CN117677611A - Purification process for 5- (methoxycarbonyl) furan-2-carboxylic acid (MCFC) - Google Patents
Purification process for 5- (methoxycarbonyl) furan-2-carboxylic acid (MCFC) Download PDFInfo
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- CN117677611A CN117677611A CN202280050831.2A CN202280050831A CN117677611A CN 117677611 A CN117677611 A CN 117677611A CN 202280050831 A CN202280050831 A CN 202280050831A CN 117677611 A CN117677611 A CN 117677611A
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- 238000000746 purification Methods 0.000 title claims description 34
- AETGYSUEDWYSME-UHFFFAOYSA-N 5-methoxycarbonylfuran-2-carboxylic acid Chemical compound COC(=O)C1=CC=C(C(O)=O)O1 AETGYSUEDWYSME-UHFFFAOYSA-N 0.000 title abstract description 13
- 238000000034 method Methods 0.000 claims abstract description 72
- 239000002904 solvent Substances 0.000 claims description 121
- 238000007254 oxidation reaction Methods 0.000 claims description 117
- 230000003647 oxidation Effects 0.000 claims description 107
- CHTHALBTIRVDBM-UHFFFAOYSA-N furan-2,5-dicarboxylic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)O1 CHTHALBTIRVDBM-UHFFFAOYSA-N 0.000 claims description 84
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 81
- 239000003054 catalyst Substances 0.000 claims description 56
- 150000001875 compounds Chemical class 0.000 claims description 49
- 230000008569 process Effects 0.000 claims description 42
- -1 alkyl 5-formylfuran-2-carboxylate Chemical compound 0.000 claims description 27
- 239000007789 gas Substances 0.000 claims description 26
- SHNRXUWGUKDPMA-UHFFFAOYSA-N 5-formyl-2-furoic acid Chemical compound OC(=O)C1=CC=C(C=O)O1 SHNRXUWGUKDPMA-UHFFFAOYSA-N 0.000 claims description 24
- 125000000217 alkyl group Chemical group 0.000 claims description 24
- 230000001590 oxidative effect Effects 0.000 claims description 21
- 239000010941 cobalt Substances 0.000 claims description 20
- 229910017052 cobalt Inorganic materials 0.000 claims description 20
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 20
- 239000007800 oxidant agent Substances 0.000 claims description 20
- 229910052794 bromium Inorganic materials 0.000 claims description 19
- 239000011572 manganese Substances 0.000 claims description 19
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 18
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 18
- 125000004432 carbon atom Chemical group C* 0.000 claims description 18
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 18
- 239000000047 product Substances 0.000 claims description 17
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical group [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 14
- 239000001301 oxygen Substances 0.000 claims description 14
- 229910052760 oxygen Inorganic materials 0.000 claims description 14
- 239000012265 solid product Substances 0.000 claims description 14
- 239000001257 hydrogen Substances 0.000 claims description 12
- 229910052739 hydrogen Inorganic materials 0.000 claims description 12
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 7
- 238000004519 manufacturing process Methods 0.000 claims description 7
- JHJLBTNAGRQEKS-UHFFFAOYSA-M sodium bromide Chemical compound [Na+].[Br-] JHJLBTNAGRQEKS-UHFFFAOYSA-M 0.000 claims description 6
- 150000002431 hydrogen Chemical class 0.000 claims description 5
- BMYNFMYTOJXKLE-UHFFFAOYSA-N 3-azaniumyl-2-hydroxypropanoate Chemical compound NCC(O)C(O)=O BMYNFMYTOJXKLE-UHFFFAOYSA-N 0.000 claims description 4
- 238000005984 hydrogenation reaction Methods 0.000 claims description 4
- 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 claims description 2
- 150000002763 monocarboxylic acids Chemical class 0.000 claims 1
- 239000007858 starting material Substances 0.000 abstract description 21
- XBYZJUMTKHUJIY-UHFFFAOYSA-N methyl 5-methylfuran-2-carboxylate Chemical compound COC(=O)C1=CC=C(C)O1 XBYZJUMTKHUJIY-UHFFFAOYSA-N 0.000 abstract description 16
- 239000002994 raw material Substances 0.000 abstract description 15
- SMNDYUVBFMFKNZ-UHFFFAOYSA-N 2-furoic acid Chemical compound OC(=O)C1=CC=CO1 SMNDYUVBFMFKNZ-UHFFFAOYSA-N 0.000 abstract description 7
- 125000004453 alkoxycarbonyl group Chemical group 0.000 abstract description 3
- 239000007788 liquid Substances 0.000 description 75
- 239000012452 mother liquor Substances 0.000 description 66
- 238000000926 separation method Methods 0.000 description 56
- 239000007787 solid Substances 0.000 description 53
- 239000000203 mixture Substances 0.000 description 36
- 239000012535 impurity Substances 0.000 description 35
- NOEGNKMFWQHSLB-UHFFFAOYSA-N 5-hydroxymethylfurfural Chemical compound OCC1=CC=C(C=O)O1 NOEGNKMFWQHSLB-UHFFFAOYSA-N 0.000 description 31
- 229960000583 acetic acid Drugs 0.000 description 26
- 238000006243 chemical reaction Methods 0.000 description 26
- 239000002002 slurry Substances 0.000 description 25
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 23
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 18
- 238000005406 washing Methods 0.000 description 17
- KDPOOUQFAUOHHX-UHFFFAOYSA-N methyl 5-formylfuran-2-carboxylate Chemical compound COC(=O)C1=CC=C(C=O)O1 KDPOOUQFAUOHHX-UHFFFAOYSA-N 0.000 description 16
- 238000002425 crystallisation Methods 0.000 description 14
- 230000008025 crystallization Effects 0.000 description 14
- 239000011541 reaction mixture Substances 0.000 description 14
- 238000000605 extraction Methods 0.000 description 13
- 229910052748 manganese Inorganic materials 0.000 description 13
- 239000008247 solid mixture Substances 0.000 description 13
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 12
- 125000003118 aryl group Chemical group 0.000 description 11
- 125000000753 cycloalkyl group Chemical group 0.000 description 11
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 10
- 238000001816 cooling Methods 0.000 description 10
- 238000001704 evaporation Methods 0.000 description 10
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 10
- YLQBMQCUIZJEEH-UHFFFAOYSA-N Furan Chemical compound C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 9
- 239000006227 byproduct Substances 0.000 description 9
- 230000008020 evaporation Effects 0.000 description 9
- VQKFNUFAXTZWDK-UHFFFAOYSA-N 2-Methylfuran Chemical compound CC1=CC=CO1 VQKFNUFAXTZWDK-UHFFFAOYSA-N 0.000 description 8
- 125000005599 alkyl carboxylate group Chemical group 0.000 description 8
- 238000011084 recovery Methods 0.000 description 8
- 239000002699 waste material Substances 0.000 description 8
- GSNUFIFRDBKVIE-UHFFFAOYSA-N 2,5-dimethylfuran Chemical compound CC1=CC=C(C)O1 GSNUFIFRDBKVIE-UHFFFAOYSA-N 0.000 description 7
- SMNDYUVBFMFKNZ-UHFFFAOYSA-M 2-furoate Chemical compound [O-]C(=O)C1=CC=CO1 SMNDYUVBFMFKNZ-UHFFFAOYSA-M 0.000 description 7
- CPELXLSAUQHCOX-UHFFFAOYSA-N Hydrogen bromide Chemical compound Br CPELXLSAUQHCOX-UHFFFAOYSA-N 0.000 description 7
- 230000015572 biosynthetic process Effects 0.000 description 7
- KFSLWBXXFJQRDL-UHFFFAOYSA-N Peracetic acid Chemical compound CC(=O)OO KFSLWBXXFJQRDL-UHFFFAOYSA-N 0.000 description 6
- 239000000543 intermediate Substances 0.000 description 6
- 238000010926 purge Methods 0.000 description 6
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 5
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 5
- 239000000706 filtrate Substances 0.000 description 5
- 239000011261 inert gas Substances 0.000 description 5
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 150000007513 acids Chemical class 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 4
- 229910002091 carbon monoxide Inorganic materials 0.000 description 4
- 229910002090 carbon oxide Inorganic materials 0.000 description 4
- HYBBIBNJHNGZAN-UHFFFAOYSA-N furfural Chemical compound O=CC1=CC=CO1 HYBBIBNJHNGZAN-UHFFFAOYSA-N 0.000 description 4
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 4
- 239000007791 liquid phase Substances 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 230000035484 reaction time Effects 0.000 description 4
- 238000010977 unit operation Methods 0.000 description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical group CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 238000002485 combustion reaction Methods 0.000 description 3
- 238000010924 continuous production Methods 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 229910000042 hydrogen bromide Inorganic materials 0.000 description 3
- 150000002696 manganese Chemical class 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- JTJMJGYZQZDUJJ-UHFFFAOYSA-N phencyclidine Chemical class C1CCCCN1C1(C=2C=CC=CC=2)CCCCC1 JTJMJGYZQZDUJJ-UHFFFAOYSA-N 0.000 description 3
- 229920000139 polyethylene terephthalate Polymers 0.000 description 3
- 239000005020 polyethylene terephthalate Substances 0.000 description 3
- 238000005201 scrubbing Methods 0.000 description 3
- 230000007704 transition Effects 0.000 description 3
- HIXDQWDOVZUNNA-UHFFFAOYSA-N 2-(3,4-dimethoxyphenyl)-5-hydroxy-7-methoxychromen-4-one Chemical compound C=1C(OC)=CC(O)=C(C(C=2)=O)C=1OC=2C1=CC=C(OC)C(OC)=C1 HIXDQWDOVZUNNA-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
- KAZRCBVXUOCTIO-UHFFFAOYSA-N 5-(chloromethyl)furan-2-carbaldehyde Chemical compound ClCC1=CC=C(C=O)O1 KAZRCBVXUOCTIO-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 238000002835 absorbance Methods 0.000 description 2
- 238000010923 batch production Methods 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 150000001868 cobalt Chemical class 0.000 description 2
- 239000003599 detergent Substances 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- 229910001882 dioxygen Inorganic materials 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000008241 heterogeneous mixture Substances 0.000 description 2
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- KQNPFQTWMSNSAP-UHFFFAOYSA-N isobutyric acid Chemical compound CC(C)C(O)=O KQNPFQTWMSNSAP-UHFFFAOYSA-N 0.000 description 2
- 238000004811 liquid chromatography Methods 0.000 description 2
- 238000000622 liquid--liquid extraction Methods 0.000 description 2
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 description 2
- QMTFZBVUCNNIPC-UHFFFAOYSA-N methyl 5-(ethoxymethyl)furan-2-carboxylate Chemical compound CCOCC1=CC=C(C(=O)OC)O1 QMTFZBVUCNNIPC-UHFFFAOYSA-N 0.000 description 2
