CN114621166B - Preparation method of 2, 5-furandicarboxylic acid - Google Patents
Preparation method of 2, 5-furandicarboxylic acid Download PDFInfo
- Publication number
- CN114621166B CN114621166B CN202011455656.4A CN202011455656A CN114621166B CN 114621166 B CN114621166 B CN 114621166B CN 202011455656 A CN202011455656 A CN 202011455656A CN 114621166 B CN114621166 B CN 114621166B
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- CN
- China
- Prior art keywords
- catalyst
- reaction
- transition metal
- oxidant
- hydroxymethylfurfural
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- CHTHALBTIRVDBM-UHFFFAOYSA-N furan-2,5-dicarboxylic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)O1 CHTHALBTIRVDBM-UHFFFAOYSA-N 0.000 title claims abstract description 62
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- 239000003054 catalyst Substances 0.000 claims abstract description 88
- 238000006243 chemical reaction Methods 0.000 claims abstract description 81
- NOEGNKMFWQHSLB-UHFFFAOYSA-N 5-hydroxymethylfurfural Chemical compound OCC1=CC=C(C=O)O1 NOEGNKMFWQHSLB-UHFFFAOYSA-N 0.000 claims abstract description 65
- RJGBSYZFOCAGQY-UHFFFAOYSA-N hydroxymethylfurfural Natural products COC1=CC=C(C=O)O1 RJGBSYZFOCAGQY-UHFFFAOYSA-N 0.000 claims abstract description 61
- 229910052723 transition metal Inorganic materials 0.000 claims abstract description 48
- 150000003624 transition metals Chemical class 0.000 claims abstract description 40
- 238000000034 method Methods 0.000 claims abstract description 38
- 239000007800 oxidant agent Substances 0.000 claims abstract description 25
- 230000001590 oxidative effect Effects 0.000 claims abstract description 25
- 239000002994 raw material Substances 0.000 claims abstract description 9
- 229910052751 metal Inorganic materials 0.000 claims description 36
- 239000002184 metal Substances 0.000 claims description 36
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical group [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 34
- 239000001301 oxygen Substances 0.000 claims description 34
- 229910052760 oxygen Inorganic materials 0.000 claims description 34
- 239000002904 solvent Substances 0.000 claims description 23
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 19
- DGEZNRSVGBDHLK-UHFFFAOYSA-N [1,10]phenanthroline Chemical compound C1=CN=C2C3=NC=CC=C3C=CC2=C1 DGEZNRSVGBDHLK-UHFFFAOYSA-N 0.000 claims description 18
- 239000012298 atmosphere Substances 0.000 claims description 18
- 239000013110 organic ligand Substances 0.000 claims description 17
- 229920000877 Melamine resin Polymers 0.000 claims description 14
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 12
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 12
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 claims description 11
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 10
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 10
- 229910001862 magnesium hydroxide Inorganic materials 0.000 claims description 9
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims description 9
- 150000001875 compounds Chemical class 0.000 claims description 8
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 claims description 8
- 238000011068 loading method Methods 0.000 claims description 8
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims description 7
- 229910052802 copper Inorganic materials 0.000 claims description 7
- 239000010949 copper Substances 0.000 claims description 7
- 239000002253 acid Substances 0.000 claims description 6
- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O GDVKFRBCXAPAQJ-UHFFFAOYSA-A 0.000 claims description 6
- 229910001701 hydrotalcite Inorganic materials 0.000 claims description 6
- 229960001545 hydrotalcite Drugs 0.000 claims description 6
- 239000000395 magnesium oxide Substances 0.000 claims description 6
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 5
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 claims description 5
- 239000000292 calcium oxide Substances 0.000 claims description 5
- 229910017052 cobalt Inorganic materials 0.000 claims description 5
- 239000010941 cobalt Substances 0.000 claims description 5
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 5
- 229910052742 iron Inorganic materials 0.000 claims description 5
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 claims description 5
- 239000000347 magnesium hydroxide Substances 0.000 claims description 5
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims description 5
- 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 5
- 229910052759 nickel Inorganic materials 0.000 claims description 5
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims description 5
- 230000035484 reaction time Effects 0.000 claims description 5
- 229910001928 zirconium oxide Inorganic materials 0.000 claims description 5
- JFJNVIPVOCESGZ-UHFFFAOYSA-N 2,3-dipyridin-2-ylpyridine Chemical compound N1=CC=CC=C1C1=CC=CN=C1C1=CC=CC=N1 JFJNVIPVOCESGZ-UHFFFAOYSA-N 0.000 claims description 4
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 4
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 4
- 125000000129 anionic group Chemical group 0.000 claims description 4
- 239000004202 carbamide Substances 0.000 claims description 4
- 229910000420 cerium oxide Inorganic materials 0.000 claims description 4
- 229910000000 metal hydroxide Inorganic materials 0.000 claims description 4
- 150000004692 metal hydroxides Chemical class 0.000 claims description 4
- 229910044991 metal oxide Inorganic materials 0.000 claims description 4
- 150000004706 metal oxides Chemical group 0.000 claims description 4
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 claims description 4
- 230000020477 pH reduction Effects 0.000 claims description 4
- 229920000128 polypyrrole Polymers 0.000 claims description 4
- 230000005587 bubbling Effects 0.000 claims description 3
- 239000007789 gas Substances 0.000 claims description 3
- 239000000654 additive Substances 0.000 abstract description 9
- 230000007797 corrosion Effects 0.000 abstract description 6
- 238000005260 corrosion Methods 0.000 abstract description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 32
- 238000003756 stirring Methods 0.000 description 21
- 239000000203 mixture Substances 0.000 description 19
- 239000007795 chemical reaction product Substances 0.000 description 16
- 239000008367 deionised water Substances 0.000 description 16
- 229910021641 deionized water Inorganic materials 0.000 description 16
- 238000004128 high performance liquid chromatography Methods 0.000 description 16
- 239000000047 product Substances 0.000 description 16
- 239000000243 solution Substances 0.000 description 15
- 229910001220 stainless steel Inorganic materials 0.000 description 15
- 239000010935 stainless steel Substances 0.000 description 15
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 15
- 238000010438 heat treatment Methods 0.000 description 14
- 230000003647 oxidation Effects 0.000 description 14
- 238000007254 oxidation reaction Methods 0.000 description 14
- 230000003197 catalytic effect Effects 0.000 description 13
- 239000000126 substance Substances 0.000 description 12
- 239000003446 ligand Substances 0.000 description 11
- 239000011572 manganese Substances 0.000 description 11
- 229940071125 manganese acetate Drugs 0.000 description 10
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 description 10
- 238000002390 rotary evaporation Methods 0.000 description 10
- 229940011182 cobalt acetate Drugs 0.000 description 9
