CN115569652B - Platinum cobalt niobium heterogeneous catalyst, preparation method and application thereof, and preparation method of 2, 5-furandicarboxylic acid - Google Patents
Platinum cobalt niobium heterogeneous catalyst, preparation method and application thereof, and preparation method of 2, 5-furandicarboxylic acid Download PDFInfo
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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 84
- NSVAVJDRURIOAP-UHFFFAOYSA-N cobalt niobium platinum Chemical compound [Nb][Co][Pt] NSVAVJDRURIOAP-UHFFFAOYSA-N 0.000 title claims abstract description 39
- 239000002638 heterogeneous catalyst Substances 0.000 title claims abstract description 39
- 238000002360 preparation method Methods 0.000 title claims abstract description 35
- 239000003054 catalyst Substances 0.000 claims abstract description 80
- NOEGNKMFWQHSLB-UHFFFAOYSA-N 5-hydroxymethylfurfural Chemical compound OCC1=CC=C(C=O)O1 NOEGNKMFWQHSLB-UHFFFAOYSA-N 0.000 claims abstract description 44
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 39
- RJGBSYZFOCAGQY-UHFFFAOYSA-N hydroxymethylfurfural Natural products COC1=CC=C(C=O)O1 RJGBSYZFOCAGQY-UHFFFAOYSA-N 0.000 claims abstract description 35
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000001301 oxygen Substances 0.000 claims abstract description 21
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 21
- 230000001590 oxidative effect Effects 0.000 claims abstract description 17
- 239000007800 oxidant agent Substances 0.000 claims abstract description 13
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 112
- 239000010955 niobium Substances 0.000 claims description 94
- 239000002243 precursor Substances 0.000 claims description 71
- 239000002131 composite material Substances 0.000 claims description 47
- 229910052758 niobium Inorganic materials 0.000 claims description 39
- 229910052697 platinum Inorganic materials 0.000 claims description 36
- 229910017052 cobalt Inorganic materials 0.000 claims description 33
- 239000010941 cobalt Substances 0.000 claims description 33
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 33
- BDMHSCBWXVUPAH-UHFFFAOYSA-N cobalt niobium Chemical compound [Co].[Nb] BDMHSCBWXVUPAH-UHFFFAOYSA-N 0.000 claims description 30
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 claims description 30
- 239000003513 alkali Substances 0.000 claims description 26
- 238000002156 mixing Methods 0.000 claims description 23
- 238000007254 oxidation reaction Methods 0.000 claims description 20
- 238000001556 precipitation Methods 0.000 claims description 14
- 238000001354 calcination Methods 0.000 claims description 13
- 239000003638 chemical reducing agent Substances 0.000 claims description 13
- 238000000975 co-precipitation Methods 0.000 claims description 13
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 12
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 12
- 150000004687 hexahydrates Chemical class 0.000 claims description 7
- 238000000034 method Methods 0.000 claims description 7
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 7
- XONPDZSGENTBNJ-UHFFFAOYSA-N molecular hydrogen;sodium Chemical group [Na].[H][H] XONPDZSGENTBNJ-UHFFFAOYSA-N 0.000 claims description 6
- 230000009467 reduction Effects 0.000 claims description 6
- 239000012279 sodium borohydride Substances 0.000 claims description 3
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 3
- 230000003197 catalytic effect Effects 0.000 abstract description 27
- 238000006243 chemical reaction Methods 0.000 abstract description 20
- 239000000654 additive Substances 0.000 abstract description 3
- 230000000996 additive effect Effects 0.000 abstract description 3
- 239000002904 solvent Substances 0.000 abstract description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 36
- 239000000243 solution Substances 0.000 description 36
- 239000000047 product Substances 0.000 description 24
- 238000003756 stirring Methods 0.000 description 22
- 239000008367 deionised water Substances 0.000 description 20
- 229910021641 deionized water Inorganic materials 0.000 description 20
- 239000007787 solid Substances 0.000 description 19
- 238000011068 loading method Methods 0.000 description 18
- 229910020599 Co 3 O 4 Inorganic materials 0.000 description 12
- 239000000203 mixture Substances 0.000 description 12
- 238000009826 distribution Methods 0.000 description 10
- 229910000510 noble metal Inorganic materials 0.000 description 10
- 230000003647 oxidation Effects 0.000 description 10
- 239000000126 substance Substances 0.000 description 10
- 229910020707 Co—Pt Inorganic materials 0.000 description 9
- 238000001914 filtration Methods 0.000 description 9
- 238000004519 manufacturing process Methods 0.000 description 8
- 238000011161 development Methods 0.000 description 7
- 230000018109 developmental process Effects 0.000 description 7
- 239000002028 Biomass Substances 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 239000000706 filtrate Substances 0.000 description 6
- -1 polyethylene 2, 5-furandicarboxylate Polymers 0.000 description 6
- 238000005406 washing Methods 0.000 description 6
- 230000002378 acidificating effect Effects 0.000 description 5
- 239000006227 byproduct Substances 0.000 description 5
- 150000002500 ions Chemical class 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- SHNRXUWGUKDPMA-UHFFFAOYSA-N 5-formyl-2-furoic acid Chemical compound OC(=O)C1=CC=C(C=O)O1 SHNRXUWGUKDPMA-UHFFFAOYSA-N 0.000 description 4
- XZLABTOOVBNJCD-UHFFFAOYSA-D O.[Nb+5].[Nb+5].[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O Chemical group O.[Nb+5].[Nb+5].[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O XZLABTOOVBNJCD-UHFFFAOYSA-D 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 4
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical group [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
- 238000001095 inductively coupled plasma mass spectrometry Methods 0.000 description 4
- 239000000725 suspension Substances 0.000 description 4
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 239000002585 base Substances 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000000969 carrier Substances 0.000 description 3
- 239000012295 chemical reaction liquid Substances 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 238000013507 mapping Methods 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 229920003023 plastic Polymers 0.000 description 3
- 239000004033 plastic Substances 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N Furan Chemical compound C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 238000003917 TEM image Methods 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- 229910000428 cobalt oxide Inorganic materials 0.000 description 2
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 229920006351 engineering plastic Polymers 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 239000012847 fine chemical Substances 0.000 description 2
- 238000007210 heterogeneous catalysis Methods 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- 229910000000 metal hydroxide Inorganic materials 0.000 description 2
- 150000004692 metal hydroxides Chemical class 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- 229910000484 niobium oxide Inorganic materials 0.000 description 2
- URLJKFSTXLNXLG-UHFFFAOYSA-N niobium(5+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Nb+5].[Nb+5] URLJKFSTXLNXLG-UHFFFAOYSA-N 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 description 2
- 238000010926 purge Methods 0.000 description 2
- 238000004445 quantitative analysis Methods 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 238000007789 sealing Methods 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- PXJJKVNIMAZHCB-UHFFFAOYSA-N 2,5-diformylfuran Chemical compound O=CC1=CC=C(C=O)O1 PXJJKVNIMAZHCB-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- NIPNSKYNPDTRPC-UHFFFAOYSA-N N-[2-oxo-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 NIPNSKYNPDTRPC-UHFFFAOYSA-N 0.000 description 1