- GCVVHNKBMLQFCY-UHFFFAOYSA-N methyl 5-(hydroxymethyl)furan-2-carboxylate Chemical compound COC(=O)C1=CC=C(CO)O1 GCVVHNKBMLQFCY-UHFFFAOYSA-N 0.000 description 2
- GXYHQVZORYVUOP-UHFFFAOYSA-N methyl 5-(methoxymethyl)furan-2-carboxylate Chemical compound COCC1=CC=C(C(=O)OC)O1 GXYHQVZORYVUOP-UHFFFAOYSA-N 0.000 description 2
- 150000002762 monocarboxylic acid derivatives Chemical class 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- IOLCXVTUBQKXJR-UHFFFAOYSA-M potassium bromide Chemical compound [K+].[Br-] IOLCXVTUBQKXJR-UHFFFAOYSA-M 0.000 description 2
- 239000012429 reaction media Substances 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000000638 solvent extraction Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- KDYFGRWQOYBRFD-UHFFFAOYSA-N succinic acid Chemical compound OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 2
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 description 2
- 238000009834 vaporization Methods 0.000 description 2
- 230000008016 vaporization Effects 0.000 description 2
- QAVITTVTXPZTSE-UHFFFAOYSA-N (5-formylfuran-2-yl)methyl acetate Chemical compound CC(=O)OCC1=CC=C(C=O)O1 QAVITTVTXPZTSE-UHFFFAOYSA-N 0.000 description 1
- HYZQBNDRDQEWAN-LNTINUHCSA-N (z)-4-hydroxypent-3-en-2-one;manganese(3+) Chemical compound [Mn+3].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O HYZQBNDRDQEWAN-LNTINUHCSA-N 0.000 description 1
- RVHSTXJKKZWWDQ-UHFFFAOYSA-N 1,1,1,2-tetrabromoethane Chemical compound BrCC(Br)(Br)Br RVHSTXJKKZWWDQ-UHFFFAOYSA-N 0.000 description 1
- PXJJKVNIMAZHCB-UHFFFAOYSA-N 2,5-diformylfuran Chemical compound O=CC1=CC=C(C=O)O1 PXJJKVNIMAZHCB-UHFFFAOYSA-N 0.000 description 1
- MMEDJBFVJUFIDD-UHFFFAOYSA-N 2-[2-(carboxymethyl)phenyl]acetic acid Chemical compound OC(=O)CC1=CC=CC=C1CC(O)=O MMEDJBFVJUFIDD-UHFFFAOYSA-N 0.000 description 1
- MLXDUYUQINCFFV-UHFFFAOYSA-N 2-acetyloxyacetic acid Chemical compound CC(=O)OCC(O)=O MLXDUYUQINCFFV-UHFFFAOYSA-N 0.000 description 1
- CCDRPZFMDMKZSZ-UHFFFAOYSA-N 5-(ethoxymethyl)furan-2-carbaldehyde Chemical compound CCOCC1=CC=C(C=O)O1 CCDRPZFMDMKZSZ-UHFFFAOYSA-N 0.000 description 1
- SMMNUDQGZVFDTO-UHFFFAOYSA-N 5-ethoxycarbonylfuran-2-carboxylic acid Chemical compound CCOC(=O)C1=CC=C(C(O)=O)O1 SMMNUDQGZVFDTO-UHFFFAOYSA-N 0.000 description 1
- FKQRDXNGJULUOJ-UHFFFAOYSA-N 6-(aminomethyl)-3',6'-dihydroxyspiro[2-benzofuran-3,9'-xanthene]-1-one Chemical compound C12=CC=C(O)C=C2OC2=CC(O)=CC=C2C21OC(=O)C1=CC(CN)=CC=C21 FKQRDXNGJULUOJ-UHFFFAOYSA-N 0.000 description 1
- 239000005708 Sodium hypochlorite Substances 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 239000004904 UV filter Substances 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 150000001299 aldehydes Chemical group 0.000 description 1
- 150000007933 aliphatic carboxylic acids Chemical class 0.000 description 1
- 125000001931 aliphatic group Chemical class 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- SWLVFNYSXGMGBS-UHFFFAOYSA-N ammonium bromide Chemical compound [NH4+].[Br-] SWLVFNYSXGMGBS-UHFFFAOYSA-N 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 159000000032 aromatic acids Chemical class 0.000 description 1
- 150000001491 aromatic compounds Chemical class 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 238000000998 batch distillation Methods 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
- 238000005119 centrifugation Methods 0.000 description 1
- 229940011182 cobalt acetate Drugs 0.000 description 1
- 150000001869 cobalt compounds Chemical class 0.000 description 1
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 description 1
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 1
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 1
- ZBYYWKJVSFHYJL-UHFFFAOYSA-L cobalt(2+);diacetate;tetrahydrate Chemical compound O.O.O.O.[Co+2].CC([O-])=O.CC([O-])=O ZBYYWKJVSFHYJL-UHFFFAOYSA-L 0.000 description 1
- GAYAMOAYBXKUII-UHFFFAOYSA-L cobalt(2+);dibenzoate Chemical compound [Co+2].[O-]C(=O)C1=CC=CC=C1.[O-]C(=O)C1=CC=CC=C1 GAYAMOAYBXKUII-UHFFFAOYSA-L 0.000 description 1
- NRLCNVYHWRDHTJ-UHFFFAOYSA-L cobalt(2+);naphthalene-1-carboxylate Chemical compound [Co+2].C1=CC=C2C(C(=O)[O-])=CC=CC2=C1.C1=CC=C2C(C(=O)[O-])=CC=CC2=C1 NRLCNVYHWRDHTJ-UHFFFAOYSA-L 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
- BZRRQSJJPUGBAA-UHFFFAOYSA-L cobalt(ii) bromide Chemical compound Br[Co]Br BZRRQSJJPUGBAA-UHFFFAOYSA-L 0.000 description 1
- FJDJVBXSSLDNJB-LNTINUHCSA-N cobalt;(z)-4-hydroxypent-3-en-2-one Chemical compound [Co].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O FJDJVBXSSLDNJB-LNTINUHCSA-N 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000001944 continuous distillation Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- CLVLJVLDCHNKOH-UHFFFAOYSA-N ethyl 5-(acetyloxymethyl)furan-2-carboxylate Chemical compound CCOC(=O)C1=CC=C(COC(C)=O)O1 CLVLJVLDCHNKOH-UHFFFAOYSA-N 0.000 description 1
- MVHXWDHQEUGBPO-UHFFFAOYSA-N ethyl 5-(ethoxymethyl)furan-2-carboxylate Chemical compound CCOCC1=CC=C(C(=O)OCC)O1 MVHXWDHQEUGBPO-UHFFFAOYSA-N 0.000 description 1
- LNBVKBSYQAXCSA-UHFFFAOYSA-N ethyl 5-(hydroxymethyl)furan-2-carboxylate Chemical compound CCOC(=O)C1=CC=C(CO)O1 LNBVKBSYQAXCSA-UHFFFAOYSA-N 0.000 description 1
- AAVWQWIICMTWPK-UHFFFAOYSA-N ethyl 5-(methoxymethyl)furan-2-carboxylate Chemical compound CCOC(=O)C1=CC=C(COC)O1 AAVWQWIICMTWPK-UHFFFAOYSA-N 0.000 description 1
- CDQUPTICIPKERO-UHFFFAOYSA-N ethyl 5-methylfuran-2-carboxylate Chemical compound CCOC(=O)C1=CC=C(C)O1 CDQUPTICIPKERO-UHFFFAOYSA-N 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 239000012362 glacial acetic acid Substances 0.000 description 1
- 150000002334 glycols Chemical class 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 238000004128 high performance liquid chromatography Methods 0.000 description 1
- 239000008240 homogeneous mixture Substances 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 229940040102 levulinic acid Drugs 0.000 description 1
- 229940071125 manganese acetate Drugs 0.000 description 1
- 150000002697 manganese compounds Chemical class 0.000 description 1
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical class [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 description 1
- BDLGYWMNSPNNIV-UHFFFAOYSA-N manganese(3+);borate Chemical class [Mn+3].[O-]B([O-])[O-] BDLGYWMNSPNNIV-UHFFFAOYSA-N 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
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- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- IUGYQRQAERSCNH-UHFFFAOYSA-N pivalic acid Chemical compound CC(C)(C)C(O)=O IUGYQRQAERSCNH-UHFFFAOYSA-N 0.000 description 1
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- ATKJLLMGXIXFDT-UHFFFAOYSA-N propyl 5-(hydroxymethyl)furan-2-carboxylate Chemical compound OCC1=CC=C(O1)C(=O)OCCC ATKJLLMGXIXFDT-UHFFFAOYSA-N 0.000 description 1
- JGBQJPLTDPOTPW-UHFFFAOYSA-N propyl 5-(methoxymethyl)furan-2-carboxylate Chemical compound COCC1=CC=C(O1)C(=O)OCCC JGBQJPLTDPOTPW-UHFFFAOYSA-N 0.000 description 1
- JJKJGICTNBUYGQ-UHFFFAOYSA-N propyl 5-methylfuran-2-carboxylate Chemical compound CCCOC(=O)C1=CC=C(C)O1 JJKJGICTNBUYGQ-UHFFFAOYSA-N 0.000 description 1
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Landscapes
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
Disclosed herein are methods for preparing 5- (alkoxycarbonyl) furan-2-carboxylic Acid (ACFC) from a starting material consisting of furoate. When a raw material consisting of methyl 5-methylfuran-2-carboxylate (MMFC) was used, a product consisting of 5- (methoxycarbonyl) furan-2-carboxylic acid (MCFC) was obtained in high yield.
Description
Technical Field
The present invention relates generally to the field of organic chemistry. It relates in particular to a process for the preparation of 5- (alkoxycarbonyl) furan-2-carboxylic Acid (ACFC) and to compositions containing such acids.
Background
Aromatic dicarboxylic acids, such as terephthalic acid and isophthalic acid, are used to produce a variety of polyesters. Examples of such polyesters include polyethylene terephthalate (PET) and copolymers thereof. These aromatic dicarboxylic acids are typically synthesized by catalytic oxidation of the corresponding dialkyl aromatic compounds obtained from fossil fuels.
There is an increasing interest in using renewable resources as raw materials in the chemical industry, mainly due to the progressive reduction of fossil reserves and their associated environmental impact. Furan-2, 5-dicarboxylic acid (FDCA) and ACFC are versatile intermediates that are considered promising closest biobased alternatives to terephthalic acid and isophthalic acid. Like aromatic diacids, ACFC and FDCA can be condensed with glycols such as ethylene glycol to make polyester resins like PET.
Thus, there is a need in the art to provide alternative and/or improved processes for producing carboxylic acid compositions, particularly those containing ACFC. There is also a need to provide ACFC compositions having high purity and low color.
The present invention addresses this need, as well as other needs, which will become apparent from the following description and appended claims.
Summary of The Invention
In one embodiment of the invention, there is a process for preparing a compound of formula (I):
the method comprises reacting a compound of structural formula (II):
in the presence of an oxidation catalyst and a solvent with an oxidizing agent,
wherein:
the oxidation catalyst comprises cobalt, manganese and bromine;
the solvent comprises a monocarboxylic acid having 2 to 6 carbon atoms;
R 1 is hydrogen, R 3 O-or R 3 C(O)O-；
R 2 Is an alkyl group having 1 to 6 carbon atoms; and
R 3 is hydrogen or an alkyl group having 1 to 6 carbon atoms;
wherein R is 3 Is hydrogen or alkyl having 1 to 3 carbon atoms, and wherein R 2 Not methyl; and said mother liquor stream is in a solvent recovery zone to form an impurity-enriched waste stream; and passing a portion of the impurity-enriched waste stream to a solid-liquid separation zone to form a purge mother liquor stream, and optionally wherein a portion of the solvent is recycled from the purge. A method of producing the composition is also provided.