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 description 9
- 238000000197 pyrolysis Methods 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 230000000996 additive effect Effects 0.000 description 6
- 238000001035 drying Methods 0.000 description 6
- 239000002028 Biomass Substances 0.000 description 5
- ROFVEXUMMXZLPA-UHFFFAOYSA-N Bipyridyl Chemical compound N1=CC=CC=C1C1=CC=CC=N1 ROFVEXUMMXZLPA-UHFFFAOYSA-N 0.000 description 5
- 230000001588 bifunctional effect Effects 0.000 description 5
- 150000003839 salts Chemical class 0.000 description 5
- POILWHVDKZOXJZ-ARJAWSKDSA-M (z)-4-oxopent-2-en-2-olate Chemical compound C\C([O-])=C\C(C)=O POILWHVDKZOXJZ-ARJAWSKDSA-M 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 4
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- 229910002651 NO3 Inorganic materials 0.000 description 4
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 4
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 4
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 4
- 238000007172 homogeneous catalysis Methods 0.000 description 4
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 239000003513 alkali Substances 0.000 description 3
- 238000007210 heterogeneous catalysis Methods 0.000 description 3
- QWXYZCJEXYQNEI-OSZHWHEXSA-N intermediate I Chemical compound COC(=O)[C@@]1(C=O)[C@H]2CC=[N+](C\C2=C\C)CCc2c1[nH]c1ccccc21 QWXYZCJEXYQNEI-OSZHWHEXSA-N 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 229920000728 polyester Polymers 0.000 description 3
- -1 2' -bipyridine Chemical compound 0.000 description 2
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- YNPNZTXNASCQKK-UHFFFAOYSA-N Phenanthrene Natural products C1=CC=C2C3=CC=CC=C3C=CC2=C1 YNPNZTXNASCQKK-UHFFFAOYSA-N 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 239000000969 carrier Substances 0.000 description 2
- 239000001913 cellulose Substances 0.000 description 2
- 229920002678 cellulose Polymers 0.000 description 2
- 238000010668 complexation reaction Methods 0.000 description 2
- 238000006297 dehydration reaction Methods 0.000 description 2
- 229910001882 dioxygen Inorganic materials 0.000 description 2
- 239000001307 helium Substances 0.000 description 2
- 229910052734 helium Inorganic materials 0.000 description 2
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 2
- 239000002638 heterogeneous catalyst Substances 0.000 description 2
- 238000005470 impregnation Methods 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- SHNRXUWGUKDPMA-UHFFFAOYSA-N 5-formyl-2-furoic acid Chemical compound OC(=O)C1=CC=C(C=O)O1 SHNRXUWGUKDPMA-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229930091371 Fructose Natural products 0.000 description 1
- RFSUNEUAIZKAJO-ARQDHWQXSA-N Fructose Chemical compound OC[C@H]1O[C@](O)(CO)[C@@H](O)[C@@H]1O RFSUNEUAIZKAJO-ARQDHWQXSA-N 0.000 description 1
- 239000005715 Fructose Substances 0.000 description 1
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 1
- 229920002488 Hemicellulose Polymers 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 230000000536 complexating effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000000921 elemental analysis Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000008103 glucose Substances 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 238000009616 inductively coupled plasma Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 239000012286 potassium permanganate Substances 0.000 description 1
- 239000011949 solid catalyst Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000010025 steaming Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
- C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
- C07D307/34—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
- C07D307/56—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D307/68—Carbon atoms having three bonds to hetero atoms with at the most one bond to halogen
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/1616—Coordination complexes, e.g. organometallic complexes, immobilised on an inorganic support, e.g. ship-in-a-bottle type catalysts
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
- B01J31/1805—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing nitrogen
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
- B01J31/1805—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing nitrogen
- B01J31/181—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine
- B01J31/1815—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine with more than one complexing nitrogen atom, e.g. bipyridyl, 2-aminopyridine
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
- B01J31/1805—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing nitrogen
- B01J31/181—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine
- B01J31/1825—Ligands comprising condensed ring systems, e.g. acridine, carbazole
- B01J31/183—Ligands comprising condensed ring systems, e.g. acridine, carbazole with more than one complexing nitrogen atom, e.g. phenanthroline
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/70—Oxidation reactions, e.g. epoxidation, (di)hydroxylation, dehydrogenation and analogues
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/10—Complexes comprising metals of Group I (IA or IB) as the central metal
- B01J2531/16—Copper
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/70—Complexes comprising metals of Group VII (VIIB) as the central metal
- B01J2531/72—Manganese
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
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Abstract
The application discloses a preparation method of 2, 5-furandicarboxylic acid, which comprises the following steps: reacting a raw material containing 5-hydroxymethylfurfural in the presence of a catalyst and an oxidant to obtain the 2, 5-furandicarboxylic acid; wherein the catalyst is selected from supported transition metal catalysts. The method is simple to operate, mild in condition, free of alkaline additives and capable of avoiding corrosion to reaction equipment.
Description
Technical Field
The application relates to a preparation method of 2, 5-furandicarboxylic acid, belonging to the field of chemistry and chemical engineering.
Background
Biomass is a renewable organic carbon source with abundant reserves in nature, and has important significance in designing a high-efficiency catalytic process and catalytically converting biomass into high-added-value chemicals. The 5-hydroxymethylfurfural is an important bio-based platform compound obtained by hydrolysis-isomerization-dehydration of cellulose and hemicellulose which are derived from biomass, and the oxidation product 2, 5-furandicarboxylic acid of the important bio-based platform compound has a furan cyclic structure and two carboxyl functional groups and can be used as a monomer for preparing bio-based polyester PEF. The PEF polyester and the petroleum-based polyester PET are similar in monomer structural characteristics, have biodegradability, pass European food safety certification, and have good application prospects. At present, a great deal of literature reports that 5-hydroxymethylfurfural (Xu Jie, ren Qiuhe, huang Yizheng, maroon, miao Hong, advanced) is prepared by taking biomass-derived cellulose, glucose and the like as raw materials through dehydration, and a method for preparing 5-hydroxymethylfurfural by catalytic fructose conversion by using a solid catalyst, 201310272819.9) provides feasibility for developing a new method for preparing 2, 5-furandicarboxylic acid by catalytic oxidation of 5-hydroxymethylfurfural in a non-petroleum route.