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 description 1
- 229910001429 cobalt ion Inorganic materials 0.000 description 1
- 229940044175 cobalt sulfate Drugs 0.000 description 1
- 229910000361 cobalt sulfate Inorganic materials 0.000 description 1
- XLJKHNWPARRRJB-UHFFFAOYSA-N cobalt(2+) Chemical compound [Co+2] XLJKHNWPARRRJB-UHFFFAOYSA-N 0.000 description 1
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 description 1
- 125000001142 dicarboxylic acid group Chemical group 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 238000007172 homogeneous catalysis Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000002905 metal composite material Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000029553 photosynthesis Effects 0.000 description 1
- 238000010672 photosynthesis Methods 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 239000012286 potassium permanganate Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000035755 proliferation Effects 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000004451 qualitative analysis Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000011946 reduction process Methods 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 238000007142 ring opening reaction Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
Classifications
-
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
- B01J23/8933—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/898—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with vanadium, tantalum, niobium or polonium
-
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
-
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
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Abstract
The invention provides a platinum cobalt niobium heterogeneous catalyst, a preparation method and application thereof, and a preparation method of 2, 5-furandicarboxylic acid, and belongs to the technical field of catalysts. The platinum cobalt niobium heterogeneous catalyst has excellent catalytic activity and extremely high selectivity on 2, 5-furandicarboxylic acid, can be used for preparing 2, 5-furandicarboxylic acid by selectively oxidizing 5-hydroxymethylfurfural, can oxidize 5-hydroxymethylfurfural to generate 2, 52-furandicarboxylic acid in high-efficiency and high-selectivity under the environment-friendly pollution-free condition that water is taken as a solvent and oxygen is taken as an oxidant and no acid-base additive is added, and has the product selectivity of more than 99%, so that the specific and high-efficiency value-added conversion of 5-hydroxymethylfurfural is realized.
Description
Technical Field
The invention relates to the technical field of catalysts, in particular to a platinum cobalt niobium heterogeneous catalyst, a preparation method and application thereof, and a preparation method of 2, 5-furandicarboxylic acid.
Background
In view of the concepts of economic development and sustainable development of green chemistry, how to effectively improve the catalytic efficiency of the catalyst is of great importance for scientific research and industrial production. For the catalyst, various factors such as the composition, morphology, structure and the like of the catalyst have great influence on the catalytic performance of the catalyst. In particular, for supported noble metal catalysts, the elemental composition and elemental distribution of the support can affect the catalytic performance of the catalyst in addition to the particle size, distribution, and morphology of the supported noble metal. Therefore, the research on the optimal preparation method of the catalyst has extremely important significance for catalyst design and application, and the catalytic activity of the catalyst can be effectively modulated by modulating the carrier structure and element distribution of the supported catalyst.
The development of the traditional chemical industry is severely dependent on petrochemical derived chemicals, however with the increasing depletion of non-renewable petrochemical energy sources, the production of petrochemical products is becoming lower and the price is increasing. These factors have greatly limited the development of the chemical industry. In addition, the massive utilization of petrochemical resources causes environmental pollution problems that are becoming serious, and the shortage of energy sources has prompted people to find new sustainable and renewable green chemical energy sources. Biomass is various organisms synthesized by plants through photosynthesis, has the characteristics of low pollution, rapid regeneration, wide sources, rich reserves and the like, and is an ideal potential substitute for petrochemical energy. Biomass energy is the fourth largest energy source next to coal, oil and natural gas, and thus it is extremely important to develop utilization and value-added approaches of biomass resources. Since the 60 s of the last century, there has been great attention paid to efficient development, proliferation and utilization of biomass resources in countries around the world, and researchers have also actively studied and developed biomass application technologies, and excellent results have been achieved at present.
The 5-hydroxymethylfurfural is an important fine chemical raw material obtained from biomass, and can be applied to the production of various liquid fuels, functional polyesters and various fine chemicals. 2, 5-furandicarboxylic acid prepared by the selective oxidation of 5-hydroxymethylfurfural is a widely used furan chemical with symmetrical dicarboxylic acid structure that can be used to produce bio-based polyesters such as PEF plastics and the like. The bio-based engineering plastic PEF (polyethylene 2, 5-furandicarboxylate, named polyethylene furanoate) is degradable, recyclable and has excellent performance compared with petrochemical-derived PET plastic, and has been applied to various aspects of chemical industry and production and life at present. However, the production process of 2, 5-furandicarboxylic acid is complex, the production technology is not mature enough, the development of PEF plastic is greatly limited by the problems, and the application of the green and environment-friendly renewable bio-based engineering plastic is greatly limited.
Therefore, how to develop a more efficient production strategy of 2, 5-furandicarboxylic acid is of great importance for the application and development of bio-based chemicals. Earlier than the 19 th century, researchers have begun to use 5-hydroxymethylfurfural to produce 2, 5-furandicarboxylic acid. So far, the research on the preparation of 2, 5-furandicarboxylic acid by selective oxidation of 5-hydroxymethylfurfural has been greatly developed. The catalytic systems developed so far are largely divided into homogeneous catalytic and heterogeneous catalytic systems. Compared with homogeneous catalysis, the heterogeneous catalysis system has the advantages that the catalyst and the product are easier to separate, and the heterogeneous catalysis system has better application prospect. However, in most heterogeneous catalytic systems, soluble alkali acids such as sodium hydroxide, potassium hydroxide, sodium carbonate or sulfuric acid, hydrochloric acid and the like are required to be added; or using some organic solvents; or using some oxidizing agent such as hydrogen peroxide, potassium permanganate, t-butyl peroxide, etc. The use of these soluble bases, organic solvents, and oxidizing agents easily causes problems such as corrosion damage to reaction equipment, environmental pollution, and increased production cost.