Brief description of the drawings
Fig. 1 illustrates various embodiments of the present invention in which a process for producing a dried carboxylic acid 410 is provided.
Fig. 2 shows an embodiment of the invention wherein a purge stream is generated. This figure is a detailed illustration of region 700 in fig. 1.
Detailed Description
In one aspect, the present invention provides a process for preparing a compound of formula (I):
wherein R is 2 Is an alkyl group having 1 to 6 carbon atoms. The alkyl group may be branched or straight chain. Examples of such groups include methyl, ethyl, propyl, isopropyl, butyl, methylpropyl, pentyl, ethylpropyl, hexyl, methylpentyl, and ethylbutyl.
In various embodiments, R 2 Is an alkyl group having 1 to 3 carbon atoms.
In various other embodiments, R 2 Is methyl.
Compound (I) may be referred to as 5- (alkoxycarbonyl) furan-2-carboxylic Acid (ACFC). When R is 2 When methyl, compound (I) is 5- (methoxycarbonyl) furan-2-carboxylic acid (MCFC).
The process for preparing compound (I) comprises reacting a compound of formula (II):
is contacted with an oxidizing agent in the presence of an oxidizing catalyst and a solvent.
R in formula (II) 1 Is hydrogen, R 3 O-or R 3 C (O) O-, wherein R 3 Is hydrogen or an alkyl group having 1 to 6 carbon atoms. As R 2 ，R 3 The alkyl groups of (2) may be branched or straight chain.
In various embodiments, R 3 Is hydrogen or an alkyl group having 1 to 3 carbon atoms.
In various other embodiments, R 1 Is hydrogen.
In still various other embodiments, R 1 Is R 3 O-, wherein R 3 Is hydrogen, methyl, ethyl, propyl or isopropyl.
In still various other embodiments, R 1 Is R 3 C (O) O-, wherein R 3 Is hydrogen, methyl, ethyl, propyl or isopropyl.
R in formula (II) 2 As in formula (I), i.e. an alkyl group having 1 to 6 carbon atoms or 1 to 3 carbon atoms, or a methyl group.
Specific examples of the compound (II) include the following:
in various embodiments, compound (II) may be selected from methyl 5-methylfuran-2-carboxylate (MMFC), methyl 5- (hydroxymethyl) furan-2-carboxylate, methyl 5- (methoxymethyl) furan-2-carboxylate, methyl 5- (ethoxymethyl) furan-2-carboxylate, ethyl 5-methylfuran-2-carboxylate, ethyl 5- (hydroxymethyl) furan-2-carboxylate, ethyl 5- (methoxymethyl) furan-2-carboxylate, ethyl 5- (ethoxymethyl) furan-2-carboxylate, propyl 5-methylfuran-2-carboxylate, propyl 5- (hydroxymethyl) furan-2-carboxylate, propyl 5- (methoxymethyl) furan-2-carboxylate, isopropyl 5- (ethoxymethyl) furan-2-carboxylate, isopropyl 5- (hydroxymethyl) furan-2-carboxylate, isopropyl 5- (methoxymethyl) furan-2-carboxylate, methyl 5- ((formyloxy) furan-2-carboxylate, methyl 5- (acetoxymethyl) furan-2-carboxylate, methyl 5- ((acetoxymethyl) furan-2-carboxylate, methyl) 2-carboxylate, methyl- ((ethoxymethyl) furan-2-carboxylate, methyl) 2-carboxylate, ethyl 5- ((formyloxy) methyl) furan-2-carboxylate, ethyl 5- (acetoxymethyl) furan-2-carboxylate, ethyl 5- ((propionyloxy) methyl) furan-2-carboxylate, propyl 5- (acetoxymethyl) furan-2-carboxylate, propyl 5- ((propionyloxy) methyl) furan-2-carboxylate, isopropyl 5- ((formyloxy) methyl) furan-2-carboxylate, isopropyl 5- (acetoxymethyl) furan-2-carboxylate, isopropyl 5- ((propionyloxy) methyl) furan-2-carboxylate, and isopropyl 5- (ethoxymethyl) furan-2-carboxylate, and mixtures thereof.
In various other embodiments, compound (II) may be selected from the group consisting of methyl 5-methylfuran-2-carboxylate (MMFC), methyl 5- (hydroxymethyl) furan-2-carboxylate, methyl 5- (methoxymethyl) furan-2-carboxylate, methyl 5- (ethoxymethyl) furan-2-carboxylate, methyl 5- ((formyloxy) methyl) furan-2-carboxylate, methyl 5- (acetoxymethyl) furan-2-carboxylate, methyl 5- ((propionyloxy) methyl) furan-2-carboxylate, and mixtures thereof.
In still various other embodiments, compound (II) comprises methyl 5-methylfuran-2-carboxylate (MMFC).
Compound (II) can be prepared from renewable raw materials by literature methods and/or can be obtained commercially, such as from xF Technologies inc.
The oxidizing agent usable in the present method is not particularly limited. Which refers to an oxygen source. Preferably, the oxidizing agent is an oxygen-containing gas. Examples include molecular oxygen, air, and other oxygen-containing gases. The oxygen-containing gas introduced into the reactor may have 5 to 80 mole%, 5 to 60 mole%, 5 to 45 mole%, or 15 to 25 mole% molecular oxygen. The balance of the oxygen-containing gas may be one or more oxidizing inert gases, such as nitrogen and argon.
The oxidation catalyst comprises cobalt, manganese and bromine. Cobalt, manganese, and bromine may be supplied from any suitable source. The catalyst component is typically derived from a compound that is soluble in the solvent or in one or more reactants fed to the oxidation zone under the reaction conditions. Preferably, the source of the catalyst component is soluble in the solvent at 25 ℃, 30 ℃ or 40 ℃ and 1atm, and/or soluble in the solvent under the reaction conditions.
Cobalt may be used as an inorganic cobalt salt such as cobalt bromide, cobalt nitrate or cobalt chloride; or as an organic cobalt compound, such as cobalt salts of aliphatic or aromatic acids having 2 to 22 carbon atoms, including cobalt acetate, cobalt octoate, cobalt benzoate, cobalt acetylacetonate and cobalt naphthalate, are provided in ionic form.
When added as a compound to the reaction mixture, the oxidation state of cobalt is not limited and includes +2 and +3 oxidation states.
Manganese may be provided as one or more inorganic manganese salts, such as manganese borates, manganese halides, manganese nitrates; or as an organometallic manganese compound such as manganese salts of lower aliphatic carboxylic acids including manganese acetate, and manganese salts of beta-diketones including manganese acetylacetonate.
The bromine component may be added as elemental bromine, in combination, or as an anion. Suitable bromine sources include hydrogen bromide, hydrobromic acid (sometimes referred to as aqueous hydrogen bromide or aqueous HBr), sodium bromide, potassium bromide, ammonium bromide, and tetrabromoethane. Hydrobromic acid or sodium bromide may be preferred bromine sources.
Cobalt may be used in an amount of 2 to 10,000ppmw, 500 to 6,000ppmw, 1,000 to 6,000ppmw, 700 to 4,500ppmw, or 1,000 to 4,000 ppmw.
Manganese may be used in an amount of 2 to 10,000ppmw, 2 to 600ppmw, 20 to 400ppmw, or 20 to 200 ppmw.
Bromine may be used in an amount of 2 to 10,000ppmw, 300 to 4,500ppmw, 700 to 4,000ppmw, or 1,000 to 4,000 ppmw.
These exemplary ranges of Co, mn and Br are based on the total weight of the reaction mixture.
Alternatively, the amount of catalyst may be expressed based on the weight of the starting material, i.e., compound (II). In this case, the reaction may be carried out with a cobalt content of, for example, 0.50 to 5.0 wt%, a Mn content of 0.15 to 3.0 wt% and a Br content of 0.11 to 3.2 wt% based on the weight of the compound (II).
In various embodiments, the cobalt content may be from 0.50 to 1.0 wt%, the Mn content may be from 1.5 to 2.3 wt%, and the bromine content may be from 0.32 to 3.2 wt%, based on the weight of compound (II).
In various embodiments, the weight ratio of cobalt to manganese in the oxidation catalyst may be at least 0.01:1, at least 0.1:1, at least 1:1, at least 10:1, at least 20:1, at least 50:1, at least 100:1, or at least 400:1.
In various other embodiments, the Co to Mn weight ratio in the oxidation catalyst may be 1:1 to 400:1, 10:1 to 400:1, or 20:1 to 400:1.
In still various other embodiments, the Co to Mn weight ratio in the oxidation catalyst may be from 0.1:1 to 100:1, from 0.1:1 to 10:1, from 0.1:1 to 1:1, from 1:1 to 100:1, from 10:1 to 100:1, or from 20:1 to 100:1.
In various embodiments, the weight ratio of cobalt to bromine may vary from 0.7:1 to 3.5:1, from 0.5:1 to 10:1, or from 0.5:1 to 5:1.
The above ratios of Co: mn and Co: br can result in high yields of ACFC, reduced formation of impurities (including those that cause color in the product), as measured by b, and/or keep the amount of CO and CO2 in the exhaust gas to a minimum.
The solvent used for the reaction comprises a monocarboxylic acid having 2 to 6 carbon atoms or 2 to 4 carbon atoms. Examples of such acids include acetic acid, propionic acid, n-butyric acid, isobutyric acid, n-valeric acid, trimethylacetic acid, and caproic acid. Mixtures of such acids, as well as mixtures of one or more acids with water, may also be used. The solvent may be selected based on its ability to dissolve the catalyst component under the reaction conditions. The solvent may also be selected based on its volatility under the reaction conditions so that it can be withdrawn from the oxidation reactor as an off-gas.
In various embodiments, the solvent comprises anhydrous acetic acid, a mixture of peracetic acid and acetic acid, a mixture of acetic acid and water, or a mixture of peracetic acid, acetic acid and water.
In various other embodiments, the solvent used for the oxidation is an aqueous acetic acid solution typically having an acetic acid concentration of 50 to 99 wt.%, 75 to 99 wt.%, or 80 to 99 wt.%.
The solvent and catalyst used in the process may be recycled and reused. For example, the crude ACFC composition may be withdrawn from the oxidation reactor and subjected to various mother liquor exchange, separation, purification, and/or recovery processes. These processes may provide recovered solvent and catalyst components for recycle back to the oxidation reactor. Thus, a portion of the solvent introduced into the oxidation reactor may be from a recycle stream obtained by replacing, for example, 80 to 90 wt.% of the mother liquor in the crude reaction mixture withdrawn from the oxidation reactor. The mother liquor may be replaced with fresh wet acetic acid, for example acetic acid containing more than 0 to 20% by weight or more than 0 to 15% by weight of water.
Generally, the oxidation reaction may be performed at a temperature of 50 to 220 ℃, 75 to 200 ℃, 75 to 180 ℃, 100 to 180 ℃, 110 to 180 ℃, 130 to 180 ℃, 100 to 160 ℃, 110 to 160 ℃, or 130 to 160 ℃. A typical oxidation reactor is characterized in that in the lower section, gas bubbles are dispersed in the continuous liquid phase. Solids may also be present in the lower section. In the upper section of the reactor, the gas is the continuous phase, in which entrained droplets may also be present. These oxidation temperatures refer to the temperature of the reaction mixture within the oxidation reactor where the liquid exists as a continuous phase.