The current method for preparing 2, 5-furandicarboxylic acid by oxidizing 5-hydroxymethylfurfural mainly comprises a metering oxidation method, a homogeneous catalysis method and a heterogeneous catalysis method. The metered oxidation method mainly uses KMnO4, N2O4, HNO3 and the like as oxidizing agents, the oxidizing agents have corrosiveness to reaction equipment and pollute the environment, the limited (L.Cottier,G.Descotes,J.Lewkowski,et al.Pol.J.Chem.,1994,68,693-698;M.Toshinari,K.Hirokazu,K.Takenobu,M.Hirohide,US Pat.,232815,2007). homogeneous catalysis method for a long time mainly uses Co (OAc) 2/Mn (OAc) 2/Br-or Co (OAc) 2/Zn (OAc) 2/Br-catalysis systems, the 5-hydroxymethylfurfural is catalyzed in air or oxygen to oxidize, the yield of the 2, 5-furandicarboxylic acid is not ideal, and the homogeneous catalysis systems have the defects of difficult separation of metal salts, environmental pollution caused by bromine, corrosion of a reactor and the like, compared with the metered oxidation method and the homogeneous catalysis method, the heterogeneous catalysis method has the advantages of easy separation of products, high catalytic efficiency, environmental protection and the like. At present, the heterogeneous catalysis has the problems of high price of noble metal, certain corrosiveness to reaction equipment caused by the addition of alkaline substances, and the like, and the development of a heterogeneous catalyst of non-noble metal active components and the selective oxidation of 5-hydroxymethylfurfural under the condition of no additional alkali are of great concern.
Disclosure of Invention
According to one aspect of the application, a preparation method of 2, 5-furandicarboxylic acid is provided, which is simple to operate, mild in condition, free of alkaline additives and capable of avoiding corrosion to reaction equipment.
The invention provides a method for preparing 2, 5-furandicarboxylic acid by catalytic selective oxidation of 5-hydroxymethylfurfural, which uses molecular oxygen as an oxidant under the action of a transition metal heterogeneous catalyst, and efficiently catalyzes and oxidizes 5-hydroxymethylfurfural to 2, 5-furandicarboxylic acid under mild conditions without an alkaline additive.
In the invention, the metal active component of the catalyst is prepared into a uniformly dispersed nano structure so as to improve the stability and catalytic performance of the catalyst. The metal components, nitrogen-containing organic ligands and basic carriers used in the catalyst strongly influence the catalytic performance of the catalyst.
The preparation method of the 2, 5-furandicarboxylic acid comprises the following steps: reacting a raw material containing 5-hydroxymethylfurfural in the presence of a catalyst and an oxidant to obtain the 2, 5-furandicarboxylic acid;
wherein the catalyst is selected from supported transition metal catalysts.
Alternatively, the supported transition metal catalyst is a bifunctional catalyst having both oxidizing and basic properties.
Optionally, no alkaline additive is required in the process.
Optionally, the supported transition metal catalyst comprises a support and an active component;
The active component is a transition metal element;
the transition metal element comprises at least one of manganese, iron, cobalt, nickel and copper;
The carrier is an alkaline carrier;
The alkaline carrier is selected from metal oxides, metal hydroxides, and anionic lamellar compounds containing metal;
The supported transition metal catalyst also comprises a nitrogen-containing organic ligand which can coordinate with the transition metal.
Optionally, the nitrogen-containing organic ligand is selected from at least one of 1, 10-phenanthroline, 2' -bipyridine, 2' -bipyridine amine, 4' -bipyridine amine, terpyridine, urea, dicyandiamide, melamine, triethylamine, ethylenediamine, polypyrrole, and C 3N4.
Optionally, the transition metal component of the supported catalyst is uniformly dispersed and has a nano-size.
Optionally, the transition metal component of the supported catalyst has a size of 10 to 50nm.
Optionally, the metal oxide is at least one selected from lanthanum oxide, zirconium oxide, cerium oxide, calcium oxide, magnesium oxide.
Optionally, the metal hydroxide comprises magnesium hydroxide.
Optionally, the metal-containing anionic layered compound comprises hydrotalcite.
Optionally, the loading of the active component in the supported transition metal catalyst is 2.0-25.0 wt%;
wherein the mass of the active component is calculated as the mass of the transition metal element.
Optionally, the loading of the active component in the supported transition metal catalyst is 2.0-10.0 wt%;
wherein the mass of the active component is calculated as the mass of the transition metal element.
Alternatively, the upper limit of the loading of the active component in the supported transition metal catalyst is selected from 2.5wt%, 3.9wt%, 4.2wt%, 4.6wt%, 4.9wt%, 5.3wt%, 6.0wt%, 6.1wt%, 6.5wt%, 8.0wt%, 10.0wt%, 15.0wt%, 20.0wt% or 25.0; the lower limit is selected from 2.0wt%, 2.5wt%, 3.9wt%, 4.2wt%, 4.6wt%, 4.9wt%, 5.3wt%, 6.0wt%, 6.1wt%, 6.5wt%, 8.0wt%, 10.0wt%, 15.0wt% or 20.0wt%.
Alternatively, the supported transition metal catalyst is obtained by pyrolysis after impregnation.
Optionally, the preparation method of the supported transition metal catalyst comprises the following steps:
(1) Adding a nitrogen-containing organic ligand into a solution containing a transition metal source, and complexing to obtain an intermediate I;
(2) And (3) adding an alkaline carrier into the intermediate I in the step (1), carrying out load and pyrolysis to obtain the load type transition metal catalyst.
Optionally, the transition metal source in step (1) is selected from at least one of nitrate, sulfate, acetate, acetylacetonate of a transition metal.
Optionally, the transition metal source in step (1) is selected from at least one of nitrate, sulfate, acetate, acetylacetonate of transition metals manganese, iron, cobalt, nickel, copper.
Optionally, the ratio of the amount of transition metal to organic ligand species in step (1) is from 0.125 to 0.5; the concentration of the solution containing the transition metal source is 0.01-0.1M.
Alternatively, the conditions of the reaction in step (1) are: stirring.
Optionally, the stirring conditions include: the temperature of stirring is 25-80 ℃.
Optionally, the stirring conditions include: the stirring time is 0.5 to 10 hours, preferably 1 to 8 hours.
Optionally, the upper temperature limit of the stirring is selected from 30 ℃, 50 ℃, 60 ℃, 70 ℃ or 80 ℃; the lower limit is selected from 25 ℃, 30 ℃, 50 ℃, 60 ℃ or 70 ℃.
Optionally, the upper time limit of the stirring is selected from 1.5 hours, 3 hours, 4.5 hours, 6 hours or 8 hours; the lower limit is selected from 1 hour, 1.5 hours, 3 hours, 4.5 hours or 6 hours.
