CN114621166A - Preparation method of 2, 5-furandicarboxylic acid - Google Patents
Preparation method of 2, 5-furandicarboxylic acid Download PDFInfo
- Publication number
- CN114621166A CN114621166A CN202011455656.4A CN202011455656A CN114621166A CN 114621166 A CN114621166 A CN 114621166A CN 202011455656 A CN202011455656 A CN 202011455656A CN 114621166 A CN114621166 A CN 114621166A
- Authority
- CN
- China
- Prior art keywords
- catalyst
- reaction
- transition metal
- hydroxymethylfurfural
- oxidant
- 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.)
- Granted
Links
- 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 64
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 238000006243 chemical reaction Methods 0.000 claims abstract description 100
- 239000003054 catalyst Substances 0.000 claims abstract description 91
- 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 46
- 150000003624 transition metals Chemical class 0.000 claims abstract description 39
- 238000000034 method Methods 0.000 claims abstract description 35
- 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 10
- 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 27
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 23
- 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
- -1 dicyanodiamine Chemical compound 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
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 10
- 238000011068 loading method Methods 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
- 229910052802 copper Inorganic materials 0.000 claims description 8
- 239000010949 copper Substances 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
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims description 7
- 150000001875 compounds Chemical class 0.000 claims description 7
- 239000000395 magnesium oxide 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
- 230000020477 pH reduction Effects 0.000 claims description 6
- 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
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-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
- 229920000128 polypyrrole Polymers 0.000 claims description 4
- 230000005587 bubbling Effects 0.000 claims description 3
- 239000007789 gas Substances 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims 2
- 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 30
- 238000003756 stirring Methods 0.000 description 27
- 238000010438 heat treatment Methods 0.000 description 20
- 239000000047 product Substances 0.000 description 18
- 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
- 239000000243 solution Substances 0.000 description 16
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 15
- 239000004810 polytetrafluoroethylene Substances 0.000 description 15
- 230000003647 oxidation Effects 0.000 description 14
- 238000007254 oxidation reaction Methods 0.000 description 14
- 229910001220 stainless steel Inorganic materials 0.000 description 14
- 239000010935 stainless steel Substances 0.000 description 14
- 238000001035 drying Methods 0.000 description 11
- 239000003446 ligand Substances 0.000 description 11
- 239000011572 manganese Substances 0.000 description 11
- 239000000203 mixture Substances 0.000 description 11
- 238000002390 rotary evaporation Methods 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
- 230000003197 catalytic effect Effects 0.000 description 9
- 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
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 239000000126 substance Substances 0.000 description 8
- 230000000996 additive effect Effects 0.000 description 6
- 230000001588 bifunctional effect Effects 0.000 description 6
- 150000002739 metals Chemical class 0.000 description 6
- 238000002156 mixing Methods 0.000 description 6
- 238000000197 pyrolysis 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
- 238000006555 catalytic reaction Methods 0.000 description 5
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical class [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 5
- 150000003839 salts Chemical class 0.000 description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 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
- 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
- 238000007172 homogeneous 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
- 229920000728 polyester Polymers 0.000 description 3
- 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 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 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
- 229910002651 NO3 Inorganic materials 0.000 description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-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
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 150000001242 acetic acid derivatives Chemical class 0.000 description 2
- 125000005595 acetylacetonate group Chemical group 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000001913 cellulose Substances 0.000 description 2
- 229920002678 cellulose Polymers 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
- 239000000178 monomer Substances 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 239000010970 precious metal Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 2
- 238000003786 synthesis reaction 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
- PYXZMXHEFIQJJU-UHFFFAOYSA-L C(C)(=O)[O-].[Co+2].C(C)O.C(C)(=O)[O-] Chemical compound C(C)(=O)[O-].[Co+2].C(C)O.C(C)(=O)[O-] PYXZMXHEFIQJJU-UHFFFAOYSA-L 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
- YLQBMQCUIZJEEH-UHFFFAOYSA-N Furan Chemical group C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 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
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 230000004075 alteration Effects 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
- 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
- 239000000969 carrier Substances 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
- 230000000694 effects Effects 0.000 description 1
- 238000000921 elemental analysis Methods 0.000 description 1
- 230000007613 environmental effect 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
- 238000007210 heterogeneous catalysis Methods 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 238000009616 inductively coupled plasma Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 230000007774 longterm Effects 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
- 239000010959 steel Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 229910002001 transition metal nitrate Inorganic materials 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
-
- 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
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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
The biomass is a renewable organic carbon source with abundant reserves in the nature, a high-efficiency catalytic process is designed, and the catalytic conversion of the biomass into high-added-value chemicals is of great significance. 5-hydroxymethylfurfural is an important bio-based platform compound obtained by hydrolyzing, isomerizing and dehydrating biomass-derived cellulose and hemicellulose, and an oxidation product 2, 5-furandicarboxylic acid of the compound has a furan ring structure and two carboxyl functional groups and can be used as a monomer for preparing bio-based polyester PEF. The PEF polyester is similar to petroleum-based polyester PET in monomer structure characteristics, has biodegradability, passes food safety certification of European Union, and has good application prospect. At present, a great deal of literature reports that 5-hydroxymethylfurfural is prepared by dehydrating cellulose, glucose and the like which are derived from biomass as raw materials (Xujie, Argent autumn and crane, Huangyi war, Malong, Miao hong, Gaohong, Gaohao, a method for preparing 5-hydroxymethylfurfural by catalyzing fructose conversion by using a solid catalyst, 201310272819.9), which provides feasibility for developing a novel method for preparing 2, 5-furandicarboxylic acid by catalyzing and oxidizing 5-hydroxymethylfurfural in a non-petroleum route.
