of biological processes, and low selectivity of catalytic cracking products. Patent US8314267B2 discloses a synthetic method for obtaining bio-based terephthalic acid by reacting 2, 5-dimethylfuran with bio-derived ethylene to produce para-xylene, followed by oxidation. The 2, 5-dimethylfuran is mainly obtained by hydrodeoxygenation of a fructose dehydration product, namely 5-hydroxymethylfurfural, but the fructose is accompanied by various side reactions in the dehydration process, so that other byproducts such as humins, levulinic acid, formic acid and the like are generated, and finally, the selectivity of HMF is relatively low, and the separation cost is high. Therefore, development of a new synthetic route to reduce the cost of raw materials is urgently required. Furfuryl alcohol, in turn, is a representative platform molecule for hemicellulose, and is obtained in large quantities by hydrolysis of pentose units in biomass followed by hydrogenation. If furfuryl alcohol is used as a raw material for synthesizing terephthalic acid, the production cost of bio-based terephthalic acid is greatly reduced.
Based on the above, the application provides a method for preparing the bio-based terephthalic acid by reacting furfuryl alcohol with formaldehyde to generate 2, 5-furandimethanol, then hydrodeoxygenation to generate 2, 5-dimethylfuran, and then reacting with bio-based ethanol or bio-based ethylene to generate p-xylene and oxidizing. The reaction path takes bio-based da Zong chemical furfuryl alcohol as a reaction raw material, so that the raw material cost and the equipment cost are greatly reduced, and a new thought is provided for the industrialized development of bio-based terephthalic acid.
Disclosure of Invention
The invention provides a method for producing bio-based terephthalic acid by using furfuryl alcohol as a raw material through four-step reaction.
The application adopts the following technical scheme:
A process for preparing bio-based terephthalic acid from furfuryl alcohol, the synthesis process comprising the steps of:
(1) Furfuryl alcohol, formaldehyde and catalyst are added into a reaction kettle according to a certain proportion to react for 1-24 hours at normal temperature, and the obtained mixture is filtered, extracted and distilled to obtain 2, 5-furandimethanol.
(2) Mixing the obtained 2, 5-furandimethanol, a solvent and a hydrodeoxygenation catalyst according to a certain proportion, and then placing the mixture into a reaction kettle. The pressure of the introduced hydrogen is 0.1-5MPa, the reaction time is 1-24 hours, and the reaction temperature is 50-300 ℃. Filtering, extracting and distilling the reacted mixture to obtain 2, 5-dimethylfuran.
(3) The obtained 2, 5-dimethylfuran, solvent and catalyst are put into a reaction kettle according to a certain proportion, ethylene pressure is introduced to be 0.1-5MPa, and reaction time is 1-24 hours. The reaction temperature is 50-350 ℃. And filtering, extracting and distilling the reacted mixture to obtain the paraxylene.
(4) The obtained paraxylene and the catalyst are put into a reaction kettle according to a certain proportion, the pressure of the introduced oxygen is 0.1-5MPa, the reaction time is 1-24 hours, and the reaction temperature is 50-200 ℃. Filtering and recrystallizing the reacted mixture to obtain the bio-based terephthalic acid.
In the step (1), the mass ratio of furfuryl alcohol to formaldehyde to the catalyst is x to y to z, wherein x is 0.05-2, y is 0.1-10, and z is 0.01-1. The catalyst is one or more of hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, hydrogen ion exchange resin, H-type molecular sieve, niobium phosphate, titanium phosphate, aluminum phosphate, zirconium phosphate, tin phosphate, phosphotungstic acid and phosphotungstic acid.
In the step (2), the mass ratio of the 2, 5-furandimethanol to the solvent to the catalyst is x to y to z, wherein x is 0.1-2, y is 1-100, and z is 0.01-1. The hydrodeoxygenation catalyst is one or more metal supported catalysts in Fe, co, ni, cu, and the metal loading is 0.1-15%. The carrier is one or more of active carbon, alumina, titanium dioxide, silicon dioxide, magnesium oxide and molecular sieve.