Optionally, the solution in step (1) includes a solvent therein; preferably the solvent comprises ethanol.
Optionally, the step (1) includes: mixing active metal salt and nitrogen-containing organic ligand in ethanol, and carrying out complexation reaction at 25-80 ℃ to obtain a complex or a mixture formed by the active metal and the organic ligand.
Optionally, the mass ratio of the intermediate I to the alkaline carrier in the step (2) is 0.15-0.4.
Optionally, the conditions of the load in step (2) include: stirring; preferably, the stirring is carried out at 60 to 80℃for 1 to 6 hours.
Optionally, the conditions of the pyrolysis in step (2) are: pyrolysis is carried out for at least 1h at 300-900 ℃.
Optionally, the upper temperature limit of the pyrolysis is selected from 350 ℃, 450 ℃, 500 ℃, 600 ℃, 750 ℃, 800 ℃, or 900 ℃; the lower limit is selected from 300 ℃, 350 ℃, 450 ℃, 500 ℃, 600 ℃, 750 ℃ or 800 ℃.
Alternatively, the pyrolysis time is 1 to 3 hours, preferably 2 to 3 hours.
Optionally, the pyrolysis is performed under an inert atmosphere; preferably, the inert atmosphere comprises at least one of nitrogen and inert gas.
Optionally, the inert atmosphere is selected from at least one of nitrogen, helium and argon.
Optionally, removing the solvent after the loading; the solvent is preferably removed by rotary evaporation.
Optionally, the solvent is removed followed by drying.
Optionally, the step (2) includes: loading the complex or mixture formed by the active metal and the organic ligand on an alkaline carrier, removing the solvent, and pyrolyzing at 300-900 ℃ for not less than 1h in an inactive atmosphere to obtain the catalyst.
The catalyst has mild synthesis condition and easy operation.
According to the invention, complex compounds or mixtures formed by organic ligands such as 1, 10-phenanthroline, 2' -bipyridine, 2' -bipyridine amine, 4' -bipyridine, terpyridine, urea, dicyandiamide, melamine, triethylamine, ethylenediamine, polypyrrole, C3N4 and the like and nitrate, sulfate, acetate and acetylacetonate of transition metals such as manganese, iron, cobalt, nickel and copper are loaded on different alkaline carriers (lanthanum oxide, zirconium oxide, cerium oxide, calcium oxide, magnesium hydroxide and hydrotalcite), and pyrolysis treatment is carried out. The obtained catalyst has low cost and excellent performance. Under the condition of no alkaline additive, the catalyst has high activity of catalyzing the selective oxidation of 5-hydroxymethylfurfural to prepare 2, 5-furandicarboxylic acid.
The catalysts described in the present application can be obtained according to the prior art, according to the actual needs.
Optionally, the oxidizing agent is an oxygen-containing atmosphere.
Optionally, the oxidizing agent comprises oxygen.
Optionally, the oxidant is oxygen or air.
Optionally, the raw materials further comprise a solvent.
Optionally, the solvent is water.
Optionally, the concentration of 5-hydroxymethylfurfural in the raw material is 0.05-0.2 mol/L; preferably 0.1mol/L.
Optionally, the reaction is followed by acidification.
Optionally, the acid is in excess during the acidification.
Optionally, the acid comprises hydrochloric acid, sulfuric acid, nitric acid.
Optionally, the acidifying comprises: and (3) acidizing at room temperature by adopting excessive acid for 5-30 min.
Alternatively, the concentration of the acid is 0.05 to 0.5M.
Optionally, the reaction conditions include: the reaction temperature is 30-130 ℃.
Alternatively, the temperature of the reaction is 60 to 120 ℃.
Alternatively, the upper temperature limit of the reaction is selected from 50 ℃, 60 ℃, 80 ℃, 100 ℃, 120 ℃ or 130 ℃; the lower limit is selected from 30 ℃, 50 ℃, 60 ℃, 80 ℃, 100 ℃ or 120 ℃.
Optionally, the reaction conditions include: the reaction time is 0.5-24 h.
Alternatively, the reaction time is 6 to 12 hours.
Alternatively, the upper time limit of the reaction is selected from 1h, 3h, 6h, 8h, 10h, 12h, 18h or 24h; the lower limit is selected from 0.5h, 1h, 3h, 6h, 8h, 10h, 12h or 18h.
Optionally, the reaction conditions include: the reaction pressure is between normal pressure and 2.0MPa.
Alternatively, the reaction pressure is 0.5MPa to 2.0MPa.
Optionally, the oxidant is added in the following manner: introducing an oxidant into the reaction system;
The oxidant is an oxygen-containing atmosphere;
The reaction conditions include: the reaction pressure is between normal pressure and 2.0MPa.
Alternatively, the upper limit of the reaction pressure is selected from 0.5MPa, 1MPa, 1.5MPa or 2.0MPa; the lower limit is selected from 0.1MPa, 0.5MPa, 1MPa or 1.5MPa.
Optionally, the oxidant is added in the following manner: introducing an oxidant by a bubbling method;
The oxidant is an oxygen-containing atmosphere;
The flow rate of the oxygen-containing gas is 5-60 mL/min.
Optionally, the flow rate of the oxygen-containing gas is 20mL/min.
Optionally, the molar ratio of the catalyst to the 5-hydroxymethylfurfural is 0.05-0.3: 1, a step of; preferably 0.15:1;
the number of moles of catalyst is calculated as the number of moles of transition metal in the catalyst.
According to the invention, air or molecular oxygen is used as an oxygen source, the reaction is carried out for 0.5 to 24 hours under the conditions that the reaction temperature is 40 to 120 ℃ and the reaction pressure is normal pressure to 2.0MPa, and the 5-hydroxymethylfurfural is efficiently and highly selectively catalyzed and oxidized into 2, 5-furandicarboxylic acid under the condition of no alkali additive.
The method for preparing the 2, 5-furandicarboxylic acid from the biomass source compound 5-hydroxymethylfurfural is high in efficiency and high in selectivity. No alkaline substances are needed to be added in the reaction process, the reaction condition is mild, and the corrosion to reaction equipment can be avoided.
The application discloses a method for preparing 2, 5-furandicarboxylic acid by catalytic selective oxidation of 5-hydroxymethylfurfural, which utilizes a transition metal multiphase bifunctional catalyst with oxidizing property and alkalinity to prepare 2, 5-furandicarboxylic acid by high-efficiency and high-selectivity catalytic oxidation of 5-hydroxymethylfurfural in green solvent water by taking oxygen or air as an oxidant. The method is simple to operate, mild in condition, free of alkaline additives and capable of avoiding corrosion to reaction equipment. When the 5-hydroxymethylfurfural is completely converted, the selectivity of the product 2, 5-furandicarboxylic acid can reach more than 90 percent.