Disclosure of Invention
The invention aims to provide a platinum cobalt niobium heterogeneous catalyst, a preparation method and application thereof, and a preparation method of 2, 5-furandicarboxylic acid, wherein the platinum cobalt niobium heterogeneous catalyst can be used for efficiently and exclusively oxidizing 5-hydroxymethylfurfural to generate 2, 5-furandicarboxylic acid in a mild temperature and in a short time under the condition of using a green oxidant (air or oxygen) in a green solvent (water) and no acid-base additive.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a platinum cobalt niobium heterogeneous catalyst, which comprises a cobalt niobium composite oxide carrier and platinum loaded on the surface of the cobalt niobium composite oxide carrier.
Preferably, the platinum is supported on the cobalt-niobium composite oxide carrier in an amount of 0.5 to 3wt%.
The invention provides a preparation method of the platinum cobalt niobium heterogeneous catalyst, which comprises the following steps:
mixing a niobium precursor, a cobalt precursor and alkali liquor, and performing coprecipitation to obtain a precipitation product;
calcining the precipitation product to obtain a cobalt-niobium composite oxide carrier;
and mixing the cobalt-niobium composite oxide carrier, a platinum source, polyvinylpyrrolidone, water and a reducing agent, and reducing to obtain the platinum-cobalt-niobium heterogeneous catalyst.
Preferably, the mixing of the niobium precursor, the cobalt precursor and the alkali solution comprises: adjusting the pH value of the niobium precursor to 6-8 by adopting alkali liquor, adding the cobalt precursor, and adjusting the pH value to 9-10; or mixing the niobium precursor and the cobalt precursor, and adjusting the pH value to 9-10 by adopting alkali liquor; or, alkali liquor is adopted to adjust the pH value of the cobalt precursor to 6-8, and niobium precursor is added to adjust the pH value to 9-10.
Preferably, the molar ratio of the niobium precursor to the cobalt precursor is (0.01-0.3): 1; the coprecipitation time is 1-4 hours; the calcination temperature is 300-500 ℃ and the calcination time is 2-6 h.
Preferably, the platinum source is sodium dihydrogen hexachloroplatinate hexahydrate; the reducing agent is sodium borohydride; the reduction time is 1-4 h.
The invention provides an application of the platinum cobalt niobium heterogeneous catalyst prepared by the technical scheme or the preparation method of the technical scheme in preparing 2, 5-furandicarboxylic acid by oxidizing 5-hydroxymethylfurfural.
The invention provides a preparation method of 2, 5-furandicarboxylic acid, which comprises the following steps:
mixing 5-hydroxymethylfurfural, an oxidant, a catalyst and water, and performing an oxidation reaction to obtain 2, 5-furandicarboxylic acid; the catalyst is the platinum cobalt niobium heterogeneous catalyst prepared by the technical scheme or the preparation method.
Preferably, the molar ratio of the 5-hydroxymethylfurfural to the platinum element in the catalyst is (100-400): 1; the oxidant is oxygen, and the pressure of the oxygen is 1-10 bar.
Preferably, the temperature of the oxidation reaction is 90-120 ℃ and the time is 1-6 h.
The invention provides a platinum cobalt niobium heterogeneous catalyst, which comprises a cobalt niobium composite oxide carrier and platinum loaded on the surface of the cobalt niobium composite oxide carrier. In the platinum cobalt niobium heterogeneous catalyst, the carrier of the catalyst is Co-Nb composite oxide, co and Nb are transition metals, and the oxide is insoluble in water and organic acid, so that the catalyst has excellent thermal stability; the noble metal Pt and the Co-Nb composite oxide have strong interaction, so that the noble metal Pt and the Co-Nb composite oxide can be stably loaded on a Co-Nb composite oxide carrier, thereby improving the stability of the heterogeneous catalyst. In addition, platinum is used as a catalytic active component, and has excellent selective oxidation performance on hydroxyl and carbonyl in the 5-hydroxymethylfurfural; the rich acidic sites in the Co-Nb composite oxide carrier have good promotion effects on the oxidation of 5-hydroxymethylfurfural and the formation of target 2, 5-furandicarboxylic acid, so that the heterogeneous catalyst has excellent catalytic activity and extremely high selectivity on 2, 5-furandicarboxylic acid, and can be used for preparing 2, 5-furandicarboxylic acid by selectively oxidizing 5-hydroxymethylfurfural.
The platinum cobalt niobium heterogeneous catalyst provided by the invention can oxidize 5-hydroxymethylfurfural to generate 2, 5-furandicarboxylic acid with high-efficiency selectivity under the environment-friendly pollution-free condition that water is taken as a solvent and oxygen is taken as an oxidant and no acid-base additive is added, the product selectivity is more than 99%, the specific and high-efficiency value-added conversion of the 5-hydroxymethylfurfural is realized, and the problems of high production cost and a large number of byproducts caused by an organic solvent and a high-cost oxidant used in the existing catalytic system are avoided. The platinum cobalt niobium heterogeneous catalyst has excellent stability and recycling property, and the catalytic activity of the catalyst is kept unchanged in 5 times of recycling, and is easy to separate and recycle from a product.
Furthermore, the platinum cobalt niobium heterogeneous catalyst provided by the invention can be used for converting 5-hydroxymethylfurfural into a target product 2, 5-furandicarboxylic acid under the condition of no addition of any soluble alkali, so that the problems of equipment corrosion and product separation and purification caused by the soluble alkali used in the existing catalytic system are avoided.