In the step (3), the mass ratio of the 2, 5-dimethylfuran to the solvent to the catalyst is x to y to z, wherein x is 0.2 to 1, y is 1 to 50, and z is 0.01 to 1. The catalyst used is an unmodified molecular sieve or an anionically modified molecular sieve. Wherein the anions are one or more of N, P, S and Sn, and the used molecular sieve is one or more of HZSM-5 and HBEA, HY, HUSY.
In the step (4), the mass ratio of the paraxylene to the catalyst is x to y, wherein x is 0.2-1, and y is 0.01-0.1. The catalyst is one or more metal supported catalysts of Au, co and Cu or homogeneous catalysts of cobalt acetate, manganese acetate and potassium bromide, and the metal loading is 0.1-15%. The carrier used is one or more of nitrogen doped carbon, cerium oxide, titanium dioxide, silicon dioxide and magnesium oxide.
The extractant in the step 1-4 is one or more of ethyl acetate, diethyl ether, toluene and C5-C10 fatty alcohol.
The solvent in the steps 2 and 3 is one or more of water, methanol, ethanol and isopropanol.
The at least one technical scheme adopted by the application can achieve the following beneficial effects:
furfuryl alcohol is used as a raw material, and is subjected to a hydroxymethyl reaction to obtain a carbon growth strategy, and hydrodeoxygenation, diels and Alder cyclization reaction and oxidation reaction to finally generate the bio-based terephthalic acid. Compared with the traditional 5-hydroxymethyl furfural route, the method has the advantages that the raw material cost is greatly reduced by taking furfuryl alcohol as the raw material, the upper hemicellulose biomass resource is utilized to a greater extent, and the concept of green sustainable development is met.
Detailed Description
In order to make the objects, technical solutions and advantages of the present application more apparent, the technical solutions of the present application will be clearly and completely described below in connection with specific embodiments of the present application. It will be apparent that the described embodiments are only some, but not all, embodiments of the application. All other embodiments, which can be made by those skilled in the art based on the embodiments of the application without making any inventive effort, are intended to be within the scope of the application.
Example 1
(1) Synthesis of 2, 5-furandimethanol by reaction of furfuryl alcohol and formaldehyde
In this example, 6mL of formaldehyde was used as the reaction solution, and 1mL of furfuryl alcohol and 0.8g of niobium phosphate were added. After 4h at room temperature, the catalyst was filtered and the product was extracted with ethyl acetate and analyzed by gas chromatography, wherein the furfuryl alcohol conversion was 55% and the yield of 2, 5-furandimethanol was 47%.
(2) Synthesis of 2, 5-dimethylfuran by hydrodeoxygenation of 2, 5-furandimethanol
Taking the 2, 5-furandimethanol obtained in the first step as a raw material, and sequentially adding 0.75g of 2, 5-furandimethanol, 0.1g of Cu/SiO2 and 35g of 1, 4-dioxane into a reaction kettle. After reacting at 180℃and 1.5MPa for 4 hours under hydrogen pressure, the catalyst was filtered, and the mixed liquid was subjected to component analysis by gas chromatography, wherein the conversion of 2, 5-furandimethanol was 95%, and the yield of 2, 5-dimethylfuran was 92%.
(3) Synthesis of paraxylene by reaction of 2, 5-dimethylfuran with ethylene
2G of 2, 5-dimethylfuran, 0.5g P-BEA and 50mL of n-heptane were added in this order to the reaction vessel using the 2, 5-dimethylfuran obtained in the second step as a raw material. After 24 hours of reaction at 250℃and 0.3MPa of ethylene pressure, the catalyst was filtered, and the mixed liquid was subjected to component analysis by gas chromatography, wherein the conversion of 2, 5-dimethylfuran was 100%, and the yield of p-xylene was 95%.
(4) Synthesis of bio-based terephthalic acid by oxidation of p-xylene
Taking paraxylene obtained in the third step as a raw material, sequentially adding 0.5g paraxylene, 0.015g NaBr, 0.010g manganese acetate, 0.025g cobalt acetate and 5mL acetic acid into a reaction kettle, and reacting for 4 hours at 140 ℃ under the condition of 1.5MPa oxygen. After filtering the catalyst, the mixed liquid was subjected to component analysis by high performance liquid chromatography, wherein the conversion of paraxylene was 100%, and the yield of terephthalic acid was 95%.