At present, the methods for preparing 2, 5-furandicarboxylic acid by oxidizing 5-hydroxymethylfurfural mainly comprise a metering oxidation method, a homogeneous phase catalysis method and a multi-phase catalysis method. KMnO4, N2O4, HNO3, etc. are used as oxidizing agents in the metered oxidation method, and these oxidizing agents are corrosive to reaction equipment, pollute the environment, and have limited long-term use (l.cotter, g.descots, j.lewkowski, et al.pol.j.chem.,1994,68, 693-one 698; m.toshinari, k.hirokazu, k.takenobu, m.hirohide, US Pat. No. 232815,2007). The homogeneous catalysis method mostly uses a Co (OAc)2/Mn (OAc) 2/Br-or Co (OAc)2/Zn (OAc) 2/Br-catalysis system to catalyze the oxidation of 5-hydroxymethylfurfural in air or oxygen, the yield of 2, 5-furandicarboxylic acid is not ideal, and the homogeneous catalysis system has the defects of difficult separation of metal salt, bromine pollution to the environment, corrosion of a reactor and the like (W.Partenheimer, V.Grushin.RSC adv.,2001,343, 102-111; X.Zuo, D.H.Busch, B.Subramaniam, SuACS.chem.Eng., 2016,4, 3659-3668). Compared with a metering oxidation method and a homogeneous catalysis method, the multi-phase catalysis method has the advantages of easy product separation, reusable catalyst, high catalysis efficiency, environmental protection and the like. At present, heterogeneous catalysis has the problems that precious metals are expensive, alkaline substances are added to cause certain corrosivity to reaction equipment and the like, a heterogeneous catalyst with non-precious metal active components is developed, and a reaction route for preparing 2, 5-furandicarboxylic acid by catalyzing selective oxidation of 5-hydroxymethylfurfural without adding alkali is concerned.
Disclosure of Invention
According to one aspect of the application, the preparation method of the 2, 5-furandicarboxylic acid is provided, the operation is simple, the condition is mild, alkaline additives are not needed, and the corrosion to reaction equipment can be avoided.
The invention provides a method for preparing 2, 5-furandicarboxylic acid by catalytic selective oxidation of 5-hydroxymethylfurfural, which is characterized in that under the action of a transition metal heterogeneous catalyst, molecular oxygen is used as an oxidant, an alkaline additive is not needed, and the 5-hydroxymethylfurfural is efficiently catalytically oxidized to the 2, 5-furandicarboxylic acid under mild conditions.
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 component, nitrogen-containing organic ligand and basic carrier 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.
Optionally, the supported transition metal catalyst is a bifunctional catalyst, having both oxidative and basic properties.
Optionally, the method does not require the addition of a basic additive.
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 basic carrier is selected from metal oxides, metal hydroxides, metal-containing anionic layered compounds;
the supported transition metal catalyst also comprises a nitrogen-containing organic ligand capable of coordinating with the transition metal.
Optionally, the nitrogen-containing organic ligand is selected from 1, 10-phenanthroline, 2' -bipyridine, 2' -bipyridine amine, 4' -bipyridine amine, terpyridine, urea, dicyanodiamine, melamine, triethylamine, ethylenediamine, polypyrrole, C3N4At least one of (1).
Optionally, the transition metal component in the supported catalyst is uniformly dispersed and has a nanometer size.
Optionally, the size of the transition metal component in the supported catalyst is 10-50 nm.
Optionally, the metal oxide is selected from at least one of lanthanum oxide, zirconium oxide, cerium oxide, calcium oxide, and magnesium oxide.
Optionally, the metal hydroxide comprises magnesium hydroxide.
Alternatively, the metal-containing anionic layered compound comprises hydrotalcite.
Optionally, the loading amount of the active component in the supported transition metal catalyst is 2.0 wt% to 25.0 wt%;
wherein the mass of the active component is calculated as the mass of the transition metal element.
Optionally, the loading amount of the active component in the supported transition metal catalyst is 2.0 wt% to 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 2.5 wt%, 3.9 wt%, 4.2 wt%, 4.6 wt%, 4.9 wt%, 5.3 wt%, 6.0 wt%, 6.1 wt%, 6.5 wt%, 8.0 wt%, 10.0 wt%, 15.0 wt%, 20.0 wt%, or 25.0 wt%; the lower limit is selected from 2.0 wt%, 2.5 wt%, 3.9 wt%, 4.2 wt%, 4.6 wt%, 4.9 wt%, 5.3 wt%, 6.0 wt%, 6.1 wt%, 6.5 wt%, 8.0 wt%, 10.0 wt%, 15.0 wt%, or 20.0 wt%.
Alternatively, the supported transition metal catalyst is obtained by impregnation followed by pyrolysis.