In the present application, "room temperature" means 25 ℃.
In the application, "Phen", "Bpy", "DCD", "HT", "Melamine" respectively represent 1, 10-phenanthroline, 2' -bipyridine, dicyandiamide, hydrotalcite and Melamine.
The application has the beneficial effects that:
1) In the method provided by the application, a multiphase transition metal bifunctional catalyst is used to realize the efficient catalytic oxidation of 5-hydroxymethylfurfural into 2, 5-furandicarboxylic acid in one step under mild conditions;
2) The method provided by the application has the advantages of low cost and small dosage of the transition metal catalyst;
3) The catalyst prepared by the invention has the metal in the form of nano particles and has stability in the reaction process; the coordination of heteroatom nitrogen and metal promotes the catalytic oxidation of 5-hydroxymethylfurfural to prepare 2, 5-furandicarboxylic acid;
4) The prepared transition metal bifunctional catalyst can avoid adding an alkali additive into a reaction system, slows down corrosion to reaction equipment, and is a green and environment-friendly synthetic route;
5) The catalyst and the preparation method of the 2, 5-furandicarboxylic acid provided by the invention have innovation and stronger popularization and application values.
Detailed Description
The present application is described in detail below with reference to examples, but the present application is not limited to these examples.
Unless otherwise indicated, all starting materials in the examples of the present application were purchased commercially.
The analysis method in the embodiment of the application is as follows:
Elemental analysis was performed using a Perkinelmer inductively coupled plasma emission spectrometer (model: ICP-OES7300 DV).
In the embodiment of the application, the conversion rate and selectivity are calculated as follows:
in the examples of the present application, the feedstock conversion and product selectivity are calculated based on the moles of material:
HMF conversion= (HMF addition-HMF residual amount)/HMF addition 100%
Product selectivity = molar amount of product/molar amount of all products
The catalyst in the embodiment of the application is characterized by SEM morphology, and the catalyst with nano-size (10-50 nm) is confirmed to be obtained by uniformly dispersing the transition metal component.
According to one embodiment of the application, the method for preparing 2, 5-furandicarboxylic acid by catalytic selective oxidation of 5-hydroxymethylfurfural comprises the following steps: under the action of a difunctional transition metal catalyst, an alkaline additive is not needed, and oxygen or air is used as an oxidant to oxidize the 5-hydroxymethylfurfural into 2, 5-furandicarboxylic acid.
As one embodiment, the dual function transition metal catalyst is both oxidative and basic.
As one specific embodiment, the preparation of the bifunctional transition metal catalyst comprises the following steps:
a) Mixing active metal salt and a nitrogen-containing organic ligand in ethanol, and carrying out complexation reaction at 25-80 ℃ to obtain a complex or a mixture formed by the active metal and the organic ligand;
b) And loading a complex or a mixture formed by the active metal and the organic ligand on an alkaline carrier by using an impregnation method, removing an ethanol solvent, and performing pyrolysis at 300-900 ℃ for not less than 1h in an inactive atmosphere to obtain the catalyst.
As one specific embodiment, the active metal salt is selected from at least one of nitrate, sulfate, acetate and acetylacetonate of transition metals manganese, iron, cobalt, nickel and copper;
the nitrogen-containing organic ligand is selected from at least one of 1, 10-phenanthroline, 2' -bipyridine, 2' -bipyridine amine, 4' -bipyridine amine, terpyridine, urea, dicyandiamide, melamine, triethylamine, ethylenediamine, polypyrrole and C3N 4;
the alkaline carrier is at least one selected from lanthanum oxide, zirconium oxide, cerium oxide, calcium oxide, magnesium hydroxide and hydrotalcite.
As one specific embodiment, the inert atmosphere is at least one selected from nitrogen, helium and argon.
As one embodiment, the ratio of the amount of the active metal to the amount of the organic ligand substance is 0.125 to 0.5; the concentration of the ethanol solution containing the active metal salt is 0.01-0.1M.
As one specific embodiment, the mass ratio of the complex or mixture formed by the active metal and the organic ligand to the alkaline carrier is 0.15-0.4; the total loading of active metal in the catalyst is 2.0-25.0 wt%.
As one specific embodiment, an aqueous solution containing a 5-hydroxymethylfurfural raw material is contacted and reacted with a catalyst in an oxygen-containing atmosphere to prepare 2, 5-furandicarboxylic acid; the catalyst is selected from at least one of the catalysts prepared by the method.
As one specific implementation, the reaction temperature is 30-130 ℃, the reaction time is 0.5-24 h, and the reaction pressure is normal pressure-2.0 MPa; after the reaction, an acid is added to obtain 2, 5-furandicarboxylic acid.
In the embodiment of the application, the method comprises the following steps: acidification is carried out with an excess of 0.2M sulfuric acid at room temperature for 10min.
Example 1:
1, 10-phenanthroline ligand (the ratio of manganese acetate to 1, 10-phenanthroline substance is 1:6) is added into 50ml of ethanol solution of manganese acetate (the concentration is 0.01M), the mixture is stirred for 1h at room temperature, zirconium oxide (0.692 g) as a carrier is added, the mixture is continuously stirred for 6h at 60 ℃, the solvent is removed by rotary evaporation, the mixture is dried for 12h in an oven at 80 ℃, the obtained product is heated in N 2 at a heating rate of 20 ℃/min, and the temperature is kept at 800 ℃ for 2h, so that Mn-Phen@ZrO 2 catalyst (Mn, 4.6 wt%) is obtained.
Mn-Phen@ZrO 2 (Mn 4.6 wt%) catalyst, 0.5mmol of 5-hydroxymethylfurfural and 5 ml of deionized water were added to a stainless steel autoclave, an inner agglomerated tetrafluoroethylene liner, where the metal: 5-hydroxymethylfurfural = 0.15:1 (mol: mol). And (3) adopting an automatic temperature controller to raise the temperature to 100 ℃ by programming, adding 1.0MPa of oxygen, and reacting for 12 hours, wherein the pressure is kept unchanged in the reaction process. The reaction products were acidified and analyzed by HPLC, and the reaction results are shown in table one.
Example 2:
To 50ml of an ethanol solution (0.01M) of ferric nitrate was added 2,2 '-bipyridine ligand (the ratio of ferric nitrate to 2,2' -bipyridine matter was 1:4), stirred at room temperature for 1h, carrier calcium oxide (0.692 g) was added, stirring was continued for 5h at 80℃and the solvent was removed by rotary evaporation, drying was carried out in an oven at 80℃for 12h, and the obtained product was heated in an inert atmosphere Ar at a heating rate of 10℃per minute and maintained at 900℃for 3h to obtain Fe-Bpy@CaO catalyst (Fe 5.3 wt%).