In various embodiments, the liquid phase in the oxidation reactor has a pH of from-4.0 to 2.0.
Typically, the oxidation reaction can be carried out with a pressure above the reaction mixture, for example, 50 to 1, 000psig, 50 to 750psig, 50 to 500psig, 50 to 400psig, 50 to 200psig, 100 to 1000psig, 100 to 750psig, 100 to 500psig, 100 to 400psig, 100 to 300psig, or 100 to 200 psig. The pressure is typically chosen such that the solvent is predominantly in the liquid phase.
The oxidation process may be carried out in batch, semi-continuous (sometimes referred to as semi-batch) or continuous mode. Batch processes generally involve adding the entire amount of the starting compound (II), catalyst and solvent to the reactor prior to starting the reaction, passing an oxidizing gas through the reaction mixture to initiate and conduct the reaction, and recovering the entire reaction mixture at once at the end of the reaction.
The semi-continuous process generally involves adding the entire amount of catalyst and solvent to a reactor, continuously introducing a compound (II) starting material and an oxidizing gas into the reactor to perform an oxidation reaction, and recovering the entire reaction mixture at once at the end of the reaction.
The continuous process generally involves continuously introducing raw materials, a catalyst, a solvent and an oxidizing gas into a reactor to perform an oxidation reaction and continuously recovering a reaction mixture containing the product compound (I).
The oxidation reaction time may vary depending on various factors such as temperature, pressure and catalyst composition/concentration used. But in general, the reaction time may be 1 to 6 hours or 1 to 3 hours.
The present process can produce compound (I) in a yield of at least 50%, at least 60%, at least 70%, at least 80%, at least 85%, at least 90%, at least 95%, at least 98%, at least 99% or at least 99.5%.
The yield can be calculated by dividing the mass of the resulting ACFC (compound (I)) by the theoretical amount that the oxidizable starting material (compound (II)) should produce based on the amount of starting material consumed. For example, in the case of MMFC as the compound (II), if 1 mole or 140.1 g of MMFC is oxidized, 1 mole or 170.1 g of MCFC will theoretically be produced. If, for example, the actual amount of MCFC formed is only 150 grams, the MCFC yield for this reaction is 88.2% (=150/170.1x100). The same calculations may be applied to oxidation reactions using other oxidizable compounds as well as other products/byproducts.
In addition to compound (I), the present process may also produce one or more by-products. These byproducts may include furan-2, 5-dicarboxylic acid (FDCA), 5-formylfuran-2-carboxylic acid (FFCA), and 5-formylfuran-2-carboxylic acid alkyl ester (AFFC). When R in the starting compound (II) 2 When methyl, AFFC is methyl 5-formylfuran-2-carboxylate (MFFC). The structural formulas of FDCA, FFCA, AFFC and MFFC are provided below.
In various embodiments, the present methods produce FDCA in a yield of less than 20%, less than 15%, less than 10%, less than 5%, less than 1%, or less than 0.5%.
In the present process, as assessed by carbon oxide formation, the extent to which the solvent burns and becomes unusable may be the same as or even lower than typical oxidation processes. While the absolute amount of carbon oxide formation can be reduced by known techniques, such a reduction can be achieved without risking acceptable conversion. Obtaining low amounts of carbon oxide formation can generally be achieved by conducting the reaction at lower oxidation temperatures and/or using catalysts with lower degrees of conversion or selectivity, but this generally results in reduced conversion and increased amounts of intermediates. However, the present process may have the advantage of maintaining a low rate of solvent burn conversion, thereby minimizing the impact on conversion compared to other oxidation processes to achieve low solvent burn.
Thus, in various embodiments, the carbon oxide formation ratio (expressed as CO x CO and CO of (c) 2 The number of moles of (C) per mole of compound (II) fed may be not more than 1.0 mole of CO x Or not more than 0.5 mole CO x Or not more than 0.3 mole CO x In each case relative to the molar amount of compound (II) fed to the reactor.
At the end of the reaction, the reaction mixture is typically depressurized and cooled to obtain a slurry comprising the product compound (I). The product slurry may be subjected to one or more solid-liquid separation (e.g., filtration and/or centrifugation) and washing steps to obtain a wet cake. The wet cake may then be dried (optionally at elevated temperature and under vacuum) to obtain a dried solid product composition.
In various embodiments, the present process may include one or more steps to obtain a dried solid product composition comprising compound (I).
These steps include, at the end of the oxidation reaction, passing at least a portion of the oxidation reaction mixture to a crystallization zone to form a crystallization slurry. Typically, the crystallization zone comprises at least one crystallizer. In the crystallization zone, the reaction mixture may be cooled to a temperature of 20 ℃ to 175 ℃, 40 ℃ to 175 ℃, 50 ℃ to 170 ℃, 60 ℃ to 165 ℃, 25 ℃ to 100 ℃, or 25 ℃ to 50 ℃ to form a crystallization slurry. The vapor from the crystallization zone may be condensed in at least one condenser and sent back to or from the crystallization zone. Alternatively, the vapor from the crystallization zone may be recycled or sent to the energy recovery device without condensing. As another option, the crystallizer vapor may be vented and sent to a recovery system where the solvent is removed and recycled and any VOCs may be treated, for example, by incineration in a catalytic oxidation unit.
The crystallization slurry may be further cooled in a cooling zone to produce a cooled crystallization slurry. Cooling may be achieved by any means known in the art. Typically, the cooling zone comprises a flash tank. The temperature of the cooled crystallization slurry may be 20 ℃ to 160 ℃, 35 ℃ to 160 ℃, 20 ℃ to 140 ℃, 50 ℃ to 140 ℃, 20 ℃ to 120 ℃, 25 ℃ to 120 ℃, 45 ℃ to 120 ℃, 70 ℃ to 120 ℃, 55 ℃ to 95 ℃, 75 ℃ to 95 ℃, or 20 ℃ to 70 ℃.
In various embodiments, at least a portion (up to 100%) of the oxidation mixture may be directed to the cooling zone without first passing through the crystallization zone.
In various other embodiments, at least a portion (up to 100%) of the crystallization slurry may be directed to the solid-liquid separation zone without first passing through the cooling zone.
The cooled crystallization slurry may be sent to a solid-liquid separation zone. The solid-liquid separation zone typically comprises one or more solid-liquid separation devices configured to separate solids from liquids. In the solid-liquid separation zone, the solids can be washed with a wash solvent and dewatered by reducing the moisture content of the washed solids to less than 30 wt%, less than 25 wt%, less than 20 wt%, less than 15 wt%, or less than 10 wt%.
Suitable equipment for the solid-liquid separation zone typically includes centrifuges, cyclones, drum filters, belt filters, pressurized leaf filters, candle filters, and the like.
In various embodiments, the solid-liquid separation zone comprises a rotary drum filter press.
The wash solvent comprises a liquid suitable for displacing and washing the mother liquor from the solids.
In various embodiments, the wash solvent comprises acetic acid and water.
In various other embodiments, the wash solvent comprises water (up to 100%).
The temperature of the washing solvent may be 20 to 135 ℃, 40 to 110 ℃, 50 to 90 ℃, or 20 to 70 ℃. The amount of wash solvent used can be characterized as a wash ratio, which corresponds to the mass of wash liquid divided by the mass of solids on a batch or continuous basis. The wash ratio may be 0.3 to 5,0.4 to 4, or 0.5 to 3.
After the solids are washed in the solid-liquid separation zone, they are typically dewatered to produce a purified wet cake. Dewatering involves reducing the moisture content of the solids to less than 30 wt%, less than 25 wt%, less than 20 wt%, less than 15 wt%, or less than 10 wt%.
In various embodiments, after the solids have been washed with the washing solvent, dehydration is achieved in a filter by passing the gas stream through the solids to displace the free liquid.
In various other embodiments, dewatering is achieved by centrifugal force in a porous drum or solid drum centrifuge.
The filtrate produced in the solid-liquid separation zone is a mother liquor comprising the oxidation solvent, catalyst and some impurities/oxidation byproducts. The filtrate may be sent to a purge zone (purgezone) or back to the oxidation reactor or both.
In the purification zone, a portion of the impurities present in the mother liquor may be separated and removed. The remaining solvent and catalyst may be separated and recycled to the oxidation reactor.
In various embodiments, the remaining solvent from the purification zone may contain more than 30 wt%, more than 50 wt%, more than 70 wt%, or more than 90 wt% of the catalyst entering the purification zone on a continuous or batch basis.
The wash liquid from the solid-liquid separation zone typically comprises a portion of the mother liquor and wash solvent. The ratio of the mass of mother liquor to the mass of wash solvent may be less than 3 or less than 2.
The purified wet cake from the solid-liquid separation zone can be sent to a drying zone to produce a dried solid product and a vapor stream. The vapor stream may comprise a scrubbing solvent vapor and/or an oxidizing solvent vapor.
The drying zone typically includes one or more dryers capable of evaporating at least 10% of the volatiles remaining in the wet cake. Examples of such dryers include indirect contact dryers, such as rotary steam tube dryers, single-stream portcupine TM Dryer and Bepex Solidaire TM Dryers, and direct contact dryers such as fluid bed dryers and ovens equipped with conveyors.
In various embodiments, a vacuum system may be used to draw the vapor stream from the drying zone. If a vacuum system is used in this manner, the pressure of the vapor stream at the dryer outlet may be 760 to 400mm Hg, 760 to 600mmHg, 760 to 700mm Hg, 760 to 720mm Hg, or 760 to 740mm Hg, with the pressure measured at mmHg above absolute vacuum.
The process according to the invention makes it possible to produce a dry solid product containing compound (I), which is surprisingly pure and low in colour, without the need to carry out reactive purification steps such as secondary oxidation (sometimes referred to as post-oxidation), hydrogenation and/or treatment with oxidizing agents such as sodium hypochlorite and/or hydrogen peroxide.
In the batch process, secondary oxidation refers to the step of continuing to supply oxidizing gas to the reactor after oxygen absorption in the reaction medium has ceased. In the semi-continuous or continuous process, the secondary oxidation means a step of continuing the supply of the oxidizing gas to the reaction zone when the supply of the compound (II) raw material is stopped.
Thus, in a second aspect, the present invention provides a dry solid composition comprising at least 70% by weight of a compound of formula (I):
Wherein R is 2 As defined above and the weight% of compound (I) is based on the total weight of the composition.
In various embodiments, the dry solid composition comprises at least 80 wt%, at least 90 wt%, at least 95 wt%, at least 97 wt%, at least 98 wt%, at least 99 wt%, or at least 99.5 wt% of compound (I), based on the total weight of the composition.
In various embodiments, the dry solid composition comprises less than 30 wt%, less than 20 wt%, less than 10 wt%, less than 5 wt%, less than 3 wt%, less than 2 wt%, less than 1 wt%, or less than 0.05 wt% furan-2, 5-dicarboxylic acid (FDCA), based on the total weight of the composition. The content of FDCA may be greater than 0% by weight in each case.