Alternatively, the preparation method of the supported transition metal catalyst comprises:
(1) adding a nitrogen-containing organic ligand into a solution containing a transition metal source, and complexing to obtain an intermediate I;
(2) and (2) adding an alkaline carrier into the intermediate I in the step (1), carrying, and pyrolyzing to obtain the supported transition metal catalyst.
Optionally, the transition metal source in step (1) is selected from at least one of nitrate, sulfate, acetate, and acetylacetonate of a transition metal.
Optionally, the transition metal source in step (1) is selected from at least one of transition metal nitrates, sulfates, acetates, acetylacetonates of manganese, iron, cobalt, nickel, copper.
Optionally, the ratio of the amount of the transition metal to the organic ligand in step (1) is 0.125-0.5; the concentration of the solution containing the transition metal source is 0.01-0.1M.
Alternatively, the reaction conditions in step (1) are: and (4) stirring.
Optionally, the conditions of agitation include: the stirring temperature is 25-80 ℃.
Optionally, the conditions of stirring 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 deg.C, 30 deg.C, 50 deg.C, 60 deg.C or 70 deg.C.
Alternatively, the upper limit of time for 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; preferably, the solvent comprises ethanol.
Optionally, the step (1) comprises: mixing the active metal salt and the nitrogen-containing organic ligand in ethanol, and carrying out a complex 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 basic carrier in the step (2) is 0.15-0.4.
Optionally, the conditions of the load in step (2) include: stirring; preferably, the mixture is stirred for 1 to 6 hours at a temperature of between 60 and 80 ℃.
Optionally, the pyrolysis conditions in step (2) are: pyrolyzing for not less than 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 deg.C, 350 deg.C, 450 deg.C, 500 deg.C, 600 deg.C, 750 deg.C or 800 deg.C.
Optionally, the pyrolysis time is 1 to 3 hours, preferably 2 to 3 hours.
Optionally, the pyrolysis is carried out under an inert atmosphere; preferably, the inert atmosphere comprises at least one of nitrogen and an inert gas.
Optionally, the inert atmosphere is selected from at least one of nitrogen, helium, and argon.
Optionally, removing the solvent after said loading; preferably, the solvent is removed by rotary evaporation.
Optionally, the solvent is removed followed by drying.
Optionally, the step (2) comprises: and loading a complex or a mixture formed by the active metal and the organic ligand on an alkaline carrier, removing the solvent, and pyrolyzing for not less than 1h at 300-900 ℃ in an inactive atmosphere to obtain the catalyst.
The catalyst has mild synthesis condition and easy operation.
The method comprises the steps of loading a complex or a mixture of organic ligands such as 1, 10-phenanthroline, 2' -bipyridine, 2' -bipyridine amine, 4' -bipyridine, terpyridine, urea, dicyanodiamide, melamine, triethylamine, ethylenediamine, polypyrrole, C3N4 and the like and transition metals such as manganese, iron, cobalt, nickel and copper nitrates, sulfates, acetates and acetylacetonates on different basic carriers (lanthanum oxide, zirconium oxide, cerium oxide, calcium oxide, magnesium hydroxide and hydrotalcite) and carrying out pyrolysis treatment. 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 by the prior art, according to the actual requirements.
Optionally, the oxidant is an oxygen-containing atmosphere.
Optionally, the oxidant 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 the 5-hydroxymethylfurfural in the raw material is 0.05-0.2 mol/L; preferably 0.1 mol/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 (4) acidifying with excessive acid at room temperature for 5-30 min.
Optionally, the concentration of the acid is 0.05-0.5M.
Optionally, the conditions of the reaction include: the reaction temperature is 30-130 ℃.
Optionally, the temperature of the reaction is 60-120 ℃.
Optionally, the upper temperature limit of the reaction is selected from 50 ℃, 60 ℃, 80 ℃, 100 ℃, 120 ℃ or 130 ℃; the lower limit is selected from 30 deg.C, 50 deg.C, 60 deg.C, 80 deg.C, 100 deg.C or 120 deg.C.
Optionally, the conditions of the reaction include: the reaction time is 0.5-24 h.
Optionally, the reaction time is 6-12 h.
Optionally, the upper time limit of the reaction is selected from 1h, 3h, 6h, 8h, 10h, 12h, 18h, or 24 h; the lower limit is selected from 0.5h, 1h, 3h, 6h, 8h, 10h, 12h or 18 h.
Optionally, the conditions of the reaction include: the reaction pressure is normal pressure-2.0 MPa.
Optionally, the reaction pressure is between 0.5MPa and 2.0 MPa.
Optionally, the adding manner of the oxidant is as follows: introducing an oxidant into the reaction system;
the oxidant is an oxygen-containing atmosphere;
the reaction conditions include: the reaction pressure is normal pressure-2.0 MPa.
Alternatively, the upper limit of the reaction pressure is selected from 0.5MPa, 1MPa, 1.5MPa, or 2.0 MPa; the lower limit is selected from 0.1MPa, 0.5MPa, 1MPa or 1.5 MPa.
Optionally, the adding manner of the oxidant is as follows: 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 20 mL/min.