Fe-Bpy@CaO (Fe 5.3 wt%) catalyst, 0.5mmol of 5-hydroxymethylfurfural and 5 ml of deionized water were added to a stainless steel autoclave, an inner agglomerated tetrafluoroethylene liner, wherein the metal: 5-hydroxymethylfurfural = 0.15:1 (mol: mol). And (3) adopting an automatic temperature controller to raise the temperature to 100 ℃ by programming, adding 1.0MPa of oxygen, and reacting for 12 hours, wherein the pressure is kept unchanged in the reaction process. The reaction products were acidified and analyzed by HPLC, and the reaction results are shown in table one.
Example 3:
To 50ml of an ethanol solution of cobalt nitrate (0.01M) was added dicyandiamide ligand (the ratio of cobalt nitrate to dicyandiamide substance: 1:8), stirred at 30℃for 1 hour, supported hydrotalcite (0.692 g) was added, stirring was continued at 80℃for 6 hours, the solvent was removed by spin evaporation, and the resultant was dried in an oven at 80℃for 12 hours, heated at a heating rate of 5℃per minute at 900℃for 2 hours in an inert atmosphere Ar to give Co-DCD@HT catalyst (Co 6.0 wt%).
Co-DCD@HT (Co 6.0 wt%) catalyst, 0.5mmol of 5-hydroxymethylfurfural and 5 ml of deionized water were added to a stainless steel autoclave, with an inner agglomerated tetrafluoroethylene liner, where the metal: 5-hydroxymethylfurfural = 0.15:1 (mol: mol). And (3) adopting an automatic temperature controller to raise the temperature to 100 ℃ by programming, adding 1.0MPa of oxygen, and reacting for 12 hours, wherein the pressure is kept unchanged in the reaction process. The reaction products were acidified and analyzed by HPLC, and the reaction results are shown in table one.
Example 4:
Co-DCD@HT (Co 6.0 wt%) catalyst was prepared as in example 3.
Co-DCD@HT (Co 6.0 wt%) catalyst, 0.5mmol of 5-hydroxymethylfurfural and 5 ml of deionized water were added to a stainless steel autoclave, with an inner agglomerated tetrafluoroethylene liner, where the metal: 5-hydroxymethylfurfural = 0.15:1 (mol: mol). And (3) adopting an automatic temperature controller to raise the temperature to 100 ℃ by programming, adding 0.5MPa of oxygen, and reacting for 12 hours, wherein the pressure is kept unchanged in the reaction process. The reaction products were acidified and analyzed by HPLC, and the reaction results are shown in table one.
Example 5:
Co-DCD@HT (Co 6.0 wt%) catalyst was prepared as in example 3.
Co-DCD@HT (Co 6.0 wt%) catalyst, 0.5mmol of 5-hydroxymethylfurfural and 5 ml of deionized water were added to a stainless steel autoclave, with an inner agglomerated tetrafluoroethylene liner, where the metal: 5-hydroxymethylfurfural = 0.15:1 (mol: mol). And (3) adopting an automatic temperature controller to raise the temperature to 120 ℃ in a programmed way, adding 1.0MPa of oxygen, and reacting for 12 hours, wherein the pressure is kept unchanged in the reaction process. The reaction products were acidified and analyzed by HPLC, and the reaction results are shown in table one.
Example 6:
To 50ml of an ethanol solution of cobalt nitrate (0.01M) was added a C 3N4 ligand (the ratio of cobalt nitrate to C 3N4 substance: 1:4), stirred at 30℃for 1h, carrier Mg (OH) 2 (0.692 g) was added, stirring was continued at 80℃for 6h, the solvent was removed by rotary evaporation, and dried in an 80℃oven for 12h, and the resultant was heated in N 2 at a heating rate of 5℃per minute and maintained at 800℃for 2h to give Co-C 3N4@Mg(OH)2 (Co 4.9 wt%).
Co-C 3N4@Mg(OH)2 (Co 4.9 wt%) catalyst, 0.5mmol 5-hydroxymethylfurfural and 5ml deionized water were added to a stainless steel autoclave, an inner agglomerated tetrafluoroethylene liner, where the metal: 5-hydroxymethylfurfural = 0.15:1 (mol: mol). And (3) adopting an automatic temperature controller to raise the temperature to 120 ℃ in a programmed way, adding 1.0MPa of oxygen, and reacting for 12 hours, wherein the pressure is kept unchanged in the reaction process. The reaction products were acidified and analyzed by HPLC, and the reaction results are shown in table one.
Example 7:
Co-C 3N4@Mg(OH)2 (Co 4.9 wt%) catalyst was prepared as in example 6.
Co-C 3N4@Mg(OH)2 (Co 4.9 wt%) catalyst, 0.5mmol 5-hydroxymethylfurfural and 5ml deionized water were added to a stainless steel autoclave, an inner agglomerated tetrafluoroethylene liner, where the metal: 5-hydroxymethylfurfural = 0.15:1 (mol: mol). And (3) adopting an automatic temperature controller to raise the temperature to 120 ℃ in a programmed way, adding 1.0MPa of oxygen, and reacting for 6 hours, wherein the pressure is kept unchanged in the reaction process. The reaction products were acidified and analyzed by HPLC, and the reaction results are shown in table one.
Example 8:
1, 10-phenanthroline ligand (the ratio of cobalt acetate to 1, 10-phenanthroline substance is 1:2) is added into 50ml of ethanol solution (the concentration is 0.01M), the mixture is stirred for 1h at 30 ℃, the carrier MgO (0.692 g) is added, the mixture is continuously stirred for 6h at 60 ℃, the solvent is removed by rotary evaporation, the mixture is dried for 12h in an oven at 80 ℃, the obtained product is heated in N 2 at the heating rate of 10 ℃/min, and the temperature is kept at 800 ℃ for 2X h, so that the Co-Phen@MgO catalyst (Co 3.9 wt%) is obtained.
Co-Phen@MgO (Co 3.9 wt%) catalyst, 0.5mmol of 5-hydroxymethylfurfural and 5ml of deionized water were added to a stainless steel autoclave, an inner agglomerated tetrafluoroethylene liner, wherein the metal: 5-hydroxymethylfurfural = 0.15:1 (mol: mol). And (3) adopting an automatic temperature controller to raise the temperature to 120 ℃ in a programmed way, adding 1.0MPa of oxygen, and reacting for 12 hours, wherein the pressure is kept unchanged in the reaction process. The reaction products were acidified and analyzed by HPLC, and the reaction results are shown in table one.