Example 2
(1) Synthesis of 2, 5-furandimethanol by reaction of furfuryl alcohol and formaldehyde
In this example, 4mL of formaldehyde was used as the reaction solution, and 1.2mL of furfuryl alcohol and 0.4g HBEA of molecular sieve were added. After 12h reaction at room temperature, the catalyst was filtered and the product was extracted with diethyl ether and analyzed by gas chromatography for components, wherein the conversion of furfuryl alcohol was 100% and the yield of 2, 5-furandimethanol was 74%.
(2) Synthesis of 2, 5-dimethylfuran by hydrodeoxygenation of 2, 5-furandimethanol
Taking the 2, 5-furandimethanol obtained in the first step as a raw material, adding 0.4g of 2, 5-furandimethanol, 0.05g of Ni/WO3 and 20g of water into a reaction kettle in sequence. After the reaction was performed for 6 hours at 180℃under a hydrogen pressure of 1.0MPa, the catalyst was filtered, and the mixed liquid was subjected to component analysis by gas chromatography, wherein the conversion of 2, 5-furandimethanol was 92% and the yield of 2, 5-dimethylfuran was 83%.
(3) Synthesis of paraxylene by reaction of 2, 5-dimethylfuran with ethanol
2G of 2, 5-dimethylfuran, 0.3g HBEA molecular sieve, 4g of ethanol and 50mL of 1, 4-dioxane are sequentially added into a reaction kettle by taking the 2, 5-dimethylfuran obtained in the second step as a raw material. After 20h of reaction at 300℃the catalyst was filtered. The mixed liquid was subjected to component analysis by gas chromatography, wherein the conversion of 2, 5-dimethylfuran was 90%, and the yield of p-xylene was 85%.
(4) Synthesis of bio-based terephthalic acid by oxidation of p-xylene
Taking paraxylene obtained in the third step as a raw material, sequentially adding 0.5g paraxylene, 0.015g NaBr, 0.010g manganese acetate, 0.025g cobalt acetate and 5mL acetic acid into a reaction kettle, and reacting for 3 hours at 140 ℃ under the condition of 2.0MPa oxygen. After filtering the catalyst, the mixed liquid was subjected to component analysis by high performance liquid chromatography, wherein the conversion of paraxylene was 86%, and the yield of terephthalic acid was 71%.
Example 3
(1) Synthesis of 2, 5-furandimethanol by reaction of furfuryl alcohol and formaldehyde
In this example, 8mL of formaldehyde was used as the reaction solution, and 2mL of furfuryl alcohol and 1.0g of phosphoric acid were added. After 16h reaction at room temperature, the catalyst was filtered and the product was extracted with diethyl ether and analyzed by gas chromatography for components, wherein the conversion of furfuryl alcohol was 100% and the yield of 2, 5-furandimethanol was 84%.
(2) Hydrodeoxygenation of 2, 5-furandimethanol to 2, 5-dimethylfuran
Taking 2, 5-furandimethanol obtained in the first step as a raw material, sequentially adding 1.2g of 2, 5-furandimethanol, 0.15g of Co/WO3 and 30g of water into a reaction kettle. After the reaction was carried out at 250℃under a hydrogen pressure of 2.0MPa for 3 hours, the catalyst was filtered, and the mixed liquid was subjected to component analysis by gas chromatography, wherein the conversion of 2, 5-furandimethanol was 78% and the yield of 2, 5-dimethylfuran was 67%.
(3) Synthesis of paraxylene by reaction of 2, 5-dimethylfuran with ethylene
With the 2, 5-dimethylfuran obtained in the second step as a raw material, 4g of 2, 5-dimethylfuran, 0.5g of HZSM-5 molecular sieve and 50mL of C12 alkane are sequentially added into a reaction kettle. After reacting for 14 hours at 280℃and an ethylene pressure of 5.0MPa, the catalyst was filtered, and the mixed liquid was subjected to component analysis by gas chromatography, wherein the conversion of 2, 5-dimethylfuran was 72%, and the yield of p-xylene was 65%.