Optionally, the molar ratio of the catalyst to the 5-hydroxymethylfurfural is 0.05-0.3: 1; preferably 0.15: 1;
the moles of the catalyst are calculated as the moles of the 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 0.5-24 h under the conditions that the reaction temperature is 40-120 ℃ and the reaction pressure is normal pressure-2.0 MPa, and the 5-hydroxymethylfurfural is efficiently and selectively catalytically oxidized into the 2, 5-furandicarboxylic acid under the condition of no alkali additive.
The method provides a method for preparing 2, 5-furandicarboxylic acid from a biomass source compound 5-hydroxymethylfurfural, and the catalyst is efficient and high in selectivity. In the reaction process, alkaline substances are not required to be additionally added, 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 is characterized in that a transition metal heterogeneous dual-function catalyst with oxidability and alkalinity is utilized, oxygen or air is used as an oxidant in green solvent water, and the oxidation of the 5-hydroxymethylfurfural is efficiently and selectively catalyzed to prepare the 2, 5-furandicarboxylic acid. The method has simple operation and mild condition, does not need alkaline additives, and can avoid corrosion to reaction equipment. When the 5-hydroxymethylfurfural is completely converted, the selectivity of the product 2, 5-furandicarboxylic acid can reach over 90 percent.
In the present application, "room temperature" means 25 ℃.
In the present application, "Phen", "Bpy", "DCD", "HT" and "Melamine" respectively represent 1, 10-phenanthroline, 2' -bipyridine, dicyanodiamide, hydrotalcite and Melamine.
The beneficial effects that this application can produce include:
1) in the method provided by the application, a heterogeneous transition metal bifunctional catalyst is used to realize the one-step efficient catalytic oxidation of 5-hydroxymethylfurfural into 2, 5-furandicarboxylic acid under mild conditions;
2) the method provided by the application has the advantages that the transition metal catalyst has low cost and small using amount;
3) the catalyst prepared by the invention has the advantages that metal exists in the form of nano particles, and the catalyst 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 is used, so that an alkali additive can be prevented from being added into a reaction system, the corrosion to reaction equipment is slowed down, and the preparation method is a green and environment-friendly synthesis route;
5) the catalyst and the preparation method of the 2, 5-furandicarboxylic acid provided by the invention have innovativeness and high popularization and application values.
Detailed Description
The present application will be described in detail with reference to examples, but the present application is not limited to these examples.
The raw materials in the examples of the present application were all purchased commercially, unless otherwise specified.
The analysis method in the examples of the present application is as follows:
elemental analysis was performed using a Perkinelmer inductively coupled plasma emission spectrometer (model: ICP-OES7300 DV).
The conversion, selectivity, in the examples of the present application were calculated as follows:
in the examples of the present application, the feedstock conversion and product selectivity were calculated on the basis of moles of species:
HMF conversion ═ (HMF add-HMF remainder)/HMF add 100%
Product selectivity-molar amount of product/molar amount of all products
The morphology of the catalyst in the embodiment of the application is characterized by SEM, and the catalyst with uniformly dispersed transition metal components and nanometer size (10-50 nm) is confirmed to be obtained.
According to one embodiment of the present application, the method for preparing 2, 5-furandicarboxylic acid by catalytic selective oxidation of 5-hydroxymethylfurfural comprises: under the action of a bifunctional transition metal catalyst, 5-hydroxymethylfurfural is oxidized into 2, 5-furandicarboxylic acid by using oxygen or air as an oxidant without a basic additive.
As one embodiment, the bifunctional transition metal catalyst is both oxidative and basic.
As one 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 a complex reaction at 25-80 ℃ to obtain a complex or a mixture formed by the active metal and the organic ligand;
b) 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 pyrolyzing for not less than 1h at 300-900 ℃ in an inactive atmosphere to obtain the catalyst.
As a specific embodiment, the active metal salt is selected from at least one of nitrate, sulfate, acetate and acetylacetonate of transition metal 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, dicyanodiamide, 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 a specific embodiment, the inert atmosphere is selected from at least one of nitrogen, helium and argon.
In one embodiment, the ratio of the amount of the active metal to the amount of the organic ligand is 0.125 to 0.5; the concentration of the ethanol solution containing the active metal salt is 0.01-0.1M.
In one embodiment, the mass ratio of the complex or mixture of the active metal and the organic ligand to the basic carrier is 0.15-0.4; the total loading of active metals in the catalyst is 2.0 wt% -25.0 wt%.
As a specific embodiment, an aqueous solution containing a 5-hydroxymethylfurfural raw material is in contact reaction 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 embodiment, 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 is finished, adding acid to obtain the 2, 5-furandicarboxylic acid.
In the examples of the present application, acidification is: acidification was carried out with excess 0.2M sulfuric acid at room temperature for 10 min.
Example 1:
adding 1, 10-phenanthroline ligand (the amount ratio of manganese acetate to 1, 10-phenanthroline is 1:6) into 50ml of ethanol solution (the concentration is 0.01M) of manganese acetate, stirring at room temperature for 1h, adding carrier zirconium oxide (0.692g), continuing stirring at 60 ℃ for 6h, removing the solvent by rotary evaporation, drying in an oven at 80 ℃ for 12h, and putting the obtained product in an N-type solvent (N-type solvent) to obtain a solution2Heating at a heating rate of 20 ℃/min, and keeping the temperature at 800 ℃ for 2h to obtain Mn-Phen @ ZrO2Catalyst (Mn, 4.6 wt%).