Example 9:
Co-Phen@MgO (Co 3.9 wt%) catalyst was prepared as in example 8.
Co-Phen@MgO (Co 3.9 wt%) catalyst, 0.5mmol of 5-hydroxymethylfurfural and 5 ml of deionized water were added to a stainless steel autoclave, an inner agglomerated tetrafluoroethylene liner, wherein the metal: 5-hydroxymethylfurfural = 0.15:1 (mol: mol). And (3) adopting an automatic temperature controller to raise the temperature to 120 ℃ in a programmed way, adding 1.0MPa of oxygen, and reacting for 8 hours, wherein the pressure is kept unchanged in the reaction process. The reaction products were acidified and analyzed by HPLC, and the reaction results are shown in table one.
Example 10:
1, 10-phenanthroline ligand (the ratio of cobalt acetate to 1, 10-phenanthroline substance is 1:2) is added into 50ml of ethanol solution of cobalt acetate (the concentration is 0.01M), stirring is carried out for 1h at 30 ℃, carrier Mg (OH) 2 (0.692 g) is added, stirring is continued for 8h at 80 ℃, solvent is removed by rotary evaporation, drying is carried out for 12h in an oven at 80 ℃, the obtained product is heated in N 2 at the heating rate of 10 ℃/min, and the temperature is kept at 800 ℃ for 2h, thus obtaining Co-Phen@Mg (OH) 2 catalyst (Co 4.2 wt%).
Co-Phen@Mg (OH) 2 (Co 4.2 wt%) catalyst, 0.5mmol of 5-hydroxymethylfurfural and 5 ml of deionized water were added to a stainless steel autoclave, an inner agglomerated tetrafluoroethylene liner, where the metal: 5-hydroxymethylfurfural = 0.15:1 (mol: mol). And (3) adopting an automatic temperature controller to raise the temperature to 120 ℃ in a programmed way, adding 1.0MPa of oxygen, and reacting for 12 hours, wherein the pressure is kept unchanged in the reaction process. The reaction products were acidified and analyzed by HPLC, and the reaction results are shown in table one.
Example 11:
Adding 1, 10-phenanthroline ligand (the ratio of manganese acetate to cobalt acetate to 1, 10-phenanthroline substances is 0.5:0.5:2) into 50ml of ethanol solution of a mixture of manganese acetate and cobalt acetate, stirring for 2h at 30 ℃, adding carrier magnesium oxide (0.692 g), continuously stirring for 8h at 80 ℃, steaming to remove solvent, drying for 12h in an oven at 80 ℃, heating the obtained product in inert atmosphere Ar at a heating rate of 10 ℃/min, and keeping at 800 ℃ for 2h to obtain the MnCo-Phen@MgO catalyst (Mn 3.8wt% Co 2.3 wt%).
MnCo-Phen@MgO (Mn 3.8wt% Co 2.3 wt%) catalyst, 0.5mmol of 5-hydroxymethylfurfural and 5ml of deionized water were added to a stainless steel autoclave, an inner agglomerated tetrafluoroethylene liner, wherein the metal: 5-hydroxymethylfurfural = 0.15:1 (mol: mol). And (3) adopting an automatic temperature controller to raise the temperature to 120 ℃ in a programmed way, adding 1.0MPa of oxygen, and reacting for 12 hours, wherein the pressure is kept unchanged in the reaction process. The reaction products were acidified and analyzed by HPLC, and the reaction results are shown in table one.
Example 12:
Adding melamine ligand (the ratio of manganese acetate to cobalt acetate to melamine material is 0.5:0.5:8) into 50ml ethanol solution of a mixture of manganese acetate and cobalt acetate, stirring for 1h at 30 ℃, adding carrier magnesium oxide (0.692 g), continuously stirring for 6h at 80 ℃, removing solvent by rotary evaporation, drying for 12h in an oven at 80 ℃, heating the obtained product in inert atmosphere Ar at a heating rate of 5 ℃/min, and keeping at 750 ℃ for 3h to obtain the MnCo-melamine@MgO catalyst (Mn 4.1wt%Co 2.4 wt%).
MnCo-melamine@MgO (Mn 4.1wt% Co 2.4 wt%) catalyst, 0.5mmol of 5-hydroxymethylfurfural and 5 ml of deionized water were added to a stainless steel autoclave, an inner agglomerated tetrafluoroethylene liner, where the metal: 5-hydroxymethylfurfural = 0.15:1 (mol: mol). And (3) adopting an automatic temperature controller to raise the temperature to 120 ℃ in a programmed way, adding 1.0MPa of oxygen, and reacting for 12 hours, wherein the pressure is kept unchanged in the reaction process. The reaction products were acidified and analyzed by HPLC, and the reaction results are shown in table one.
Example 13:
Melamine ligand (the ratio of cobalt acetate, copper nitrate to melamine material is 0.5:0.5:8) was added to 50ml of an ethanol solution (0.01M) of a mixture of cobalt acetate and copper nitrate, stirred at 60℃for 1h, carrier magnesium hydroxide 0.692g was added, stirring was continued at 60℃for 8h, solvent was removed by rotary evaporation, dried in an oven at 80℃for 12h, and the resulting product was heated in N 2 at a heating rate of 5℃per minute and maintained at 750℃for 3h to give CoCu-melamine@Mg (OH) 2 catalyst (Co 3.1wt% Cu 3.4 wt%).
A CoCu-melamine@mg (OH) 2 (Co 3.1wt% cu 3.4 wt%) catalyst, 0.5mmol of 5-hydroxymethylfurfural and 5ml of deionized water were added to a stainless steel autoclave, an inner agglomerated tetrafluoroethylene liner, where the metal: 5-hydroxymethylfurfural = 0.15:1 (mol: mol). And (3) adopting an automatic temperature controller to raise the temperature to 120 ℃ in a programmed way, adding 1.0MPa of oxygen, and reacting for 12 hours, wherein the pressure is kept unchanged in the reaction process. The reaction products were acidified and analyzed by HPLC, and the reaction results are shown in table one.
Example 14
1, 10-Phenanthroline ligand (the ratio of manganese acetate to 1, 10-phenanthroline substance is 1:2) is added into 50ml of ethanol solution of manganese acetate (the concentration is 0.01M), the mixture is stirred for 1h at 30 ℃, mgO (0.692 g) as a carrier is added, the mixture is continuously stirred for 6h at 60 ℃, the solvent is removed by rotary evaporation, the mixture is dried for 12h in an oven at 80 ℃, and the obtained product is heated in N 2 at a heating rate of 10 ℃/min and is kept at 800 ℃ for 2h, so that Mn-Phen@MgO catalyst (Mn, 4.2 wt%) is obtained.