Furthermore, in the platinum-cobalt-niobium heterogeneous catalyst provided by the invention, the loading amount of noble metal platinum is as low as 0.5wt.%, the catalyst dosage used in the catalytic process is very small (the molar ratio of HMF/Pt is 100:1), and the catalyst cost is low.
Furthermore, the platinum cobalt niobium heterogeneous catalyst provided by the invention can be used for efficiently converting 5-hydroxymethylfurfural into 2, 5-furandicarboxylic acid in 6h under the conditions of low reaction temperature (100 ℃) and low oxygen pressure (10 bar), no other byproducts are generated, and under the mild conditions, the platinum cobalt niobium heterogeneous catalyst can be used for rapidly oxidizing 5-hydroxymethylfurfural into 2, 5-furandicarboxylic acid, the product selectivity is 100%, the problems of extremely severe reaction conditions of the existing high-loading noble metal catalyst, larger catalyst dosage and non-noble metal catalyst are solved, the problems of high reaction temperature (140-160 ℃) and high oxygen pressure (20-40 bar) and long reaction time (12-36 h) required by the existing catalytic system are avoided, and meanwhile, the problems of transitional oxidation byproducts or ring-opening products generated by the existing catalyst are avoided.
Furthermore, the platinum cobalt niobium catalyst with the same components but different catalyst structures and element distribution of the catalyst carrier can be prepared by modulating the precipitation sequence of cobalt ions and niobium ions in the preparation process; the acidity of the carrier and the property of the supported noble metal cobalt are modulated by changing the element distribution in the carrier, so that the excellent catalytic performance of the catalyst is ensured.
Drawings
FIG. 1 is a flow chart of preparing 2, 5-furandicarboxylic acid by using the platinum cobalt niobium heterogeneous catalyst provided by the invention to catalyze the selective oxidation of 5-hydroxymethylfurfural;
FIG. 2 shows Nb@Co-Pt and Co prepared in examples 1 to 3&Nb-Pt and Co@Nb-Pt catalyst and Nb 2 O 5 -Pt and Co 3 O 4 -XRD pattern of Pt;
FIG. 3 is a bright field TEM image and corresponding elemental mapping image of Nb@Co-Pt, co & Nb-Pt and Co@Nb-Pt catalysts prepared in examples 1-3;
FIG. 4 shows Nb@Co, co prepared in examples 1 to 3 and comparative examples 1 to 2&Nb and Co@Nb carriers and Nb 2 O 5 And Co 3 O 4 NH of support 3 -a TPD map;
FIG. 5 shows Nb@Co-Pt and Co prepared in examples 1 to 3&XPS patterns of Nb-Pt and Co@Nb-Pt catalysts (including Pt4f orbitals (a), co2p 3/2 Tracks (b) and Nb3d tracks (c)).
Detailed Description
The invention provides a platinum cobalt niobium heterogeneous catalyst, which comprises a cobalt niobium composite oxide carrier and platinum loaded on the surface of the cobalt niobium composite oxide carrier.
In the present invention, the cobalt-niobium composite oxide support is a composite of cobalt oxide and niobium oxide, and the molar ratio of the cobalt oxide to the niobium oxide is preferably (0.01 to 0.3): 1, more preferably 0.1:1.
In the present invention, the platinum is preferably supported on the cobalt-niobium composite oxide support in an amount of 0.5 to 3wt%, more preferably 0.5wt%.
The invention provides a preparation method of the platinum cobalt niobium heterogeneous catalyst, which comprises the following steps:
mixing a niobium precursor, a cobalt precursor and alkali liquor, and performing coprecipitation to obtain a precipitation product;
calcining the precipitation product to obtain a cobalt-niobium composite oxide carrier;
and mixing the cobalt-niobium composite oxide carrier, a platinum source, polyvinylpyrrolidone, water and a reducing agent, and reducing to obtain the platinum-cobalt-niobium heterogeneous catalyst.
In the present invention, the preparation materials are commercially available as known to those skilled in the art unless otherwise specified.
The invention mixes the niobium precursor, the cobalt precursor and the alkali liquor for coprecipitation to obtain a precipitated product.
In the present invention, the niobium precursor is preferably niobium oxalate hydrate, the niobium precursor is preferably used in the form of an aqueous niobium precursor solution, and the concentration of the aqueous niobium precursor solution is preferably 0.01mmol/mL; the cobalt precursor is preferably cobalt nitrate, cobalt chloride or cobalt sulfate; the cobalt precursor is preferably used in the form of an aqueous cobalt precursor solution, preferably at a concentration of 0.1mmol/mL.
In the present invention, the molar ratio of the niobium precursor to the cobalt precursor is preferably (0.01 to 0.3): 1, more preferably 0.1:1.
In the present invention, the alkali solution is preferably an aqueous sodium hydroxide solution, and the concentration of the aqueous sodium hydroxide solution is preferably 0.1 to 1mol L -1 . The amount of lye according to the invention is preferably determined according to the desired pH.
In the present invention, the mixing of the niobium precursor, the cobalt precursor and the alkali solution preferably comprises: alkali liquor is adopted to adjust the pH value of the niobium precursor to 6-8 (more preferably 7), and cobalt precursor is added to adjust the pH value to 9-10; the invention preferably adds cobalt precursor under the stirring condition of 600rpm, and uses alkali liquor to further regulate pH value to 9-10 after 10-20 min.
As another aspect of the present invention, the mixing of the niobium precursor, the cobalt precursor and the alkali solution preferably includes: mixing the niobium precursor and the cobalt precursor, and adjusting the pH value to 9-10 by adopting alkali liquor.
As another aspect of the present invention, the mixing of the niobium precursor, the cobalt precursor and the alkali solution preferably includes: adjusting the pH value of the cobalt precursor to 6-8 by adopting alkali liquor, adding the niobium precursor, and adjusting the pH value to 9-10; the invention preferably adds the niobium precursor under the stirring condition of 600rpm, and uses alkali liquor to further adjust the pH value to 9-10 after 10-20 min.
After the niobium precursor, the cobalt precursor and the alkali liquor are mixed, the obtained mixture is subjected to coprecipitation; the co-precipitation is preferably carried out under stirring conditions, the stirring speed being preferably 600rpm; the time of the coprecipitation is preferably 1 to 4 hours, more preferably 2 hours; the coprecipitation is preferably carried out at room temperature. During the co-precipitation process, the niobium precursor and the cobalt precursor precipitate under alkaline conditions to form a metal hydroxide.