(4) Synthesis of bio-based terephthalic acid by oxidation of p-xylene
Taking paraxylene obtained in the third step as a raw material, sequentially adding 1.5g paraxylene, 0.03g NaBr, 0.040g manganese acetate, 0.01g cobalt acetate and 10mL acetic acid into a reaction kettle, and reacting for 4 hours at 160 ℃ under the condition of 3.0MPa oxygen. After filtering the catalyst, the mixed liquid was subjected to component analysis by high performance liquid chromatography, wherein the conversion of paraxylene was 96%, and the yield of terephthalic acid was 81%.
Example 4
(1) Synthesis of 2, 5-furandimethanol by reaction of furfuryl alcohol and formaldehyde
In this example, 10mL of formaldehyde was used as the reaction solution, and 6mL of furfuryl alcohol and 2.0g of phosphotungstic acid were added. After 24h reaction at room temperature, the catalyst was filtered and the product was extracted with toluene and analyzed by gas chromatography, wherein the furfuryl alcohol conversion was 83% and the yield of 2, 5-furandimethanol was 64%.
(2) Synthesis of 2, 5-dimethylfuran by hydrodeoxygenation of 2, 5-furandimethanol
2.0G of 2, 5-furandimethanol, 0.3g of Cu/TiO2 and 30g of water are sequentially added into a reaction kettle by taking the 2, 5-furandimethanol obtained in the first step as a raw material. After the reaction was performed for 4 hours at 280℃under a hydrogen pressure of 3.0MPa, the catalyst was filtered, and the mixed liquid was subjected to component analysis by gas chromatography, wherein the conversion of 2, 5-furandimethanol was 82% and the yield of 2, 5-dimethylfuran was 77%.
(3) Synthesis of paraxylene by reaction of 2, 5-dimethylfuran with ethylene
Taking the 2, 5-dimethylfuran obtained in the second step as a raw material, 6g of 2, 5-dimethylfuran, 1.5g of HUSY molecular sieve and 50mL of C6 alkane are sequentially added into a reaction kettle. After reacting for 18 hours at 290℃and an ethylene pressure of 2.0MPa, the catalyst was filtered, and the mixed liquid was subjected to component analysis by gas chromatography, wherein the conversion of 2, 5-dimethylfuran was 62%, and the yield of p-xylene was 55%.
(4) Synthesis of bio-based terephthalic acid by oxidation of p-xylene
Taking paraxylene obtained in the third step as a raw material, sequentially adding 2.5g paraxylene, 0.04g NaBr, 0.080g manganese acetate, 0.03g cobalt acetate and 20mL acetic acid into a reaction kettle, and reacting for 6 hours at 110 ℃ under the condition of 4.0MPa oxygen. After filtering the catalyst, the mixed liquid was subjected to component analysis by high performance liquid chromatography, wherein the conversion of paraxylene was 76%, and the yield of terephthalic acid was 61%.
Example 5
(1) Synthesis of 2, 5-furandimethanol by reaction of furfuryl alcohol and formaldehyde
In this example, 12mL of formaldehyde was used as the reaction solution, and 8mL of furfuryl alcohol and 3.0g of HMOR molecular sieve were added. After 22h reaction at room temperature, the catalyst was filtered and the product was extracted with C6 alcohol and analyzed by gas chromatography, wherein the conversion of furfuryl alcohol was 63% and the yield of 2, 5-furandimethanol was 54%.
(2) Hydrodeoxygenation of 2, 5-furandimethanol to 2, 5-dimethylfuran
Taking the 2, 5-furandimethanol obtained in the first step as a raw material, adding 3.0g of 2, 5-furandimethanol, 0.4g of Cu/MgO and 35g of water into a reaction kettle in sequence. After the reaction was performed for 6 hours at 220℃under a hydrogen pressure of 4.0MPa, the catalyst was filtered, and the mixed liquid was subjected to component analysis by gas chromatography, wherein the conversion of 2, 5-furandimethanol was 92% and the yield of 2, 5-dimethylfuran was 88%.