In various embodiments, the dry solid composition comprises less than 1 wt%, less than 0.5 wt%, less than 0.3 wt%, less than 0.1 wt%, less than 500ppmw, less than 400ppmw, less than 300ppmw, less than 200ppmw, less than 100ppmw, less than 50ppmw, less than 10ppmw, less than 5ppmw, or less than 1ppmw of 5-formylfuran-2-carboxylic acid (FFCA), based on the total weight of the composition. In each case, the content of FFCA may be greater than 0 wt%.
In various embodiments, the dry solid composition comprises less than 1 wt%, less than 0.5 wt%, less than 0.3 wt%, less than 0.1 wt%, less than 500ppmw, less than 400ppmw, less than 300ppmw, less than 200ppmw, less than 100ppmw, less than 50ppmw, or less than 10ppmw of alkyl 5-formylfuran-2-carboxylate (AFFC), based on the total weight of the composition. The AFFC content may be greater than 0 wt.% in each case.
When R in the compound (I) 2 Where methyl, the dry solids composition comprises less than 1 wt%, less than 0.5 wt%, less than 0.3 wt%, less than 0.1 wt%, less than 500ppmw, less than 400ppmw, less than 300ppmw, less than 200ppmw, and,Less than 100ppmw, less than 50ppmw, or less than 10ppmw of methyl 5-formylfuran-2-carboxylate (MFFC). The content of MFFC may be greater than 0 wt% in each case.
In various embodiments, the dry solid composition may have a b-x value of less than 4, less than 2, less than 1, -1 to +1, or-0.5 to +0.5.
The b value is one of the three color properties measured on a spectral reflectance-based instrument (spectroscopic reflectance-based instrument). The color may be measured by any means known in the art. Hunter Ultrascan XE the instrument is typically a measuring device. A positive reading indicates yellowness (or absorbance of blue), while a negative reading indicates blueness (or absorbance of yellow).
In one embodiment, the dry solid composition comprises:
(a) At least 70% by weight of compound (I);
(b) Less than 30 weight percent furan-2, 5-dicarboxylic acid (FDCA);
(c) Less than 500ppmw of 5-formylfuran-2-carboxylic acid (FFCA); and
(d) Less than 1000ppmw of alkyl 5-formylfuran-2-carboxylate (AFFC), all amounts based on the total weight of the composition, and
wherein the composition has a b-value of less than 4.
In another embodiment, the dry solid composition comprises:
(a) At least 70 wt% of 5- (methoxycarbonyl) furan-2-carboxylic acid (MCFC);
(b) Less than 30 weight percent furan-2, 5-dicarboxylic acid (FDCA);
(c) Less than 500ppmw of 5-formylfuran-2-carboxylic acid (FFCA); and
(d) Less than 500ppmw of methyl 5-formylfuran-2-carboxylate (MFFC),
all amounts being based on the total weight of the composition, and
wherein the composition has a b-value of less than 4.
In yet another embodiment, the dry solid composition comprises:
(a) At least 99 weight percent 5- (methoxycarbonyl) furan-2-carboxylic acid (MCFC);
(b) Less than 500ppmw furan-2, 5-dicarboxylic acid (FDCA);
(c) Less than 10ppmw of 5-formylfuran-2-carboxylic acid (FFCA); and
(d) Less than 100ppmw of methyl 5-formylfuran-2-carboxylate (MFFC),
All amounts being based on the total weight of the composition, and
wherein the composition has a b-value of-1 to +1.
In yet another embodiment, the dry solid composition comprises:
(a) At least 99 weight percent 5- (methoxycarbonyl) furan-2-carboxylic acid (MCFC);
(b) Less than 500ppmw furan-2, 5-dicarboxylic acid (FDCA);
(c) Less than 10ppmw of 5-formylfuran-2-carboxylic acid (FFCA); and
(d) Less than 100ppmw of methyl 5-formylfuran-2-carboxylate (MFFC),
all amounts being based on the total weight of the composition, and
wherein the composition has a b-value of-0.5 to +0.5.
In various embodiments, a dry solid composition is obtained without performing or being subjected to a reactive purification step.
In various other embodiments, the dry solid composition is obtained without performing or being subjected to a secondary oxidation step, a hydrogenation step, and/or a step of treatment with an oxidizing agent.
In still various other embodiments, the dry solid composition is polymer grade, i.e., it is of sufficient purity to be used in the manufacture of a polymer, without performing or being subjected to reactive purification steps, such as a secondary oxidation step, a hydrogenation step, and/or a step of treatment with an oxidizing agent.
To the extent that any doubt is eliminated, the invention includes and explicitly contemplates and discloses any and all combinations of embodiments, elements, features, parameters, and/or ranges set forth herein. That is, the subject matter of the present disclosure may be defined by any combination of the embodiments, features, characteristics, parameters, and/or ranges mentioned herein.
It is contemplated that any ingredient, component or step not specifically mentioned or specified as part of the present invention may be explicitly excluded.
Any process/method, device, compound, composition, embodiment or component of the invention can be modified by the transitional term "comprising," "consisting essentially of …," or "consisting of …," or variants of these terms.
The indefinite articles "a" and "an" as used herein mean one or more unless the context clearly indicates otherwise. Similarly, unless the context clearly indicates otherwise, the singular forms of nouns include their plural forms and vice versa.
Notwithstanding that the accuracy is intended, the numerical values and ranges described herein are to be regarded as approximations unless the context clearly dictates otherwise. These values and ranges may differ from those recited, depending on the desired properties sought to be obtained by the present disclosure, as well as the variations caused by standard deviations present in the measurement techniques. Furthermore, ranges described herein are intended and expressly contemplated to include all sub-ranges and values within the specified range. For example, a range of 50 to 100 is intended to include all values within the range, including sub-ranges, such as 60 to 90, 70 to 80, etc.
Any two values of the same property or parameter reported in an operational embodiment may define a range. These values may be rounded to the nearest thousandth, percentile, tenth, integer, tenth, hundred, or thousand to define the range.
The contents of all documents, including patent and non-patent documents, cited herein are hereby incorporated by reference in their entirety. To the extent that any of the incorporated subject matter contradicts any disclosure herein, the disclosure herein should take precedence over the incorporated matter.
The invention may be further illustrated by the following working examples, but it should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the invention.
Additional disclosure
It should be understood that the following is not intended to constitute an exclusive list of defined terms. Other definitions may be provided in the above description, such as, for example, when used herein with the defined terms. When appropriate raw materials are used, the method can also be used for MCFC and ACFC as described above. Suitable raw materials are also previously described.
The terms "a" and "an" as used herein mean one or more.
The term "and/or" as used herein when used in reference to the enumeration of two or more items means that any one of the enumerated items may be used alone, or any combination of two or more of the enumerated items may be used. For example, if the composition is described as containing components A, B and/or C, the composition may contain a alone; b alone; c alone; a and B in combination; a and C in combination; a combination of B and C; or A, B and C in combination.
The terms "comprising," "including," and "containing" as used herein are open-ended transition terms used to transition from an object recited before the term to one or more elements recited after the term, where the one or more elements recited after the transition term are not necessarily the only elements that make up the object.
The terms "having," "having," and "with" as used herein have the same open-ended meaning as "comprising," "including," and "comprising" provided above.
The terms "comprising," "including," and "comprising," as used herein, have the same open-ended meaning as "comprising," "including," and "comprising," provided above.
The present specification uses a range of values to quantify certain parameters relating to the invention. It should be understood that when numerical ranges are provided, these ranges should be construed as literally supporting claim limitations that list only the lower limits of the ranges and claim limitations that list only the upper limits of the ranges. For example, a numerical range of 10 to 100 is literally supported by the claims reciting "greater than 10" (without an upper limit) and by the claims reciting "less than 100" (without a lower limit).
The present specification uses specific values to quantify certain parameters relating to the invention, where the specific values are not explicitly part of a range of values. It should be understood that each specific numerical value provided herein should be construed as providing broad, medium, and narrow range literal support. The wide range associated with each particular value is the addition and subtraction of that value by 60% of that value, rounded to the two significant digits. The mid-range associated with each particular value is the value plus and minus 30% of the value, rounded to the two significant digits. The narrow range associated with each particular numerical value is the addition and subtraction of 15% of the numerical value, rounded to the two significant digits. For example, if the specification describes a particular temperature of 62°f, such descriptions provide literal support for a wide range of values from 25°f to 99°f (62°f +/-37°f), a medium range of values from 43°f to 81°f (62°f +/-19°f), and a narrow range of values from 53°f to 71°f (62°f +/-9°f). These broad, medium and narrow numerical ranges should not only be applicable to the particular values, but also to the differences between the particular values. Thus, if the present specification describes a first pressure of 110psia and a second pressure of 48psia (difference 62 psi), the wide, medium and narrow ranges of pressure differences between the two streams will be 25 to 99psi, 43 to 81psi, and 53 to 71psi, respectively.
One embodiment of the present invention is shown in fig. 1 and 2. The present invention provides a process for recovering a portion of the oxidation solvent, a portion of the oxidation catalyst, and removing a portion of the oxidation byproducts and raw material impurities from a solvent stream produced in a process for making furan-2, 5-dicarboxylic acid (FDCA). The methods discussed below may be combined with the previous methods in any logical order.
Step (a) comprises feeding an oxidation solvent, a catalyst system, a gas stream comprising oxygen, and an oxidizable raw material comprising at least one compound selected from the group consisting of the following formulas into an oxidation zone 100 to produce a crude carboxylic acid slurry 110 comprising furan-2, 5-dicarboxylic acid (FDCA): 5- (hydroxymethyl) furfural (5-HMF), 5- (chloromethyl) furfural (5-CMF), 2, 5-dimethylfuran (2, 5-DMF), 5-HMF esters (5-R (CO) OCH) 2 -furfural, wherein r=alkyl, cycloalkyl and aryl), 5-HMF ether (5-R' OCH 2 -furfural, wherein R' =alkyl, cycloalkyl and aryl), 5-alkylfurfural (5-R "-furfural, wherein R" =alkylCycloalkyl and aryl), alkyl carboxylates of methylfuran (5-R ' "O (CO) -methylfuran, wherein R '" =alkyl, cycloalkyl), alkyl carboxylates of alkoxyfuran (5-R "" "O (CO) -OR" "' furan, wherein R" "=alkyl, cycloalkyl and aryl, and R" "" =alkyl, cycloalkyl and aryl), mixed starting materials of 5-HMF and 5-HMF esters and mixed starting materials of 5-HMF and 5-HMF ethers, mixed starting materials of 5-HMF and 5-alkylfurfural, mixed starting materials of 5-HMF and 5-CMF, mixed starting materials of 5-HMF and 2,5-DMF, mixed starting materials of 5-HMF and alkyl carboxylates of methylfuran, mixed starting materials of 5-HMF and alkyl carboxylates of alkoxyfuran.
The structure of the preferred oxidizable starting material compounds is summarized below:
preferred 5-HMF derivative feeds
With element O in a multi-step reaction 2 The 5-HMF feed is oxidized to form FDCA (formula 1) containing 5-formylfuran-2-carboxylic acid (FFCA) as a key intermediate. Oxidation of 5- (acetoxymethyl) furfural (5-AMF) containing oxidizable ester and aldehyde moieties produces FDCA, FFCA, and acetic acid (formula 2). Similarly, oxidation of 5- (ethoxymethyl) furfural (5-EMF) produces FDCA, FFCA, 5- (ethoxycarbonyl) furan-2-carboxylic acid (EFCA), and acetic acid (formula 3).