After completion of the co-precipitation, the present invention preferably filters the resulting product and the resulting solid is washed with excess deionized water until the pH of the filtrate is neutral to provide a precipitated product. The specific process of the filtration and washing is not particularly limited in the present invention, and may be carried out according to a process well known in the art.
After the precipitation product is obtained, the precipitation product is calcined to obtain the cobalt-niobium composite oxide carrier.
In the present invention, the temperature of the calcination is preferably 300 to 500 ℃, more preferably 400 ℃; the time is preferably 2 to 6 hours, more preferably 4 hours. The present invention calcines the metal hydroxide in the precipitated product to a metal oxide by calcination.
The invention controls the distribution of Co and Nb elements in the Co-Nb composite metal oxide by modulating the precipitation sequence of Co salt and Nb salt, taking Nb@Co composite oxide carrier as an example: nb dispersed in aqueous solution 5+ The ions and added NaOH are crystallized to generate Nb (OH) 5 Precipitation, subsequent addition of Co 2+ And (3) ions, and finally adding NaOH to adjust the pH. In this process, co 2+ Ions will preferentially nucleate unevenly in Nb (OH) 5 Surface crystal growth eventually results in the formation of Co-Nb composite oxides in which cobalt is primarily distributed in the outer surface layer of the composite and niobium is primarily concentrated in the core phase of the composite, i.e., the Co and Nb distribution in the Co-Nb composite oxide is successfully modulated.
After the cobalt-niobium composite oxide carrier is obtained, the cobalt-niobium composite oxide carrier, a platinum source, polyvinylpyrrolidone, water and a reducing agent are mixed for reduction, and the platinum-cobalt-niobium heterogeneous catalyst is obtained.
In the present invention, the platinum source is preferably sodium dihydrogen hexachloroplatinate hexahydrate or potassium dihydrogen hexachloroplatinate hexahydrate; the reducing agent is preferably sodium borohydride; the reducing agent is preferably used in the form of an aqueous reducing agent solution, preferably at a concentration of 4mg/mL.
In the invention, the dosage ratio of the platinum source, polyvinylpyrrolidone and the aqueous solution of the reducing agent is preferably 0.01mmol (5-15) mg (1-5) mL; more preferably 0.01mmol:10mg:2.5mL.
In the present invention, the cobalt-niobium composite oxide carrier, platinum source, polyvinylpyrrolidone, water and reducing agent are preferably mixed as follows: mixing platinic acid and PVP in water, stirring for 1-2 h, adding cobalt-niobium composite oxide carrier, continuously stirring for 1-4 h (preferably 2 h), and dripping aqueous solution of reducing agent; the stirring rate is preferably 600rpm.
In the present invention, the time of the reduction is preferably 1 to 4 hours, more preferably 2 hours; the reduction is preferably carried out under stirring; the stirring rate is preferably 600rpm. Pt ions are adsorbed on the surface of the cobalt-niobium composite oxide carrier in a chemical adsorption mode, and form adsorption chemical bonds through mutual electron transfer, exchange or mutual electron sharing, so that the Pt ions are stably loaded on the surface of the cobalt-niobium composite oxide carrier, and then a platinum source is reduced in the reduction process to form metal simple substance Pt.
After completion of the reduction, the present invention preferably filters the resulting product and repeatedly washes the resulting solid with excess cold/hot deionized water (removal of PVP, na) + And Cl-), and drying the obtained solid at 110-130 ℃ for 12h to obtain the platinum cobalt niobium heterogeneous catalyst.
The invention provides an application of the platinum cobalt niobium heterogeneous catalyst prepared by the technical scheme or the preparation method of the technical scheme in preparing 2, 5-furandicarboxylic acid by oxidizing 5-hydroxymethylfurfural.
The invention provides a preparation method of 2, 5-furandicarboxylic acid, which comprises the following steps:
mixing 5-hydroxymethylfurfural, an oxidant, a catalyst and water, and performing an oxidation reaction to obtain 2, 5-furandicarboxylic acid; the catalyst is the platinum cobalt niobium heterogeneous catalyst prepared by the technical scheme or the preparation method.
In the present invention, the molar ratio of the 5-hydroxymethylfurfural to the platinum element in the catalyst is preferably (100 to 400): 1, more preferably (200 to 300): 1. The water consumption is not particularly limited, and the water consumption can be adjusted according to actual requirements.
In the present invention, the oxidizing agent is preferably oxygen, and the pressure of the oxygen is preferably 1 to 10bar, more preferably 5bar.
In the present invention, the 5-hydroxymethylfurfural, the oxidizing agent, the catalyst and the water are preferably mixed as follows: adding 5-hydroxymethylfurfural, water, a catalyst and a magnetic stirrer into a polytetrafluoroethylene lining of a high-pressure reaction kettle at the same time, sealing the reaction kettle, purging for three times by 5bar of oxygen, filling oxygen to reach the required pressure, and performing leak detection test on the reaction kettle to ensure perfect air tightness.
In the present invention, the temperature of the oxidation reaction is preferably 90 to 120 ℃, more preferably 100 ℃; the time is preferably 1 to 6 hours; the oxidation reaction is preferably carried out under stirring, preferably at a rate of 2000rpm.
FIG. 1 is a flow chart of preparing 2, 5-furandicarboxylic acid by using the platinum cobalt niobium heterogeneous catalyst provided by the invention to catalyze 5-hydroxymethylfurfural to selectively oxidize, mixing 5-hydroxymethylfurfural, the catalyst and water, and carrying out an oxidation reaction (100 ℃ and 10 bar) under an oxygen condition to obtain the product 2, 5-furandicarboxylic acid.