Adding Mn-Phen @ ZrO2(Mn 4.6 wt%) catalyst, 0.5mmol of 5-hydroxymethylfurfural and 5 ml of deionized water were added to the stainless steelThe steel high-pressure reaction kettle is internally attached with a polytetrafluoroethylene lining, wherein the metal: 5-hydroxymethylfurfural ═ 0.15:1 (mol: mol). The temperature is increased to 100 ℃ by adopting an automatic temperature controller, 1.0MPa oxygen is added, the reaction is carried out for 12 hours, and the pressure is kept unchanged in the reaction process. The reaction product was acidified and analyzed by HPLC, and the reaction results are shown in Table I.
Example 2:
to 50ml of an ethanol solution of ferric nitrate (0.01M) was added a 2,2 '-bipyridine ligand (the ratio of the amount of ferric nitrate to the amount of 2,2' -bipyridine species was 1:4), stirred at room temperature for 1 hour, added a supported calcium oxide (0.692g), stirred at 80 ℃ for 5 hours, rotary evaporated to remove the solvent, dried at 80 ℃ for 12 hours, and the resulting product was heated at a temperature rise rate of 10 ℃/min in an inert atmosphere Ar and held at 900 ℃ for 3 hours to give Fe-Bpy @ CaO catalyst (Fe 5.3 wt%).
Adding Fe-Bpy @ CaO (Fe 5.3 wt%) catalyst, 0.5mmol of 5-hydroxymethylfurfural and 5 ml of deionized water into a stainless steel high-pressure reaction kettle, and attaching a polytetrafluoroethylene lining inside, wherein the weight ratio of metal: 5-hydroxymethylfurfural ═ 0.15:1 (mol: mol). The temperature is increased to 100 ℃ by adopting an automatic temperature controller, 1.0MPa oxygen is added, the reaction is carried out for 12 hours, and the pressure is kept unchanged in the reaction process. The reaction product was acidified and analyzed by HPLC, and the reaction results are shown in Table I.
Example 3:
adding dicyandiamide ligand (the amount ratio of cobalt nitrate to dicyandiamide substance is 1:8) into 50ml of ethanol solution of cobalt nitrate (0.01M), stirring for 1h at 30 ℃, adding supported hydrotalcite (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 an inert atmosphere Ar at the heating rate of 5 ℃/min, and keeping for 2h at 900 ℃ to obtain the Co-DCD @ HT catalyst (Co 6.0 wt%).
Adding Co-DCD @ HT (Co 6.0 wt%) catalyst, 0.5mmol of 5-hydroxymethyl furfural and 5 ml of deionized water into a stainless steel high-pressure reaction kettle, and attaching a polytetrafluoroethylene lining inside, wherein the weight ratio of metals: 5-hydroxymethylfurfural ═ 0.15:1 (mol: mol). The temperature is increased to 100 ℃ by adopting an automatic temperature controller, 1.0MPa oxygen is added, the reaction is carried out for 12 hours, and the pressure is kept unchanged in the reaction process. The reaction product was acidified and analyzed by HPLC, and the reaction results are shown in Table I.
Example 4:
the Co-DCD @ HT (Co 6.0 wt%) catalyst was prepared as in example 3.
Adding Co-DCD @ HT (Co 6.0 wt%) catalyst, 0.5mmol of 5-hydroxymethyl furfural and 5 ml of deionized water into a stainless steel high-pressure reaction kettle, and attaching a polytetrafluoroethylene lining inside, wherein the weight ratio of metals: 5-hydroxymethylfurfural ═ 0.15:1 (mol: mol). The temperature is increased to 100 ℃ by adopting an automatic temperature controller, 0.5MPa oxygen is added, the reaction is carried out for 12 hours, and the pressure is kept unchanged in the reaction process. The reaction product was acidified and analyzed by HPLC and the reaction results are shown in table one.
Example 5:
the Co-DCD @ HT (Co 6.0 wt%) catalyst was prepared as in example 3.
Adding Co-DCD @ HT (Co 6.0 wt%) catalyst, 0.5mmol of 5-hydroxymethyl furfural and 5 ml of deionized water into a stainless steel high-pressure reaction kettle, and attaching a polytetrafluoroethylene lining inside, wherein the weight ratio of metals: 5-hydroxymethylfurfural ═ 0.15:1 (mol: mol). And (3) adopting an automatic temperature controller to program the temperature to 120 ℃, adding 1.0MPa of oxygen, reacting for 12 hours, and keeping the pressure unchanged in the reaction process. The reaction product was acidified and analyzed by HPLC, and the reaction results are shown in Table I.
Example 6:
to 50ml of an ethanol solution (0.01M) of cobalt nitrate was added C3N4Ligand (cobalt nitrate and C)3N4The mass ratio of the substances is 1:4), stirring for 1h at 30 ℃, adding a carrier Mg (OH)2(0.692g), stirring at 80 ℃ for 6h, removing the solvent by rotary evaporation, drying in an oven at 80 ℃ for 12h, and adding N to the obtained product2Heating at a heating rate of 5 ℃/min, and keeping the temperature at 800 ℃ for 2h to obtain Co-C3N4@Mg(OH)2(Co 4.9wt%)。
Mixing Co-C3N4@Mg(OH)2(Co 4.9 wt%) catalyst, 0.5mmol of 5-hydroxymethylfurfural and 5 ml of deionized water were added into a stainless steel high-pressure reaction kettle, and a polytetrafluoroethylene lining was attached inside, wherein the molar ratio of the metals: 5-hydroxymethylfurfural ═ 0.15:1 (mol: mol). Using automatic temperature control programsHeating to 120 deg.c, adding 1.0MPa oxygen for 12 hr while maintaining the pressure unchanged. The reaction product was acidified and analyzed by HPLC, and the reaction results are shown in Table I.