The streams to the primary oxidation zone 100 include a gaseous stream 10 comprising oxygen, and a stream 30 comprising an oxidation solvent, and a stream 20 comprising an oxidizable raw material. In another embodiment, the stream to the oxidation zone 100 comprises a gas stream 10 comprising oxygen and a stream 20 comprising an oxidation solvent, catalyst, and oxidizable raw materials. In yet another embodiment, the oxidation solvent, oxygen-containing gas, catalyst system, and oxidizable raw material may be fed into oxidation zone 100 as separate and individual streams, or mixed in any combination prior to entering oxidation zone 100, wherein the feed streams may enter oxidizer zone 100 at a single location or at multiple locations.
Suitable catalyst systems are at least one compound selected from, but not limited to, cobalt, bromine and manganese compounds, which are soluble in the selected oxidation solvent. Preferred catalyst systems comprise cobalt, manganese and bromine, wherein the weight ratio of cobalt to manganese in the reaction mixture is from about 10 to about 400 and the weight ratio of cobalt to bromine is from about 0.7 to about 3.5. The data shown in table 1 demonstrate that very high FDCA yields can be obtained using 5-HMF or derivatives thereof and using the above catalyst composition.
Suitable oxidizing solvents include, but are not limited to, aliphatic monocarboxylic acids, preferably containing from 2 to 6 carbon atoms, and mixtures thereof, as well as mixtures of these compounds with water. In one embodiment, the oxidizing solvent comprises acetic acid, wherein the weight% of acetic acid in the oxidizing solvent is greater than 50%, greater than 75%, greater than 85%, and greater than 90%. In another embodiment, the oxidizing solvent comprises acetic acid and water, wherein the ratio of acetic acid to water is greater than 1:1, greater than 6:1, greater than 7:1, greater than 8:1, and greater than 9:1.
The temperature in the oxidation zone may be from 100 ℃ to 220 ℃, or from 100 ℃ to 200 ℃, or from 130 ℃ to 180 ℃, or from 100 ℃ to 180 ℃, and may preferably be from 110 ℃ to 160 ℃. In another embodiment, the temperature in the oxidation zone may be 105 ℃ to 140 ℃.
As shown in table 1, one advantage of the disclosed oxidation conditions is low carbon combustion. The oxidizer off-gas stream 120 is sent to an oxidizer off-gas treatment zone 800 to produce an inert gas stream 810, a liquid stream 820 comprising water, and a recovered oxidation solvent stream 830 comprising condensed solvent. In one embodiment, to scrub the solids present in the solid-liquid separation zone, at least a portion of recovered oxidation solvent stream 830 is sent to scrubbing solvent stream 320 to become a portion of scrubbing solvent stream 320. In another embodiment, inert gas stream 810 may be vented to the atmosphere. In yet another embodiment, at least a portion of inert gas stream 810 can be used as an inert gas in a process for inerting a vessel and/or a transport gas for solids in a process. In another embodiment, at least a portion of the energy in stream 120 is recovered in the form of steam and/or electricity.
In another embodiment of the present invention, a method for producing furan-2, 5-dicarboxylic acid (FDCA) in high yield by liquid phase oxidation is provided that minimizes solvent and raw material losses due to carbon combustion. The process comprises oxidizing at least one oxidizable compound in an oxidizable raw material stream 30 in the presence of an oxidizing gas stream 10, an oxidizing solvent stream 20, and at least one catalyst system in an oxidation zone 100; wherein the oxidizable compound is 5- (hydroxymethyl) furfural (5-HMF); wherein the solvent stream comprises acetic acid with or without water; wherein the catalyst system comprises cobalt, manganese and bromine, wherein the weight ratio of cobalt to manganese in the reaction mixture is from about 10 to about 400. In this process, the temperature may vary from about 100 ℃ to about 220 ℃, from about 105 ℃ to about 180 ℃, and from about 110 ℃ to about 160 ℃. The cobalt concentration of the catalyst system may be from about 1000ppm to about 6000ppm, and the amount of manganese may be from about 2ppm to about 600ppm, and the amount of bromine may be from about 300ppm to about 4500ppm, relative to the total weight of liquid in the reaction medium.
Step (b) includes passing the crude carboxylic acid slurry 110 comprising FDCA to a cooling zone 200 to produce a cooled crude carboxylic acid slurry stream 210 and a 1 st vapor stream 220 comprising oxidation solvent vapor. The cooling of the crude carboxylic acid slurry stream 110 may be accomplished by any method known in the art. Typically, the cooling zone 200 comprises a flash tank. In another embodiment, a portion of up to 100% of the crude carboxylic acid slurry stream 110 is sent directly to the solid-liquid separation zone 300, whereby the portion of up to 100% is not cooled in the cooling zone 200. The temperature of stream 210 can be from 35 ℃ to 210 ℃, from 55 ℃ to 120 ℃, and preferably from 75 ℃ to 95 ℃.
Step (c) includes separating, washing, and dewatering solids present in the cooled crude carboxylic acid slurry stream 210 in a solid-liquid separation zone 300 to produce a crude carboxylic acid wetcake stream 310 comprising FDCA. These functions may be performed in a single solid-liquid separation device or in multiple solid-liquid separation devices. The solid-liquid separation zone comprises at least one solid-liquid separation device capable of separating solids and liquids, washing the solids with a wash solvent stream 320, and reducing the moisture% in the washed solids to less than 30 wt%, less than 20 wt%, less than 15 wt%, and preferably less than 10 wt%.
The apparatus suitable for the solid liquid separation zone may generally be at least one of the following types of devices: centrifuges, cyclones, drum filters, belt filters, pressurized leaf filters, candle filters, and the like. The preferred solid-liquid separation device for the solid-liquid separation zone is a rotary drum filter press.
The temperature of the cooled crude carboxylic acid slurry stream 210 fed to the solid-liquid separation zone 300 can be from 35 ℃ to 210 ℃, from 55 ℃ to 120 ℃, and preferably from 75 ℃ to 95 ℃. The wash solvent stream 320 comprises a liquid suitable for displacing and washing the mother liquor from the solids. In one embodiment, a suitable wash solvent comprises acetic acid. In another embodiment, a suitable wash solvent comprises acetic acid and water. In yet another embodiment, a suitable wash solvent comprises water, and may be 100% water. The temperature of the washing solvent may be 20 to 160 ℃, 40 to 110 ℃, and preferably 50 to 90 ℃.
The amount of wash solvent used is defined as the wash ratio and is equal to the mass of detergent divided by the mass of solids (on a batch or continuous basis). The wash ratio may be from about 0.3 to about 5, from about 0.4 to about 4, and preferably from about 0.5 to 3. After the solids are washed in the solid-liquid separation zone, they are dewatered. Dewatering involves reducing the mass of moisture present with the solids to less than 30 wt%, less than 25 wt%, less than 20 wt%, and most preferably less than 15 wt%, resulting in the formation of a crude carboxylic acid wet cake stream 310 comprising FDCA.
In one embodiment, after washing the solids with the washing solvent, dewatering is achieved in the filter by passing a stream comprising gas through the solids to displace free liquid. In one embodiment, dewatering of the wetcake solids in the solid-liquid separation zone 300 can be performed before and after the wetcake solids in the wash zone 300 to minimize the amount of oxidizer solvent present in the wash liquor stream 340. In another embodiment, the dewatering is achieved by centrifugal force in a porous drum or solid drum centrifuge.
The mother liquor stream 330 generated in the solid-liquid separation zone 300 comprises oxidation solvent, catalyst, and impurities. From 5 wt% to 95 wt%, from 30 wt% to 90 wt%, and most preferably from 40 wt% to 80 wt% of the mother liquor present in the crude carboxylic acid slurry 110 is separated in the solid-liquid separation zone 300 to produce a mother liquor stream 330, resulting in dissolved species comprising impurities present in the mother liquor stream 330 not advancing in the process.
In one embodiment, a portion of the mother liquor stream 330 is sent to a mother liquor purification zone 700, where a portion is at least 5 wt%, at least 25 wt%, at least 45 wt%, at least 55 wt%, at least 75 wt%, or at least 90 wt%. In another embodiment, at least a portion of the mother liquor stream 330 is returned to the oxidation zone 100, with a portion of at least 5 wt%. In yet another embodiment, at least a portion of the mother liquor stream 330 is sent to a mother liquor purification zone 700 and an oxidation zone 100, where a portion is at least 5 wt%. In one embodiment, mother liquor purification zone 700 includes an evaporation step to separate oxygenated solvent from stream 330 by evaporation. Solids may be present in the mother liquor stream 330 at about 5 wt% to about 0.5 wt%. In yet another embodiment, any portion of the mother liquor stream 330 that is sent to the mother liquor purification zone is first subjected to a solid liquid separation device to control the solids present in stream 330 to less than 1 wt.%, less than 0.5 wt.%, less than 0.3 wt.%, or less than 0.1 wt.%. Suitable solid-liquid separation devices include disk centrifuges and batch press filtration solid-liquid separation devices. Preferred solid-liquid separation devices for use in the present application include batch candle filters.
A wash liquor stream 340 is generated in the solid-liquid separation zone 300 and comprises a portion of the mother liquor and wash solvent present in stream 210, wherein the ratio of the mass of mother liquor to the mass of wash solvent is less than 3 and preferably less than 2. In one embodiment, at least a portion of the wash liquid stream 340 is sent to the oxidation zone 100, wherein a portion is at least 5 wt%. In one embodiment, at least a portion of the wash liquor stream is sent to the mother liquor purification zone 700, wherein a portion is at least 5 wt%. In another embodiment, at least a portion of the wash liquor stream 340 is sent to the oxidation zone 100 and the mother liquor purification zone 700, wherein a portion is at least 5 wt%.
In another embodiment, at least a portion (up to 100 wt%) of the crude carboxylic acid slurry stream 110 is sent directly to the solid-liquid separation zone 300, whereby that portion will bypass the cooling zone 200. In this embodiment, the feed to the solid-liquid separation zone 300 comprises at least a portion of the crude carboxylic acid slurry stream 110 and a wash solvent stream 320 to produce a crude carboxylic acid wetcake stream 310 comprising FDCA. The solids in the feed slurry are separated, washed and dewatered in a solid-liquid separation zone 300. These functions may be performed in a single solid-liquid separation device or in multiple solid-liquid separation devices. The solid-liquid separation zone comprises at least one solid-liquid separation device capable of separating solids and liquids, washing the solids with a wash solvent stream 320, and reducing the moisture% in the washed solids to less than 30 wt%, less than 20 wt%, less than 15 wt%, and preferably less than 10 wt%. The apparatus suitable for the solid liquid separation zone may generally be at least one of the following types of devices: centrifuges, cyclones, drum filters, belt filters, pressurized leaf filters, candle filters, and the like. The preferred solid liquid separation device for the solid liquid separation zone 300 is a continuous rotary drum filter press. The temperature of the crude carboxylic acid slurry stream fed to the solid-liquid separation zone 300 can be from 40 ℃ to 210 ℃, from 60 ℃ to 170 ℃, and preferably from 80 ℃ to 160 ℃. Wash stream 320 comprises a liquid suitable for displacing and washing mother liquor from solids. In one embodiment, a suitable wash solvent comprises acetic acid and water. In another embodiment, a suitable wash solvent comprises water up to 100% water. The temperature of the washing solvent may be 20 to 180 ℃, 40 to 150 ℃, and preferably 50 to 130 ℃. The amount of wash solvent used is defined as the wash ratio and is equal to the mass of detergent divided by the mass of solids on a batch or continuous basis. The wash ratio may be from about 0.3 to about 5, from about 0.4 to about 4, and preferably from about 0.5 to 3.