Mn-Phen@MgO (Mn 4.2 wt%) catalyst, 0.5mmol of 5-hydroxymethylfurfural and 5 ml of deionized water were added to a stainless steel autoclave, an inner agglomerated tetrafluoroethylene liner, wherein the metal: 5-hydroxymethylfurfural = 0.15:1 (mol: mol). And (3) adopting an automatic temperature controller to raise the temperature to 120 ℃ in a programmed way, adding 1.0MPa of oxygen, and reacting for 12 hours, wherein the pressure is kept unchanged in the reaction process. The reaction products were acidified and analyzed by HPLC, and the reaction results are shown in table one.
Example 15
Adding dicyandiamide ligand (the ratio of manganese acetate to copper nitrate to dicyandiamide substances is 0.5:0.5:8) into 50ml ethanol solution of a mixture of manganese acetate and copper nitrate, stirring for 1h at 30 ℃, adding carrier magnesium oxide 0.692g, continuously stirring for 6h at 80 ℃, removing the solvent by rotary evaporation, drying for 12h in an oven at 80 ℃, heating the obtained product in inert atmosphere Ar at a heating rate of 5 ℃/min, and keeping at 900 ℃ for 2h to obtain the MnCu-DCD@MgO catalyst (Mn 3.3wt% Cu 2.7 wt%).
MnCu-dcd@mgo (Mn 3.3wt% cu 2.7 wt%) catalyst, 0.5mmol of 5-hydroxymethylfurfural and 5 ml of deionized water were added to a stainless steel autoclave, an inner agglomerated tetrafluoroethylene liner, wherein the metal: 5-hydroxymethylfurfural = 0.15:1 (mol: mol). And (3) adopting an automatic temperature controller to raise the temperature to 120 ℃ in a programmed way, adding 1.0MPa of oxygen, and reacting for 12 hours, wherein the pressure is kept unchanged in the reaction process. The reaction products were acidified and analyzed by HPLC, and the reaction results are shown in table one.
Example 16
Co-Phen@MgO (Co 3.9 wt%) catalyst was prepared as in example 8.
Co-Phen@MgO (Co 3.9 wt%) catalyst, 0.5mmol of 5-hydroxymethylfurfural and 5ml of deionized water were added to a round bottom flask, heated in an oil bath, where the metal: 5-hydroxymethylfurfural = 0.15:1 (mol: mol). The temperature is programmed to be raised to the reaction temperature of 60 ℃ by an automatic temperature controller, and the reaction is carried out for 12 hours by an oxygen bubbling method (the oxygen flow is 20 mL/min). The reaction products were acidified and analyzed by HPLC, and the reaction results are shown in table one.
The results of catalytic oxidation of 5-hydroxymethylfurfural on different catalysts are shown
HMF: 5-hydroxymethylfurfural; FFCA: 5-formyl-2-furancarboxylic acid; FDCA:2, 5-furandicarboxylic acid; phen:1, 10-phenanthroline; bpy:2,2' -bipyridine; DCD: dicyan diamine
While the application has been described in terms of preferred embodiments, it will be understood by those skilled in the art that various changes and modifications can be made without departing from the scope of the application, and it is intended that the application is not limited to the specific embodiments disclosed.
Claims (11)
1. A preparation method of 2, 5-furandicarboxylic acid is characterized in that,
The method comprises the following steps: reacting a raw material containing 5-hydroxymethylfurfural in the presence of a catalyst and an oxidant to obtain the 2, 5-furandicarboxylic acid;
Wherein the catalyst is selected from supported transition metal catalysts;
the supported transition metal catalyst comprises a carrier and an active component;
The active component is a transition metal element;
the transition metal element comprises at least one of manganese, iron, cobalt, nickel and copper;
The carrier is an alkaline carrier;
The alkaline carrier is selected from metal oxides, metal hydroxides, and anionic lamellar compounds containing metal;
The supported transition metal catalyst also comprises a nitrogen-containing organic ligand which can coordinate with transition metal;
The nitrogen-containing organic ligand is selected from at least one of 1, 10-phenanthroline, 2' -bipyridine, 2' -bipyridine amine, 4' -bipyridine amine, terpyridine, urea, dicyandiamide, melamine, triethylamine, ethylenediamine, polypyrrole and C 3N4;
the metal oxide is at least one selected from lanthanum oxide, zirconium oxide, cerium oxide, calcium oxide and magnesium oxide;
The metal hydroxide comprises magnesium hydroxide;
The metal-containing anionic layered compound comprises hydrotalcite;
The raw materials also comprise a solvent; the solvent is water;
the reaction conditions include: the temperature of the reaction is 60-120 ℃;
acidifying after the reaction;
The acid is in excess during the acidification.
2. The method according to claim 1, wherein,
The loading amount of the active component in the supported transition metal catalyst is 2.0wt% -25.0 wt%;
wherein the mass of the active component is calculated as the mass of the transition metal element.
3. The method according to claim 1, wherein,
The load capacity of the active component in the supported transition metal catalyst is 2.0wt% -10.0 wt%;
wherein the mass of the active component is calculated as the mass of the transition metal element.
4. The method according to claim 1, wherein,
The oxidant is an oxygen-containing atmosphere;
the molar concentration of the 5-hydroxymethylfurfural in the raw materials is 0.05-0.2 mol/L.
5. The method according to claim 1, wherein,
The oxidant is oxygen or air.
6. The method according to claim 1, wherein,
The reaction conditions include: the reaction time is 0.5-24 h.
7. The method according to claim 1, wherein,
The reaction conditions include: the reaction time is 6-12 hours.
8. The method according to claim 1, wherein,
The reaction conditions include: the reaction pressure is normal pressure to 2.0MPa.
9. The method according to claim 1, wherein,
The reaction conditions include: the reaction pressure is 0.5-2.0 MPa.
10. The method according to claim 1, wherein,
The oxidant is added in the following manner: introducing an oxidant into the reaction system;
The oxidant is an oxygen-containing atmosphere;
the reaction conditions include: the reaction pressure is normal pressure to 2.0MPa; or (b)
The oxidant is added in the following manner: introducing an oxidant by a bubbling method;
The oxidant is an oxygen-containing atmosphere;
the flow rate of the oxygen-containing gas is 5-60 mL/min.
11. The method according to claim 1, wherein,
The molar ratio of the catalyst to the 5-hydroxymethylfurfural is 0.05-0.3: 1, a step of;
the number of moles of catalyst is calculated as the number of moles of transition metal in the catalyst.
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