(3) Synthesis of paraxylene by reaction of 2, 5-dimethylfuran with ethylene
8G of 2, 5-dimethylfuran, 1.7g of HY molecular sieve and 50mL of tetrahydrofuran are sequentially added into a reaction kettle by taking the 2, 5-dimethylfuran obtained in the second step as a raw material. After reacting at 320℃under an ethylene pressure of 3.0MPa for 22 hours, the catalyst was filtered, and the mixed liquid was subjected to component analysis by gas chromatography, wherein the conversion of 2, 5-dimethylfuran was 75%, and the yield of p-xylene was 63%.
(4) Synthesis of bio-based terephthalic acid by oxidation of p-xylene
Taking paraxylene obtained in the third step as a raw material, sequentially adding 2.8g paraxylene, 0.05g NaBr, 0.080g manganese acetate, 0.04g cobalt acetate and 23mL acetic acid into a reaction kettle, and reacting for 16 hours at 180 ℃ under the condition of 5.0MPa oxygen. After filtering the catalyst, the mixed liquid was subjected to component analysis by high performance liquid chromatography, wherein the conversion of paraxylene was 88%, and the yield of terephthalic acid was 79%.
Claims (7)
1. A process for preparing bio-based terephthalic acid from furfuryl alcohol, the process comprising the steps of:
(1) Furfuryl alcohol, formaldehyde and a catalyst are added into a reaction kettle according to a certain proportion to react for 1-24 hours at normal temperature, and the obtained mixture is filtered, extracted and distilled to obtain 2, 5-furandimethanol;
(2) Mixing the 2, 5-furandimethanol obtained in the first step, a solvent and a hydrodeoxygenation catalyst according to a certain proportion, and then placing the mixture into a reaction kettle; the reaction time is 1-24 hours; the reaction temperature is 50-300 ℃, and the reaction hydrogen pressure is 0.1-5.0MPa; filtering, extracting and distilling the obtained mixture to obtain 2, 5-dimethylfuran;
(3) 2, 5-dimethylfuran, solvent and catalyst obtained in the second step are put into a reaction kettle according to a certain proportion, and the reaction time is 1-24 hours; the reaction temperature is 50-350 ℃, and the reaction ethylene pressure is 0.1-5.0MPa; filtering, extracting and distilling the obtained mixture to obtain paraxylene;
(4) Putting the paraxylene obtained in the third step, a catalyst and an acetic acid solvent into a reaction kettle according to a certain proportion, wherein the reaction time is 1-24 hours; the reaction temperature is 50-200 ℃, and the reaction oxygen pressure is 0.1-5MPa; the obtained mixture is filtered and recrystallized to obtain the bio-based terephthalic acid.
2. The method according to claim 1, wherein in step 1 the mass ratio of furfuryl alcohol to formaldehyde to catalyst is x to y to z, wherein x is 0.05-2, y is 0.1-10, and z is 0.01-1; the catalyst is one or a mixture of more of hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, hydrogen ion exchange resin, H-type molecular sieve, niobium phosphate, titanium phosphate, aluminum phosphate, zirconium phosphate, tin phosphate, phosphotungstic acid and phosphotungstic acid.
3. The method according to claim 1, wherein in the step 2, the mass ratio of the 2, 5-furandimethanol to the solvent to the catalyst is x to y to z, wherein x is 0.1 to2, y is 1 to 100, and z is 0.01 to 1; the required hydrodeoxygenation catalyst is one or more metal supported catalysts in Fe, co, ni, cu, the metal load accounts for 0.1-15% of the weight of the carrier, and the carrier is one or more of active carbon, alumina, titanium dioxide, silicon dioxide, magnesium oxide and molecular sieve.
4. The method according to claim 1, wherein in the step 3, the mass ratio of the 2, 5-dimethylfuran to the solvent to the catalyst is x to y to z, wherein x is 0.2 to 1, y is 1 to 50, and z is 0.01 to 1; the required catalyst is an unmodified molecular sieve or an anionically modified molecular sieve; wherein the anions are one or more of N, P, S and Sn, and the molecular sieve is one or more of HZSM-5 and HBEA, HY, HUSY.