After the solids are washed in the solid-liquid separation zone, they are dewatered. Dewatering includes reducing the mass of moisture present with the solids to less than 30 wt.%, less than 25 wt.%, less than 20 wt.%, and most preferably less than 15 wt.%, resulting in the formation of a crude carboxylic acid wet cake stream 310. In one embodiment, after washing the solids with the washing solvent, dewatering is achieved in the filter by passing a gas stream through the solids to displace the free liquid. In another embodiment, dewatering of the wet cake in the solid-liquid separation zone 300 can be performed by any method known in the art, before and after washing the solids in the zone 300, to minimize the amount of oxidizer solvent present in the wash liquor stream 340. In yet another embodiment, the dewatering is achieved by centrifugal force in a porous drum or solid drum centrifuge.
The mother liquor stream 330 generated in the solid-liquid separation zone 300 comprises oxidation solvent, catalyst, and impurities. From 5 wt% to 95 wt%, from 30 wt% to 90 wt%, and most preferably from 40 wt% to 80 wt% of the mother liquor present in the crude carboxylic acid slurry stream 110 is separated in the solid-liquid separation zone 300 to produce a mother liquor stream 330, resulting in dissolved species comprising impurities present in the mother liquor stream 330 not advancing in the process. In one embodiment, a portion of the mother liquor stream 330 is sent to a mother liquor purification zone 700, where a portion is at least 5 wt%, at least 25 wt%, at least 45 wt%, at least 55 wt%, at least 75 wt%, or at least 90 wt%. In another embodiment, at least a portion is sent back to oxidation zone 100, wherein a portion is at least 5 wt%. In yet another embodiment, at least a portion of the mother liquor stream 330 is sent to the mother liquor purification zone and oxidation zone 100, with a portion of at least 5 weight percent. In one embodiment, mother liquor purification zone 700 includes an evaporation step to separate oxygenated solvent from stream 330 by evaporation.
A wash liquor stream 340 is generated in the solid-liquid separation zone 300 and comprises a portion of the mother liquor and wash solvent present in stream 210, wherein the ratio of the mass of mother liquor to the mass of wash solvent is less than 3 and preferably less than 2. In one embodiment, at least a portion of the wash liquid stream 340 is sent to the oxidation zone 100, wherein a portion is at least 5 wt%. In one embodiment, at least a portion of the wash liquor 340 stream is sent to the mother liquor purification zone 700, wherein a portion is at least 5 wt%. In another embodiment, at least a portion of the wash liquor stream 340 is sent to the oxidation zone 100 and the mother liquor purification zone 700, wherein a portion is at least 5 wt%.
Mother liquor stream 330 contains oxidation solvent, catalyst, soluble intermediates, and soluble impurities. It is desirable to recycle at least a portion of the catalyst and oxidation solvent present in the mother liquor stream 330 directly or indirectly back to the oxidation zone 100, with a portion of at least 5 wt%, at least 25 wt%, at least 45 wt%, at least 65 wt%, at least 85 wt%, or at least 95 wt%. Directly recycling at least a portion of the catalyst and oxidation solvent present in the mother liquor stream 330 includes directly routing a portion of stream 330 to the oxidizer zone 100. Recycling at least a portion of the catalyst and oxidation solvent present in the mother liquor stream 330 indirectly to the oxidation zone 100 includes routing at least a portion of the stream 330 to at least one intermediate zone where the stream 330 is treated to produce one or more streams comprising oxidation solvent and/or catalyst and sent to the oxidation zone 100.
Step (d) includes separating components of the mother liquor stream 330 in the mother liquor purification zone 700 for recycle to the process while also separating those components that contain impurities that are not recycled. Impurities in stream 330 can originate from one or more sources. In one embodiment of the invention, the impurities in stream 330 comprise impurities introduced into the process by feeding a stream comprising the impurities to oxidation zone 100. The mother liquor impurities include at least one impurity selected from the group consisting of: 2, 5-diformylfuran in an amount of from about 5ppm to 800ppm, 20ppm to about 1500ppm, 100ppm to about 5000ppm, 150ppm to about 2.0 wt.%; levulinic acid in an amount of from about 5ppm to 800ppm, from 20ppm to about 1500ppm, from 100ppm to about 5000ppm, from 150ppm to about 2.0 wt.%; succinic acid in an amount of about 5ppm to 800ppm, 20ppm to about 1500ppm, 100ppm to about 5000ppm, 150ppm to about 2.0 wt.%; acetoxyacetic acid in an amount of from about 5ppm to 800ppm, from 20ppm to about 1500ppm, from 100ppm to about 5000ppm, from 150ppm to about 2.0 wt.%.
Impurities are defined as any molecules not required for proper operation of the oxidation zone 100. For example, an oxidizing solvent, a catalyst system, a gas comprising oxygen, and an oxidizable raw material comprising at least one compound selected from the group consisting of: 5- (hydroxymethyl) furfural (5-HMF), 5- (chloromethyl) furfural (5-CMF), 2, 5-dimethylfuran (2, 5-DMF), 5-HMF esters (5-R (CO) OCH) 2 -furfural, wherein r=alkyl, cycloalkyl and aryl), 5-HMF ether (5-R' OCH 2 Furfural, wherein R '=alkyl, cycloalkyl and aryl), 5-alkylfurfural (5-R "-furfural, wherein R" =alkyl, cycloalkyl and aryl), alkylcarboxylates of methylfuran (5-R' "O (CO) -methylfuran, wherein R '" =alkyl, cycloalkyl), alkylcarboxylates of alkoxyfurans (5-R "" O (CO) -OR ""' furan, wherein R "" =alkyl, cycloalkyl and aryl, and R "" "" =alkyl, cycloalkyl and aryl), mixed starting materials of 5-HMF and 5-HMF esters and mixed starting materials of 5-HMF and 5-HMF ethers, mixed starting materials of 5-HMF and 5-alkylfurfural, mixed starting materials of 5-HMF and 2,5-DMF, mixed starting materials of 5-HMF and alkylcarboxylates of methylfuran, the mixed starting materials of 5-HMF and alkylcarboxylates of alkoxyfurans are molecules required for proper operation of the oxidation zone 100, and are not considered impurities. Likewise, chemical intermediates formed in oxidation zone 100 that result in or contribute to a chemical reaction that produces the desired product are not considered impurities. Oxidation byproducts that do not produce the desired product are defined as impurities. Impurities may enter oxidation zone 100 through a recycle stream to oxidation zone 100 or through an impure feed stream fed to oxidation zone 100.
In one embodiment, it is desirable to separate a portion of the impurities from the oxidizer mother liquor stream 330 and purify or remove them from the process as a purification stream 751. In one embodiment of the invention, 5 to 100 weight percent of the mother liquor stream 330 produced in the solid-liquid separation zone 300 is sent to the mother liquor purification zone 700 where a portion of the impurities present in stream 330 are separated and leave the process as purification stream 751. The portion of stream 330 entering mother liquor purification zone 700 can be 5 wt.% or greater, 25 wt.% or greater, 45 wt.% or greater, 65 wt.% or greater, 85 wt.% or greater, or 95 wt.% or greater. Recycled oxidizing solvent stream 711 contains the oxidizing solvent separated from stream 330 and can be recycled to the process. Raffinate stream 742 contains oxidation catalyst separated from stream 330, which may optionally be recycled to the process. In one embodiment, raffinate stream 742 is recycled to oxidation zone 100 and contains greater than 30 wt%, greater than 50 wt%, greater than 80 wt%, or greater than 90 wt% of the catalyst in stream 330 that enters mother liquor purification zone 700. In another embodiment, at least a portion of the mother liquor stream 330 is sent directly to the oxidation zone 100 without first being treated in the mother liquor purification zone 700. In one embodiment, mother liquor purification zone 700 includes an evaporation step to separate oxygenated solvent from stream 330 by evaporation.
One embodiment of the mother liquor purification zone 700 includes passing at least a portion of the oxidizer mother liquor stream 330 to a solvent recovery zone 710 to produce a recycled oxidation solvent stream 711 comprising oxidation solvent and an impurity-rich waste stream 712 comprising oxidation byproducts and catalyst. Any technique known in the art capable of separating volatile solvents from stream 330 may be used. Examples of suitable unit operations include, but are not limited to, batch and continuous vaporization devices operating at above atmospheric pressure, at atmospheric pressure, or under vacuum. Single or multiple evaporation steps may be used. In one embodiment of the invention, sufficient oxidizing solvent is evaporated from stream 330 to obtain stream 712, which is present as a slurry having a weight percent solids of greater than 10 wt%, 20 wt%, 30 wt%, 40 wt%, or 50 wt%. At least a portion of impurity-rich stream 712 can be sent to catalyst recovery zone 760 to generate catalyst-rich stream 761. Examples of unit operations suitable for catalyst recovery zone 760 include, but are not limited to, incineration or combustion of the stream to recover the non-combustible metal catalyst in stream 761.
Another embodiment of the mother liquor purification zone 700 includes passing at least a portion of the mother liquor stream 330 to a solvent recovery zone 710 to produce a recycled oxidation solvent stream 711 comprising oxidation solvent and an impurity-rich waste stream 712 comprising oxidation byproducts and catalyst. Any technique known in the art capable of separating volatile solvents from stream 330 may be used. Examples of suitable unit operations include, but are not limited to, batch and continuous vaporization devices operating at above atmospheric pressure, at atmospheric pressure, or under vacuum. Single or multiple evaporation steps may be used. Sufficient oxidation solvent is evaporated from stream 330 to obtain impurity-rich waste stream 712, which is present as a slurry having a weight percent solids of greater than 5 wt.%, 10 wt.%, 20 wt.%, and 30 wt.%. At least a portion of the impurity-enriched waste stream 712 is passed to a solid liquid separation zone 720 to produce a purified mother liquor stream 723 and a wet cake stream 722 comprising impurities. In another embodiment of the invention, all of stream 712 is sent to solid liquid separation zone 720. Stream 722 can be removed from the process as a waste stream. Wash stream 721 can also be sent to solid-liquid separation zone 720, which can result in the presence of wash liquid in stream 723. It should be noted that region 720 is a separate and distinct region from region 300.
Any technique known in the art capable of separating solids from a slurry may be used. Examples of suitable unit operations include, but are not limited to, batch or continuous filters, batch or continuous centrifuges, filter presses, vacuum belt filters, vacuum drum filters, continuous pressurized drum filters, candle filters, leaf filters, disk centrifuges, decanter centrifuges, basket centrifuges, and the like. A continuous pressurized drum filter is the preferred means for solid-liquid separation zone 720.