Example 7:
Co-C3N4@Mg(OH)2(Co 4.9 wt%) the catalyst was prepared as in example 6.
Mixing Co-C3N4@Mg(OH)2(Co 4.9 wt%) catalyst, 0.5mmol 5-hydroxymethylfurfural and 5 ml deionized water were added to a stainless steel high pressure reactor, lined with polytetrafluoroethylene liner, wherein the weight ratio of metal: 5-hydroxymethylfurfural ═ 0.15:1 (mol: mol). The temperature is increased to 120 ℃ by adopting an automatic temperature controller, 1.0MPa oxygen is added, the reaction is carried out for 6 hours, and the pressure is kept unchanged in the reaction process. The reaction product was acidified and analyzed by HPLC, and the reaction results are shown in Table I.
Example 8:
adding 1, 10-phenanthroline ligand (the amount ratio of the cobalt acetate to the 1, 10-phenanthroline is 1:2) into 50ml of cobalt acetate ethanol solution (the concentration is 0.01M), stirring at 30 ℃ for 1h, adding carrier MgO (0.692g), continuously stirring at 60 ℃ for 6h, removing the solvent by rotary evaporation, drying in an oven at 80 ℃ for 12h, and putting the obtained product in an N-type solvent2In (1), heating was carried out at a heating rate of 10 ℃/min, and the temperature was maintained at 800 ℃ for 2X h, to obtain a Co-Phen @ MgO catalyst (Co 3.9 wt%).
Adding Co-Phen @ MgO (Co 3.9 wt%) catalyst, 0.5mmol of 5-hydroxymethyl furfural and 5 ml of deionized water into a stainless steel high-pressure reaction kettle, and attaching a polytetrafluoroethylene lining inside, wherein the weight ratio of metal: 5-hydroxymethylfurfural ═ 0.15:1 (mol: mol). And (3) adopting an automatic temperature controller to program the temperature to 120 ℃, adding 1.0MPa of oxygen, reacting for 12 hours, and keeping the pressure unchanged in the reaction process. The reaction product was acidified and analyzed by HPLC, and the reaction results are shown in Table I.
Example 9:
the Co-Phen @ MgO (Co 3.9 wt%) catalyst was prepared as in example 8.
Adding Co-Phen @ MgO (Co 3.9 wt%) catalyst, 0.5mmol of 5-hydroxymethyl furfural and 5 ml of deionized water into a stainless steel high-pressure reaction kettle, and attaching a polytetrafluoroethylene lining inside, wherein the weight ratio of metal: 5-hydroxymethylfurfural ═ 0.15:1 (mol: mol). And (3) adopting an automatic temperature controller to program the temperature to 120 ℃, adding 1.0MPa of oxygen, reacting for 8 hours, and keeping the pressure unchanged in the reaction process. The reaction product was acidified and analyzed by HPLC and the reaction results are shown in table one.
Example 10:
adding 1, 10-phenanthroline ligand (the amount ratio of cobalt acetate to 1, 10-phenanthroline is 1:2) into 50ml of ethanol solution (with the concentration of 0.01M) of cobalt acetate, stirring at 30 ℃ for 1h, adding a carrier Mg (OH)2(0.692g), stirring at 80 ℃ for 8h, removing the solvent by rotary evaporation, drying in an oven at 80 ℃ for 12h, and adding N to the obtained product2Heating at a heating rate of 10 ℃/min, and keeping the temperature at 800 ℃ for 2h to obtain Co-Phen @ Mg (OH)2Catalyst (Co 4.2 wt%).
Mixing Co-Phen @ Mg (OH)2(Co 4.2 wt%) catalyst, 0.5mmol 5-hydroxymethylfurfural and 5 ml deionized water were added to a stainless steel high pressure reactor, lined with polytetrafluoroethylene liner, wherein the weight ratio of metal: 5-hydroxymethylfurfural ═ 0.15:1 (mol: mol). And (3) adopting an automatic temperature controller to program the temperature to 120 ℃, adding 1.0MPa of oxygen, reacting for 12 hours, and keeping the pressure unchanged in the reaction process. The reaction product was acidified and analyzed by HPLC and the reaction results are shown in table one.
Example 11:
adding 1, 10-phenanthroline ligand (the amount ratio of manganese acetate to cobalt acetate to 1, 10-phenanthroline 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 magnesium oxide (0.692g) as a carrier, continuously stirring for 8h at 80 ℃, removing a solvent by rotary evaporation, drying for 12h in an oven at 80 ℃, heating the obtained product at a heating rate of 10 ℃/min in an inert atmosphere Ar, and keeping for 2h at 800 ℃ to obtain a MnCo-Phen @ MgO catalyst (Mn 3.8 wt% of Co 2.3 wt%).