The technical solutions of the present invention will be clearly and completely described in the following in connection with the embodiments of the present invention. It will be apparent that the described embodiments are only some, but not all, embodiments of the invention. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Example 1
Dissolving 0.001mol of niobium oxalate hydrate in 100mL of deionized water to obtain Nb precursor solution, and dissolving 0.01mol of cobalt nitrate in 100mL of deionized water to obtain Co precursor solution;
preparation of Nb@Co carrier: naOH solution (1 mol L) -1 ) Adjusting the pH value of the Nb precursor solution to 7, adding the Co precursor solution under stirring at 600rpm to meet the Nb/Co molar ratio of 0.1, stirring for 10min, further adjusting the pH value of the mixture to 9 by using NaOH solution, stirring the obtained suspension at 600rpm for 2h at ambient temperature, filtering, washing the obtained solid with excessive deionized water until the pH value of the filtrate is neutral, and calcining the obtained solid at 400 ℃ for 4h to obtain the Nb@Co composite oxide carrier;
0.01mmol of sodium dihydrogen hexachloroplatinate hexahydrate and 10mg of PVP were mixed in 200mL of deionized water and stirred at 600rpm for 1h, 390mg of Nb@Co carrier was added and stirred againMix for 1h, add dropwise 2.5mL NaBH with concentration of 4mg/mL 4 And (3) continuously stirring the obtained suspension for 2 hours, filtering to recover solid, repeatedly washing with excessive deionized water, and drying the obtained solid at 110 ℃ overnight to obtain the Nb@Co-Pt catalyst with the load of 0.5wt%.
Example 2
Dissolving 0.001mol of niobium oxalate hydrate in 100mL of deionized water to obtain Nb precursor solution, and dissolving 0.01mol of cobalt nitrate in 100mL of deionized water to obtain Co precursor solution;
preparation of Co & Nb carrier: mixing a Nb precursor solution and a Co precursor solution to meet the requirement of Nb/Co molar ratio of 0.1, regulating the pH of the mixture to 9 by using a NaOH solution, stirring the obtained mixture at 600rpm for 2 hours, collecting solids by filtration, washing by using excessive deionized water until the pH value of the filtrate is 7, and calcining the obtained solids at 400 ℃ for 4 hours to obtain a Co & Nb composite oxide carrier;
0.01mmol sodium dihydrogen hexachloroplatinate hexahydrate and 10mg PVP were mixed in 200mL deionized water and stirred at 600rpm for 1h, 390mg Co was added&Nb carrier is stirred for 1h, and 2.5mL of NaBH with concentration of 4mg/mL is added dropwise 4 The solution was stirred continuously for another 2 hours, the solid was recovered by filtration, repeatedly washed with excess deionized water, and the resulting solid was dried overnight at 110 ℃ to give Co&Nb-Pt catalyst, the loading is 0.5 weight percent.
Example 3
Dissolving 0.001mol of niobium oxalate hydrate in 100mL of deionized water to obtain Nb precursor solution, and dissolving 0.01mol of cobalt nitrate in 100mL of deionized water to obtain Co precursor solution;
preparation of Co@Nb carrier: adjusting the pH value of the Co precursor solution to about 7 by using NaOH solution, adding the Nb precursor solution into the obtained suspension under the stirring condition of 600rpm to meet the Nb/Co molar ratio of 0.1, stirring for 10min, further adjusting the pH value of the mixture to 9 by using NaOH solution, stirring the obtained mixture at 600rpm for 2h, separating the obtained solid by filtration, washing with excessive deionized water until the pH value of the filtrate becomes 7, and calcining the obtained solid at 400 ℃ for 4h to obtain the Co@Nb composite oxide carrier;
mixing 0.01mmol sodium dihydrogen hexachloroplatinate hexahydrate and 10mg PVP in 200mL deionized water, stirring at 600rpm for 1h, adding 390mg Co@Nb carrier, stirring for 1h, and dropwise adding 2.5mL NaBH with concentration of 4mg/mL 4 And (3) continuously stirring the obtained suspension for 2 hours, filtering to recover solid, repeatedly washing with excessive deionized water, and drying the obtained solid at 110 ℃ overnight to obtain the Co@Nb-Pt catalyst with the load of 0.5wt%.
Example 4
The only difference from example 1 is that: the Pt loading was 1wt.%, and the amount of carrier added was: 195mg.
Example 5
The only difference from example 1 is that: the Pt loading was 2wt.%, and the amount of carrier added was 97.5mg.
Example 6
The only difference from example 1 is that: the Pt loading was 3wt.%, and the amount of carrier added was 65mg.
Example 7
The only difference from example 2 is that: the Pt loading was 1wt.%, and the amount of carrier added was: 195mg.
Example 8
The only difference from example 2 is that: the Pt loading was 2wt.%, and the amount of carrier added was 97.5mg.
Example 9
The only difference from example 2 is that: the loading of Pt was 3wt% and the amount of carrier added was 65mg.
Example 10
The only difference from example 3 is that: the loading of Pt is 1wt%, and the adding amount of the carrier is as follows: 195mg, recorded as 1wt% Co@Nb-Pt.
Example 11
The only difference from example 3 is that: the Pt loading was 2wt%, and the loading of the support was 97.5mg, noted as 2wt% Co@Nb-Pt.
Example 12
The only difference from example 3 is that: the Pt loading was 3wt%, and the loading of the support was 65mg, recorded as 3wt% Co@Nb-Pt.
Comparative example 1
Co 3 O 4 Preparation of the oxide support: the Co precursor solution was pH-adjusted to 9 using NaOH solution, stirred at 600rpm for 2 hours, the solid was collected by filtration and washed with excess deionized water until the pH of the filtrate was 7, and the resulting solid was calcined at 400℃for 4 hours to give Co 3 O 4 An oxide support;
Co 3 O 4 preparation of Pt catalyst: the difference is only that the nb@co support is replaced with Co as in example 1 3 O 4 An oxide support.
Comparative example 2
Nb 2 O 5 Preparation of the oxide support: the Nb precursor solution was adjusted to pH 9 with NaOH solution, stirred at 600rpm for 2 hours, the solid was collected by filtration and washed with excess deionized water until the pH of the filtrate was 7, and the resulting solid was calcined at 400℃for 4 hours to give Nb 2 O 5 An oxide support;
Nb 2 O 5 preparation of Pt catalyst: the difference is only that the nb@co support is replaced with Nb as in example 1 2 O 5 An oxide support.
Characterization of
1) The composition of the catalyst was characterized by ICP-MS and the results are shown in Table 1.