Purified mother liquor stream 723 comprising catalyst and impurities and stream 731 comprising catalyst solvent are sent to mixing zone 731 to allow for thorough mixing to produce extraction feed stream 732. In one embodiment, stream 731 comprises water. The mixing is allowed to proceed for at least 30 seconds, 5 minutes, 15 minutes, 30 minutes, or 1 hour. Any technique known in the art may be used for this mixing operation, including in-line static mixers, continuous stirred tanks, mixers, high shear in-line mechanical mixers, and the like.
The extraction feed stream 732, the recycled extraction solvent stream 752, and the fresh extraction solvent stream 753 are sent to a liquid-liquid extraction zone 740 to produce an extract stream 741 comprising impurities and extraction solvent, and a raffinate stream 742 comprising catalyst solvent and oxidation catalyst, which raffinate stream 742 may be recycled directly or indirectly to the oxidation zone 100. The liquid-liquid extraction zone 740 may be implemented in a single or multiple extraction units. The extraction unit may be intermittent and or continuous. Examples of equipment suitable for the extraction zone 740 include a plurality of single stage extraction units. Another example of an apparatus suitable for the extraction zone 740 is a single multi-stage liquid-liquid continuous extraction column. Extract stream 741 is passed to distillation zone 750 where the extraction solvent is separated by evaporation and condensation to produce a recycle extraction solvent stream 752. A purge stream 751 is also generated and can be removed from the process as a waste purge stream. Batch or continuous distillation may be used in distillation zone 750.
In another embodiment, the source of the oxidizer mother liquor stream 330 fed to the mother liquor purification zone 700 can be derived from any mother liquor stream comprising an oxidation solvent, an oxidation catalyst, and impurities generated during the manufacture of furan-2, 5-dicarboxylic acid (FDCA). For example, a solvent exchange zone downstream of oxidation zone 100 that separates at least a portion of the FDCA oxidation solvent from stream 110 can be the source of stream 330. An apparatus suitable for the solvent exchange zone includes a solid-liquid separation device comprising a centrifuge and a filter. Examples of equipment suitable for solvent exchange include, but are not limited to, disk centrifuges or continuous pressurized drum filters.
Examples
Analytical techniques
Liquid chromatography for sample analysis
Samples were analyzed using an Agilent 1260LC component with quaternary pump (quaternary pump), autosampler (3 uL injection), thermostatted column chamber (35 ℃) and diode array UV/vis detector (280 nm). The chromatograph was fitted with a 150mm x 4.6mm Thermo Aquasil C18 column packed with 3 micron particles. The solvent flow procedure used is shown in the table below. Column a is 0.1% phosphoric acid in water, column B is acetonitrile, and column C is Tetrahydrofuran (THF).
EZChrom elite is used for HPLC control and for data processing. For FFCA, FDCA, MCFC, MMFC and MFFC, a 5-point linear calibration was used in the (approximate) range of 0.25 to 100 ppm. Solid samples were prepared by dissolving-0.05 g (accurately weighed to 0.0001 g) in 10ml of 50:50 DMF/THF, so ppm levels of FFCA and MFFC could be detected. For purity analysis, the sample was further diluted by pipetting 100. Mu.L of the sample into a 10mL quantitative bottle and diluting to volume with 50:50 DMF/THF. Sonication was used to ensure complete dissolution of the sample in the solvent. For liquid samples, 0.1 gram of sample was weighed out and diluted to 10mL with 50:50 DMF/THF. A small portion of the prepared sample was transferred to an autovial for injection onto LC.
Color measurement
1) The Carver Press die is assembled as indicated in the specification- -the die is placed on a base and a 40mm bottom cylinder (bottom 40-mm cylinder) is placed with the polished face facing up.
2) A 40-mm plastic cup (Chemplex Plasticup, 39.7x6.4mm) was placed into the die.
3) The sample to be analyzed is filled into a cup. The exact amount of sample added is not important.
4) A40 mm top cylinder (top 40-mm cylinder) was placed with the polished face down on the sample.
5) The plunger is inserted into the die. Should not exhibit "tilting" in the assembled die.
6) The die was placed in the Carver Press to ensure that it was near the center of the lower platen. The safety door is closed.
7) The die was raised until the upper platen was in contact with the plunger. Pressure was applied > 10,000lbs. The die was then held under pressure for about 30 seconds (the exact time is not important).
8) The pressure is released and the lower platen supporting the die is lowered.
9) The die was disassembled and the cup was removed. The cup was placed in a labeled plastic bag (Nasco Whirl-Pak 4 oz).
10 Using a HunterLab UltraScan Pro colorimeter, the following methods were established (Hunterlab EasyMatchQC software, version 3.6.2 or updated):
mode: RSIN-LAV (including specular reflectivity)
Area View：0.78in.
UV filter position: nominal scale
Measurement:
CIE L*a*b*
CIE X Y Z
11 The instrument is standardized as software-proposed using an optical trap fitting and a white block (white tile) fitting pressed against the emission port.
12 Using a certified white block run green block (green block) standard and comparing the resulting CIE X, Y and Z values against the certification value for that block. On each measurement of the indicated value, the resulting value should be within + -0.15 units.
13 By pressing it against the reflecting port and obtaining spectra and values of L, a, b, the sample in the bag is analyzed. Duplicate readings were obtained and reported values averaged.
Examples
Air oxidation of methyl 5-methylfuran-2-carboxylate (MMFC)
Air oxidation of MMFC using a catalyst system containing cobalt, manganese and bromine in acetic acid solvent was performed according to the following general procedure. The reaction is shown in formula 1:
general procedure
Glacial acetic acid (125.7 g) and the amount of catalyst components described in table 1 were transferred to a 300 ml titanium autoclave equipped with a high pressure condenser, baffles and Isco pump. Cobalt, manganese and ionic bromine were provided as cobalt (II) acetate tetrahydrate, manganese (II) acetate and aqueous hydrobromic acid (48.7 wt% in water), respectively.
The autoclave was pressurized with nitrogen at about 50psig and the homogeneous mixture was heated to the desired temperature in a closed system (i.e., no gas flowing therein) with stirring.
At the desired reaction temperature, a 1500sccm air stream was introduced at the bottom of the solution and the reaction pressure was adjusted to the desired level. Liquid MMFC (this is t=0 reaction time) was fed via a high pressure Isco pump at a rate of 0.20 mL/min.
After 30 seconds from the start of substrate feed, 1.0 g peracetic acid (32 wt% in acetic acid) in 5.0 g acetic acid was introduced using a blow box to start the reaction.
After 1 hour the feed was stopped and the reaction continued for another 1 hour under the same conditions of air flow, temperature and pressure.
After the reaction time was completed, the air flow was stopped, and the autoclave was cooled to room temperature and depressurized to obtain a heterogeneous mixture.
The heterogeneous mixture was filtered to isolate the white product. The mass of the filtrate was recorded. The white product was washed twice with 60 ml of acetic acid. The washed white product was dried under vacuum at 110 ℃ overnight and then weighed. The solid product, filtrate and acetic acid washings were analyzed by liquid chromatography.
Analysis of CO and CO by ND-1R (ABB, advanced Optima) of exhaust 2 And O was analyzed by a paramagnetic detection system (Sertomex, 1440 Model) 2 。
The results are reported in table 1. LC chromatograms of the white solid products from example 3 are shown in the accompanying figures.
TABLE 1 results from semi-batch oxidation of MMFC under different conditions
/>
a =48.7 wt% in water; b =97.8 wt% purity; c =in solids, filtrate and AA washes
As seen in table 1, the oxidation reaction mainly forms MCFC instead of FDCA. This reaction produces water as a by-product, but surprisingly, under certain conditions, the methyl ester linkage is rarely hydrolyzed by water to make FDCA.
It is also notable from table 1 that it is possible to produce a high purity product having an FFCA content of only 1.71ppmw, an MFFC content of only 95.7ppmw and a b-x level of-0.11 in one (main) oxidation step. FFCA and MFFC are known chain terminators in polymerization processes. At such low levels of impurities and color, this product can be used directly to make the polymer without further purification. The polymer grade monomer can be made without additional purification steps with significant economic advantages.
The invention has been described in detail with particular reference to particular embodiments thereof, but it will be understood that variations and modifications can be effected within the spirit and scope of the invention.
Claims (20)
1. A process for preparing a compound of structural formula (I):
the method comprises reacting a compound of structural formula (II):
in the presence of an oxidation catalyst and a solvent with an oxidizing agent,
Wherein:
the oxidation catalyst comprises cobalt, manganese, and bromine;
the solvent comprises a monocarboxylic acid having 2 to 6 carbon atoms;
R 1 is hydrogen, R 3 O-or R 3 C(O)O-；
R 2 Is an alkyl group having 1 to 6 carbon atoms; and
R 3 is hydrogen or an alkyl group having 1 to 6 carbon atoms;
wherein R is 3 Is hydrogen or alkyl having 1 to 3 carbon atoms, and wherein R 2 Is methyl; and wherein a portion of the solvent is recovered from the purification process.
2. The method of claim 1, wherein the oxidant is oxygen.
3. The method according to claim 1 or 2, wherein the contacting step is performed at a temperature of 100 ℃ to 180 ℃.
4. A method according to claim 1 or 2, wherein the oxidant is oxygen, air or other oxygen-containing gas.
5. The method according to claim 4, wherein the contacting step is performed at a temperature of 100 ℃ to 180 ℃.
6. The process according to claim 5, wherein the contacting step is conducted at a pressure of 50psig to 1000 psig.
7. The method according to claim 6, wherein the solvent comprises acetic acid.
8. The method according to claim 7, wherein the bromine is derived from hydrobromic acid or sodium bromide.
9. The process according to claim 8, wherein the weight ratio of Co to Mn is from 0.1:1 to 100:1.
10. The process according to claim 9, wherein the weight ratio of Co to Mn is from 20:1 to 100:1.
11. The process according to claim 01, wherein the yield of compound (I) is at least 70%.
12. The process according to claim 11, wherein the yield of furan-2, 5-dicarboxylic acid (FDCA) is less than 20%.
13. The process according to claim 12, which produces a dried solid product comprising at least 70 wt% of compound (I), based on the total weight of the product.
14. The process according to claim 13, which produces a dried solid product comprising at least 99 wt% of compound (I), based on the total weight of the product.
15. The process according to claim 14, wherein the dried solid product comprises less than 30 weight percent furan-2, 5-dicarboxylic acid (FDCA) based on the total weight of the product.
16. The process according to claim 15, wherein the dried solid product comprises less than 500ppmw of 5-formylfuran-2-carboxylic acid (FFCA), based on the total weight of the product.
17. The process according to claim 1 or 2, wherein the dried solid product comprises less than 1000ppmw of alkyl 5-formylfuran-2-carboxylate (AFFC), based on the total weight of the product.
18. The method according to claim 17, wherein the dried solid product has a a b x value of less than 4.
19. A method according to claim 18, wherein the dried solid product has an ab x value of-1 to +1.
20. The process according to claim 19, wherein the dried solid product is obtained without performing a secondary oxidation step, a hydrogenation step or a treatment step with an oxidizing agent.
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US202163201947P | 2021-05-20 | 2021-05-20 | |
| US63/201946 | 2021-05-20 | ||
| US63/201947 | 2021-05-20 | ||
| PCT/US2022/028931 WO2022245625A1 (en) | 2021-05-20 | 2022-05-12 | Purge process for 5-(methoxycarbonyl)furan-2-carboxylic acid (mcfc) |
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