Adding MnCo-Phen @ MgO (Mn 3.8 wt% Co 2.3 wt%) catalyst, 0.5mmol 5-hydroxymethyl furfural and 5 ml deionized water into a stainless steel high-pressure reaction kettle, and attaching a polytetrafluoroethylene lining inside, wherein the metal: 5-hydroxymethylfurfural ═ 0.15:1 (mol: mol). And (3) adopting an automatic temperature controller to program the temperature to 120 ℃, adding 1.0MPa of oxygen, reacting for 12 hours, and keeping the pressure unchanged in the reaction process. The reaction product was acidified and analyzed by HPLC, and the reaction results are shown in Table I.
Example 12:
adding Melamine ligand (the amount ratio of manganese acetate to cobalt acetate to Melamine substance is 0.5:0.5:8) into 50ml of ethanol solution of a mixture of manganese acetate and cobalt acetate, stirring for 1h at 30 ℃, adding supported 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 an inert atmosphere Ar at the heating rate of 5 ℃/min, and keeping the temperature for 3h at 750 ℃ to obtain the MnCo-Melamine @ MgO catalyst (Mn 4.1 wt% Co 2.4 wt%).
Adding MnCo-Melamine @ MgO (Mn 4.1 wt% Co 2.4 wt%) catalyst, 0.5mmol 5-hydroxymethylfurfural and 5 ml deionized water into a stainless steel high-pressure reaction kettle, and attaching a polytetrafluoroethylene lining inside, wherein the metal: 5-hydroxymethylfurfural ═ 0.15:1 (mol: mol). And (3) adopting an automatic temperature controller to program the temperature to 120 ℃, adding 1.0MPa of oxygen, reacting for 12 hours, and keeping the pressure unchanged in the reaction process. The reaction product was acidified and analyzed by HPLC, and the reaction results are shown in Table I.
Example 13:
adding melamine ligand (the amount ratio of cobalt acetate, copper nitrate and melamine substance is 0.5:0.5:8) into 50ml of ethanol solution (0.01M) of a mixture of cobalt acetate and copper nitrate, stirring at 60 ℃ for 1h, adding 0.692g of magnesium hydroxide as a carrier, stirring at 60 ℃ for 8h, removing the solvent by rotary evaporation, drying at 80 ℃ in an oven for 12h, and placing the obtained product in an N-shaped container2Heating at a heating rate of 5 ℃/min, and keeping the temperature at 750 ℃ for 3h to obtain CoCu-Melamine @ Mg (OH)2Catalyst (Co 3.1 wt% Cu 3.4 wt%).
Mixing CoCu-Melamine @ Mg (OH)2(Co 3.1 wt% Cu 3.4 wt%) catalyst, 0.5mmol 5-hydroxymethylfurfural and 5 ml deionized water were added to a stainless steel high pressure reactor, with a polytetrafluoroethylene liner attached, wherein the metal: 5-hydroxymethylfurfural ═ 0.15:1 (mol: mol). Adopting an automatic temperature controller to program the temperature to 120 ℃, adding 1.0MPa oxygen, reacting for 12 hours, and reactingThe pressure is kept constant in the process. The reaction product was acidified and analyzed by HPLC, and the reaction results are shown in Table I.
Example 14
Adding 1, 10-phenanthroline ligand (the amount ratio of manganese acetate to 1, 10-phenanthroline is 1:2) into 50ml of ethanol solution of manganese acetate (the concentration is 0.01M), stirring at 30 ℃ for 1h, adding carrier MgO (0.692g), continuously stirring at 60 ℃ for 6h, removing the solvent by rotary evaporation, drying in an oven at 80 ℃ for 12h, and putting the obtained product in an N-type solvent2In (1), heating was carried out at a heating rate of 10 ℃/min, and the reaction was maintained at 800 ℃ for 2 hours to obtain an Mn-Phen @ MgO catalyst (Mn, 4.2 wt%).
Adding Mn-Phen @ MgO (Mn 4.2 wt%) catalyst, 0.5mmol of 5-hydroxymethylfurfural and 5 ml of deionized water into a stainless steel high-pressure reaction kettle, and attaching a polytetrafluoroethylene lining inside, wherein the weight ratio of metal: 5-hydroxymethylfurfural ═ 0.15:1 (mol: mol). And (3) adopting an automatic temperature controller to program the temperature to 120 ℃, adding 1.0MPa of oxygen, reacting for 12 hours, and keeping the pressure unchanged in the reaction process. The reaction product was acidified and analyzed by HPLC, and the reaction results are shown in Table I.
Example 15
Adding dicyandiamide ligand (the amount ratio of manganese acetate, copper nitrate and dicyandiamide substances is 0.5:0.5:8) into 50ml of ethanol solution of a mixture of manganese acetate and copper nitrate, stirring for 1h at 30 ℃, adding 0.692g of carrier magnesium oxide, 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 an inert atmosphere Ar at the heating rate of 5 ℃/min, and keeping the temperature at 900 ℃ for 2h to obtain the MnCu-DCD @ MgO catalyst (Mn 3.3 wt% Cu 2.7 wt%).
Adding MnCu-DCD @ MgO (Mn 3.3 wt% Cu 2.7 wt%) catalyst, 0.5mmol 5-hydroxymethyl furfural and 5 ml deionized water into a stainless steel high-pressure reaction kettle, and attaching a polytetrafluoroethylene lining inside, wherein the metal: 5-hydroxymethylfurfural ═ 0.15:1 (mol: mol). And (3) adopting an automatic temperature controller to program the temperature to 120 ℃, adding 1.0MPa of oxygen, reacting for 12 hours, and keeping the pressure unchanged in the reaction process. The reaction product was acidified and analyzed by HPLC, and the reaction results are shown in Table I.
Example 16
The Co-Phen @ MgO (Co 3.9 wt%) catalyst was prepared as in example 8.
The Co-Phen @ MgO (Co 3.9 wt%) catalyst, 0.5mmol 5-hydroxymethylfurfural and 5 ml deionized water were added to a round bottom flask and heated in an oil bath with the metals: 5-hydroxymethylfurfural ═ 0.15:1 (mol: mol). The temperature is programmed to 60 ℃ by adopting an automatic temperature controller, and the reaction is carried out for 12 hours by adopting an oxygen bubbling method (the oxygen flow is 20 mL/min). The reaction product was acidified and analyzed by HPLC, and the reaction results are shown in Table I.
TABLE-catalytic Oxidation results of 5-hydroxymethylfurfural on different catalysts
HMF: 5-hydroxymethylfurfural; FFCA: 5-formyl-2-furancarboxylic acid; FDCA: 2, 5-furandicarboxylic acid; phen: 1, 10-phenanthroline; bpy: 2,2' -bipyridine; DCD: dicyanodiamine
Although the present application has been described with reference to a few embodiments, it should be understood that various changes, substitutions and alterations can be made herein without departing from the spirit and scope of the application as defined by the appended claims.
Claims (10)
1. A method for producing 2, 5-furandicarboxylic acid, comprising: 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.
2. The production method according to claim 1, wherein 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 basic carrier is selected from metal oxides, metal hydroxides, anionic layered compounds containing metal;
the supported transition metal catalyst also comprises a nitrogen-containing organic ligand which can be coordinated with the transition metal;
preferably, the nitrogen-containing organic ligand is selected from 1, 10-phenanthroline, 2' -bipyridine, 2' -bipyridine amine, 4' -bipyridine amine, terpyridine, urea, dicyanodiamine, melamine, triethylamine, ethylenediamine, polypyrrole, C3N4At least one of;
preferably, the metal oxide is selected from at least one of lanthanum oxide, zirconium oxide, cerium oxide, calcium oxide and magnesium oxide;
preferably, the metal hydroxide comprises magnesium hydroxide;
preferably, the metal-containing anionic layered compound comprises hydrotalcite.
3. The preparation method according to claim 1, wherein the loading amount of the active component in the supported transition metal catalyst is 2.0 wt% to 25.0 wt%;
preferably, the loading amount of the active component in the supported transition metal catalyst is 2.0 wt% to 10.0 wt%;
wherein the mass of the active component is calculated as the mass of the transition metal element.
4. The method of claim 1, wherein the oxidizing agent is an oxygen-containing atmosphere;
the raw materials also comprise a solvent;
the molar concentration of the 5-hydroxymethylfurfural in the raw material is 0.05-0.2 mol/L;
preferably, the oxidant is oxygen or air;
preferably, the solvent is water.
5. The method according to claim 1, wherein the reaction is followed by acidification;
preferably, the acid is in excess during the acidification.
6. The method of claim 1, wherein the reaction conditions include: the reaction temperature is 30-130 ℃;
preferably, the reaction temperature is 60-120 ℃.
7. The method of claim 1, wherein the reaction conditions include: the reaction time is 0.5-24 h;
preferably, the reaction time is 6-12 h.
8. The method of claim 1, wherein the reaction conditions include: the reaction pressure is normal pressure-2.0 MPa;
preferably, the reaction pressure is 0.5MPa to 2.0 MPa.
9. The method according to claim 1, wherein the oxidizing agent is added in a manner of: introducing an oxidant into the reaction system;
the oxidant is an oxygen-containing atmosphere;
the reaction conditions include: the reaction pressure is normal pressure-2.0 MPa; or
The adding mode of the oxidant is as follows: 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.
10. The preparation method according to claim 1, wherein the molar ratio of the catalyst to the 5-hydroxymethylfurfural is 0.05 to 0.3: 1;
the moles of the catalyst are calculated as the moles of the transition metal in the catalyst.
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WO2015056270A1 (en) * | 2013-10-17 | 2015-04-23 | Natco Pharma Limited | Process for the preparation of 2,5-furandicarboxylic acid |
CN108084123A (en) * | 2016-11-22 | 2018-05-29 | 中国科学院大连化学物理研究所 | A kind of method for preparing 2,5- furandicarboxylic acid dimethyl esters |
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CN104177319A (en) * | 2014-09-05 | 2014-12-03 | 中国科学技术大学 | Method for preparing 2,5-furyldiformate |
CN108084123A (en) * | 2016-11-22 | 2018-05-29 | 中国科学院大连化学物理研究所 | A kind of method for preparing 2,5- furandicarboxylic acid dimethyl esters |
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