Table 1 results of ICP-MS testing of the different catalysts prepared in examples 1-3
ICP-MS in Table 1 shows that the three catalysts have almost the same composition.
2) XRD characterization was performed on the catalysts prepared in examples 1 to 3 and comparative examples 1 to 2, and the results are shown in FIG. 2; FIG. 2 shows Nb@Co-Pt and Co prepared in examples 1 to 3&Nb-Pt and Co@Nb-Pt catalyst and Nb 2 O 5 -Pt and Co 3 O 4 -XRD pattern of Pt; as shown in FIG. 2, XRD patterns of the three catalysts prepared in examples 1 to 3 each showed typical Co 3 O 4 The reason why no Nb-related diffraction peak was observed is that the content of Nb was low (Nb/Co molar ratio of 0.1:1), and Nb 2 O 5 Is in amorphous form. The reason why no Pt-related diffraction peak was observed was that the loading of Pt was extremely low (only 0.5 wt.%) and the high dispersity of the loaded Pt. Nb prepared in comparative examples 1 to 2 2 O 5 And Co 3 O 4 The XRD patterns of the support are respectively amorphous Nb 2 O 5 And cubic Co 3 O 4 Is a crystalline phase of (a). ICP-MS and XRD results confirm that the three Co-Nb composite oxide supported Pt catalysts have the same composition.
3) The morphology and structure of the catalysts prepared in examples 1 to 3 were characterized by TEM, and the results are shown in fig. 3. FIG. 3 is a bright field TEM image and corresponding elemental mapping image of Nb@Co-Pt, co & Nb-Pt and Co@Nb-Pt catalysts prepared in examples 1-3; as shown in fig. 3, the three catalysts showed similar morphology, however, the element mapping results found that the Co-Nb composite oxides with the same composition obtained by different preparation methods were quite different in bulk and surface element distribution. In the Nb@Co-Pt catalyst, the surface has rich cobalt elements and only very little Nb elements are distributed, namely, the bulk phase is rich in Nb, and the surface is rich in Co. Co & Nb-Pt catalysts exhibit uniform Co and Nb element distribution in both bulk and surface. The Co@Nb-Pt catalyst surface shows rich Nb elements, and a Nb-rich surface, namely a bulk cobalt-rich surface, is constructed, which shows that the platinum cobalt niobium catalyst containing the same components but with distinct element distribution can be prepared by modulating the precipitation sequence of cobalt and niobium ions in the preparation process of the niobium cobalt metal composite oxide.
4) FIG. 4 shows Nb@Co, co prepared in examples 1 to 3 and comparative examples 1 to 2&Nb and Co@Nb carriers and Nb 2 O 5 And Co 3 O 4 NH of support 3 -a TPD map; ammonia gas-temperature programmed desorption (NH) 3 TPD) technique is used to analyze the acidity of the oxide surface, which is weak acidic at below 250 ℃ and can be attributed to strong acidic at above 350 ℃, and the specific data are shown in Table 2. As can be seen from FIG. 4 and Table 2, the Co-Nb composite oxide exhibits a specific Nb ratio 2 O 5 And Co 3 O 4 The stronger weak and strong acidity of the carrier suggests that more acidic sites exist on its surface. Whereas the acidic site may promote oxidation of HMF and the formation of FDCA (2, 5-furandicarboxylic acid). In addition, NH 3 Quantitative analysis of TPD shows that the co@nb carrier shows the strongest acidity and thus the best catalytic performance after loading with noble metal Pt.
TABLE 2Nb@Co, co&Nb and Co@Nb carriers and Nb 2 O 5 And Co 3 O 4 Acidity of the support
5) FIG. 5 shows Nb@Co-Pt and Co prepared in examples 1 to 3&XPS patterns of Nb-Pt and Co@Nb-Pt catalysts comprising Pt4f orbitals (a) and Co2p 3/2 Tracks (b) and Nb3d tracks (c). As shown in FIG. 5, co is compared with Nb@Co-Pt catalyst&Nb-Pt catalyst and Pt0 and Co of Co@Nb-Pt catalyst 2+ 、Co 3+ Binding energy of species shifts to low values, while Nb 5+ The binding energy of the species moves towards high values, indicating that electrons are transferred from Nb species to Pt and Co species. Also disclosed is the strong interactions that exist between Pt and Co-Nb binary oxide, and the catalyst indicates the presence of electron rich Pt0 species. This is why the catalyst has excellent catalytic activity and stability.
Application example
1mmol of 5-hydroxymethylfurfural, 20mL of deionized water, catalysts prepared in different cases (the molar ratio of HMF to Pt in the catalysts is 100:1) and a magnetic stirrer are added into a polytetrafluoroethylene lining (50 mL) of a high-pressure reaction kettle at the same time, the reaction kettle is subjected to sealing treatment, 10bar of oxygen is filled into the kettle through 5bar of oxygen purging for three times, and at the moment, the reaction kettle is subjected to leak detection test to ensure that the air tightness of the reaction kettle is intact; the reaction kettle is put into a constant temperature oil bath pot with the temperature of 100 ℃, the stirring speed is 2000rpm, and the oxidation reaction is carried out for 6 hours, thus obtaining reaction product liquid.
Results
After the oxidation reaction of the application example is finished, the reaction liquid in the lining is sucked by a disposable medical injector, the catalyst existing in the solution is filtered by a filter head, so that clear reaction liquid is obtained, the reaction liquid is subjected to qualitative and quantitative analysis by using an Agilent liquid chromatograph, and the calculated results are shown in tables 3-6.
TABLE 3 Properties of the catalysts prepared in different examples for catalytic oxidation of 5-hydroxymethylfurfural
As shown in Table 3, the single or double oxide support was almost inactive for oxidation of 5-hydroxymethylfurfural. While these oxide supports show excellent catalytic activity after supporting noble metal platinum, the Co@Nb-Pt catalyst shows optimal catalytic activity, the HMF conversion rate is 100%, and the selectivity of 2, 5-furandicarboxylic acid is >99%.
TABLE 4 catalytic Performance of Co@Nb-Pt catalysts with different Pt loadings
As shown in Table 4, with increasing platinum loading in the Co@Nb-Pt catalyst, the catalytic performance of the catalyst gradually decreased, 0.5wt% Co@Nb-Pt catalyst showed the optimal catalytic performance, while the conversion of HMF of the 3wt% Co@Nb-Pt catalyst also reached 100%, the product selectivity of FDCA was only 73%, and the residual intermediate by-product in the catalytic system was 5-formyl-2-furancarboxylic acid.
TABLE 5 influence of oxygen pressure on catalytic reaction on 0.5wt.% Co@Nb-Pt catalyst
As shown in Table 5, the oxygen pressure has a great influence on the reaction results of the selective oxidation of 5-hydroxymethylfurfural over Co@Nb-Pt catalyst. When the oxygen pressure is 10bar, the conversion rate of HMF and the selectivity of the target product FDCA can reach >99%. When the oxygen pressure was reduced to 5bar, the selectivity of FDCA was reduced to 83% despite the conversion of HMF still being 100%, and the remaining by-product was the intermediate 5-formyl-2-furancarboxylic acid (15%). When the pressure was further reduced to 2bar, the selectivity for HMF remained at 100%, the selectivity for intermediate 5-formyl-2-furancarboxylic acid increased, and the selectivity for FDCA, the target product, continued to decrease. When the oxygen pressure was only 1bar, the conversion of HMF was reduced by only 86%, and there was an intermediate 2, 5-diformylfuran (15%) in addition to the intermediate 5-formyl-2-furancarboxylic acid and the target product FDCA. And FDCA selectivity was only 43%.
TABLE 60.5wt.% Co@Nb-Pt catalyst stability and reusability
As shown in Table 6, the Co@Nb-Pt catalyst has excellent stability and reusability, and can be used for preparing 2, 5-furandicarboxylic acid by efficiently and exclusively oxidizing 5-hydroxymethylfurfural after 5 catalytic cycles.
The foregoing is merely a preferred embodiment of the present invention and it should be noted that modifications and adaptations to those skilled in the art may be made without departing from the principles of the present invention, which are intended to be comprehended within the scope of the present invention.
Claims (8)
1. Application of platinum cobalt niobium heterogeneous catalyst in preparing 2, 5-furandicarboxylic acid by oxidizing 5-hydroxymethylfurfural;
the platinum cobalt niobium heterogeneous catalyst comprises a cobalt niobium composite oxide carrier and platinum loaded on the surface of the cobalt niobium composite oxide carrier;
the preparation method of the platinum cobalt niobium heterogeneous catalyst comprises the following steps:
mixing a niobium precursor, a cobalt precursor and alkali liquor, and performing coprecipitation to obtain a precipitation product;
calcining the precipitation product to obtain a cobalt-niobium composite oxide carrier;
and mixing the cobalt-niobium composite oxide carrier, a platinum source, polyvinylpyrrolidone, water and a reducing agent, and reducing to obtain the platinum-cobalt-niobium heterogeneous catalyst.
2. The use according to claim 1, wherein the platinum is supported on the cobalt-niobium composite oxide support in an amount of 0.5 to 3wt%.
3. The use according to claim 1, wherein mixing the niobium precursor, the cobalt precursor and the alkali solution comprises: adjusting the pH value of the niobium precursor to 6-8 by adopting alkali liquor, adding the cobalt precursor, and adjusting the pH value to 9-10; or mixing the niobium precursor and the cobalt precursor, and adjusting the pH value to 9-10 by adopting alkali liquor; or, alkali liquor is adopted to adjust the pH value of the cobalt precursor to 6-8, and niobium precursor is added to adjust the pH value to 9-10.
4. The use according to claim 1, wherein the molar ratio of niobium precursor to cobalt precursor is (0.01-0.3): 1; the coprecipitation time is 1-4 hours; the calcination temperature is 300-500 ℃ and the calcination time is 2-6 h.
5. The use according to claim 1, wherein the platinum source is sodium dihydrogen hexachloroplatinate hexahydrate; the reducing agent is sodium borohydride; the reduction time is 1-4 h.
6. The preparation method of the 2, 5-furandicarboxylic acid is characterized by comprising the following steps of:
mixing 5-hydroxymethylfurfural, an oxidant, a catalyst and water, and performing an oxidation reaction to obtain 2, 5-furandicarboxylic acid; the catalyst is a platinum cobalt niobium heterogeneous catalyst;
the platinum cobalt niobium heterogeneous catalyst comprises a cobalt niobium composite oxide carrier and platinum loaded on the surface of the cobalt niobium composite oxide carrier;
the preparation method of the platinum cobalt niobium heterogeneous catalyst comprises the following steps:
mixing a niobium precursor, a cobalt precursor and alkali liquor, and performing coprecipitation to obtain a precipitation product;
calcining the precipitation product to obtain a cobalt-niobium composite oxide carrier;
and mixing the cobalt-niobium composite oxide carrier, a platinum source, polyvinylpyrrolidone, water and a reducing agent, and reducing to obtain the platinum-cobalt-niobium heterogeneous catalyst.
7. The preparation method according to claim 6, wherein the molar ratio of the 5-hydroxymethylfurfural to the platinum element in the catalyst is (100-400): 1; the oxidant is oxygen, and the pressure of the oxygen is 1-10 bar.
8. The method according to claim 6 or 7, wherein the temperature of the oxidation reaction is 90 to 120 ℃ for 1 to 6 hours.
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| A coprecipitation technique to prepare CoTa2O6 and CoNb2O6;I.S. Mulla， et al;Materials Letters;第61卷;第2128页左栏第2段至右栏第1段 * |
| Guiqin Xiao, et al.Preparation of Highly Dispersed Nb2O5 Supported Cobalt-Based Catalysts for the Fischer−Tropsch Synthesis.Ind. Eng. Chem. Res..2020,第59卷第17136页左栏第2-3段及第17320页左栏第3段至右栏第1段. * |
| Preparation of Highly Dispersed Nb2O5 Supported Cobalt-Based Catalysts for the Fischer−Tropsch Synthesis;Guiqin Xiao, et al;Ind. Eng. Chem. Res.;第59卷;第17136页左栏第2-3段及第17320页左栏第3段至右栏第1段 * |
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