5. The process according to claim 1, wherein the mass ratio of paraxylene to catalyst in step 4 is x to y, wherein x is 0.2 to 1 and y is 0.01 to 0.1; the catalyst is one or more metal supported catalysts of Au, co and Cu or homogeneous catalysts of cobalt acetate, manganese acetate and potassium bromide, the metal loading amount accounts for 0.1-15% of the weight of the carrier, and the carrier is one or more of nitrogen doped carbon, cerium oxide, titanium dioxide, silicon dioxide and magnesium oxide.
6. The process of claim 1, wherein the extractant in steps 1-4 is one or more of ethyl acetate, diethyl ether, toluene and C5-C10 fatty alcohols.
7. The method according to claim 1, wherein the solvent in steps 2 and 3 is one or more of water, methanol, ethanol, isopropanol.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202410514470.3A CN118420453A (en) | 2024-04-26 | 2024-04-26 | Method for preparing bio-based terephthalic acid from furfuryl alcohol |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202410514470.3A CN118420453A (en) | 2024-04-26 | 2024-04-26 | Method for preparing bio-based terephthalic acid from furfuryl alcohol |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN118420453A true CN118420453A (en) | 2024-08-02 |
Family
ID=92309793
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202410514470.3A Pending CN118420453A (en) | 2024-04-26 | 2024-04-26 | Method for preparing bio-based terephthalic acid from furfuryl alcohol |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN118420453A (en) |
-
2024
- 2024-04-26 CN CN202410514470.3A patent/CN118420453A/en active Pending
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Cai et al. | Biomass into chemicals: One-pot production of furan-based diols from carbohydrates via tandem reactions | |
| Deng et al. | Catalytic upgrading of biomass derived furans | |
| CN108484545B (en) | Method and system for continuously synthesizing furan dicarboxylic acid | |
| CN101475441B (en) | Method for preparing ethylene glycol from oxalic ester | |
| CN109896938B (en) | Method for preparing 2, 5-hexanedione | |
| CN101475442B (en) | Method for preparing ethylene glycol from oxalic ester | |
| CN111218308B (en) | Method for preparing high-density fuel from biomass raw material | |
| CN106866331B (en) | Method for preparing cyclopentadiene or dicyclopentadiene from furfuryl alcohol | |
| CN113563289B (en) | Method for preparing 2, 5-furandicarboxylic acid from furfural | |
| CN101475443B (en) | Method for preparing ethylene glycol | |
| JP7416177B2 (en) | Alcohol manufacturing method | |
| US20170327480A1 (en) | Method for Acid-Catalyzed Acylation of the Reduction Products of 5-HydroxyMethyl Furfural | |
| CN106866345B (en) | Method for preparing JP-10 aviation fuel from furfuryl alcohol | |
| CN113620784B (en) | Alkane dehydrogenation and lignin-based ether hydrogenation reaction coupling process | |
| CN112961123B (en) | Method for preparing 3- (2-furyl) -2-methyl-2-acrolein by catalyzing oxidation condensation of furfural and n-propanol | |
| CN118420453A (en) | Method for preparing bio-based terephthalic acid from furfuryl alcohol | |
| CN112047907B (en) | Method for preparing 2, 5-furandimethanol by glucose one-pot method under synergistic catalysis of formic acid hydrogen supply and metal halide | |
| EP3023479A1 (en) | Process for the deoxygenation of alcohols and use thereof | |
| CN112625014B (en) | Method for preparing 2, 5-furan diformyl chloride from 5-chloromethyl furfural | |
| CN111434657B (en) | Preparation method of gamma-valerolactone and levulinate ester compound | |
| CN112851499A (en) | Method for preparing maleic acid by catalyzing cellulose with bifunctional solid catalyst | |
| CN111971268B (en) | Process for producing dialkyl terephthalate | |
| CN115181007B (en) | Method for generating polyalcohol and alkane by hydrogenation ring-opening conversion of furyl derivative | |
| CN112812000B (en) | Preparation method of maleic acid | |
| CN112661602B (en) | Preparation method of cyclopentanol based on copper catalyst |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |