CN110302815B - Ag @ SiO2Synthesis method of supported mesoporous niobium phosphate catalyst and application of supported mesoporous niobium phosphate catalyst in preparation of 5-hydroxymethylfurfural - Google Patents
Ag @ SiO2Synthesis method of supported mesoporous niobium phosphate catalyst and application of supported mesoporous niobium phosphate catalyst in preparation of 5-hydroxymethylfurfural Download PDFInfo
- Publication number
- CN110302815B CN110302815B CN201910536794.6A CN201910536794A CN110302815B CN 110302815 B CN110302815 B CN 110302815B CN 201910536794 A CN201910536794 A CN 201910536794A CN 110302815 B CN110302815 B CN 110302815B
- Authority
- CN
- China
- Prior art keywords
- solution
- sio
- water
- niobium
- catalyst
- 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.)
- Active
Links
- NOEGNKMFWQHSLB-UHFFFAOYSA-N 5-hydroxymethylfurfural Chemical compound OCC1=CC=C(C=O)O1 NOEGNKMFWQHSLB-UHFFFAOYSA-N 0.000 title claims abstract description 96
- RJGBSYZFOCAGQY-UHFFFAOYSA-N hydroxymethylfurfural Natural products COC1=CC=C(C=O)O1 RJGBSYZFOCAGQY-UHFFFAOYSA-N 0.000 title claims abstract description 96
- 239000003054 catalyst Substances 0.000 title claims abstract description 66
- CNHRNMLCYGFITG-UHFFFAOYSA-A niobium(5+);pentaphosphate Chemical compound [Nb+5].[Nb+5].[Nb+5].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O CNHRNMLCYGFITG-UHFFFAOYSA-A 0.000 title claims abstract description 60
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 238000000034 method Methods 0.000 title claims abstract description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 66
- 229910001868 water Inorganic materials 0.000 claims abstract description 62
- 238000006243 chemical reaction Methods 0.000 claims abstract description 55
- 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 claims abstract description 47
- 239000008103 glucose Substances 0.000 claims abstract description 47
- GAEKPEKOJKCEMS-UHFFFAOYSA-N gamma-valerolactone Chemical compound CC1CCC(=O)O1 GAEKPEKOJKCEMS-UHFFFAOYSA-N 0.000 claims abstract description 36
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims abstract description 10
- 230000002194 synthesizing effect Effects 0.000 claims abstract description 5
- 239000000463 material Substances 0.000 claims abstract description 4
- 239000000243 solution Substances 0.000 claims description 60
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 33
- 229910052681 coesite Inorganic materials 0.000 claims description 31
- 229910052906 cristobalite Inorganic materials 0.000 claims description 31
- 229910052682 stishovite Inorganic materials 0.000 claims description 31
- 229910052905 tridymite Inorganic materials 0.000 claims description 31
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 18
- 239000012279 sodium borohydride Substances 0.000 claims description 18
- 238000003756 stirring Methods 0.000 claims description 14
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(I) nitrate Inorganic materials [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 12
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 11
- 239000007864 aqueous solution Substances 0.000 claims description 11
- 239000002131 composite material Substances 0.000 claims description 9
- MAKKVCWGJXNRMD-UHFFFAOYSA-N niobium(5+);oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[O-2].[O-2].[Nb+5].[Nb+5] MAKKVCWGJXNRMD-UHFFFAOYSA-N 0.000 claims description 9
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 7
- 238000010992 reflux Methods 0.000 claims description 7
- 238000000967 suction filtration Methods 0.000 claims description 7
- 239000011975 tartaric acid Substances 0.000 claims description 7
- 235000002906 tartaric acid Nutrition 0.000 claims description 7
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 claims description 6
- 229920000604 Polyethylene Glycol 200 Polymers 0.000 claims description 5
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 claims description 5
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 claims description 5
- 230000015572 biosynthetic process Effects 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 5
- 235000019837 monoammonium phosphate Nutrition 0.000 claims description 5
- -1 polytetrafluoroethylene Polymers 0.000 claims description 5
- 238000003786 synthesis reaction Methods 0.000 claims description 5
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 4
- 238000009833 condensation Methods 0.000 claims description 4
- 230000005494 condensation Effects 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 4
- 238000002425 crystallisation Methods 0.000 claims description 4
- 230000008025 crystallization Effects 0.000 claims description 4
- 239000008367 deionised water Substances 0.000 claims description 4
- 229910021641 deionized water Inorganic materials 0.000 claims description 4
- 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 claims description 4
- 239000004033 plastic Substances 0.000 claims description 4
- 229920003023 plastic Polymers 0.000 claims description 4
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 4
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 4
- 238000007789 sealing Methods 0.000 claims description 4
- 229910001220 stainless steel Inorganic materials 0.000 claims description 4
- 239000010935 stainless steel Substances 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims description 4
- 238000001308 synthesis method Methods 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 4
- 101710134784 Agnoprotein Proteins 0.000 claims description 3
- 238000004090 dissolution Methods 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 239000002105 nanoparticle Substances 0.000 claims description 3
- ZKATWMILCYLAPD-UHFFFAOYSA-N niobium pentoxide Inorganic materials O=[Nb](=O)O[Nb](=O)=O ZKATWMILCYLAPD-UHFFFAOYSA-N 0.000 claims description 3
- 238000005303 weighing Methods 0.000 claims description 3
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 claims description 2
- 230000000694 effects Effects 0.000 abstract description 15
- 239000011973 solid acid Substances 0.000 abstract description 13
- 230000035484 reaction time Effects 0.000 abstract description 9
- 239000002994 raw material Substances 0.000 abstract description 8
- 229910052758 niobium Inorganic materials 0.000 abstract description 7
- 239000010955 niobium Substances 0.000 abstract description 7
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 abstract description 7
- OZJPLYNZGCXSJM-UHFFFAOYSA-N 5-valerolactone Chemical compound O=C1CCCCO1 OZJPLYNZGCXSJM-UHFFFAOYSA-N 0.000 abstract description 6
- 239000011258 core-shell material Substances 0.000 abstract description 5
- 239000002096 quantum dot Substances 0.000 abstract description 3
- 230000002051 biphasic effect Effects 0.000 abstract description 2
- 229910004298 SiO 2 Inorganic materials 0.000 abstract 5
- 239000000047 product Substances 0.000 description 28
- 238000002835 absorbance Methods 0.000 description 19
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 6
- 229910020057 NbOPO4 Inorganic materials 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 229930091371 Fructose Natural products 0.000 description 4
- 239000005715 Fructose Substances 0.000 description 4
- 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 4
- 230000003197 catalytic effect Effects 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 4
- 238000011160 research Methods 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 3
- 239000002841 Lewis acid Substances 0.000 description 3
- 230000032683 aging Effects 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 230000003247 decreasing effect Effects 0.000 description 3
- 150000007517 lewis acids Chemical class 0.000 description 3
- 238000011068 loading method Methods 0.000 description 3
- 239000012452 mother liquor Substances 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 230000002195 synergetic effect Effects 0.000 description 3
- 229910021556 Chromium(III) chloride Inorganic materials 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 238000007171 acid catalysis Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000004364 calculation method Methods 0.000 description 2
- QSWDMMVNRMROPK-UHFFFAOYSA-K chromium(3+) trichloride Chemical compound [Cl-].[Cl-].[Cl-].[Cr+3] QSWDMMVNRMROPK-UHFFFAOYSA-K 0.000 description 2
- 239000011636 chromium(III) chloride Substances 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 238000007865 diluting Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- XNHGKSMNCCTMFO-UHFFFAOYSA-D niobium(5+);oxalate Chemical compound [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 XNHGKSMNCCTMFO-UHFFFAOYSA-D 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 230000020477 pH reduction Effects 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- YGSDEFSMJLZEOE-UHFFFAOYSA-N salicylic acid Chemical compound OC(=O)C1=CC=CC=C1O YGSDEFSMJLZEOE-UHFFFAOYSA-N 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 239000011949 solid catalyst Substances 0.000 description 2
- 239000008399 tap water Substances 0.000 description 2
- 235000020679 tap water Nutrition 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 238000000825 ultraviolet detection Methods 0.000 description 2
- 238000000870 ultraviolet spectroscopy Methods 0.000 description 2
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- WDJHALXBUFZDSR-UHFFFAOYSA-N Acetoacetic acid Natural products CC(=O)CC(O)=O WDJHALXBUFZDSR-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 244000282866 Euchlaena mexicana Species 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N Furan Chemical group C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 229910003082 TiO2-SiO2 Inorganic materials 0.000 description 1
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 description 1
- 241000219094 Vitaceae Species 0.000 description 1
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 1
- 229910006213 ZrOCl2 Inorganic materials 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000003377 acid catalyst Substances 0.000 description 1
- 238000005903 acid hydrolysis reaction Methods 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 125000003172 aldehyde group Chemical group 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 150000001720 carbohydrates Chemical class 0.000 description 1
- 235000014633 carbohydrates Nutrition 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 150000001844 chromium Chemical class 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- WOWBFOBYOAGEEA-UHFFFAOYSA-N diafenthiuron Chemical compound CC(C)C1=C(NC(=S)NC(C)(C)C)C(C(C)C)=CC(OC=2C=CC=CC=2)=C1 WOWBFOBYOAGEEA-UHFFFAOYSA-N 0.000 description 1
- 150000001993 dienes Chemical class 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 235000021021 grapes Nutrition 0.000 description 1
- 238000004128 high performance liquid chromatography Methods 0.000 description 1
- 231100000086 high toxicity Toxicity 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000002608 ionic liquid Substances 0.000 description 1
- 238000012417 linear regression Methods 0.000 description 1
- 238000003760 magnetic stirring Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 150000002772 monosaccharides Chemical class 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 150000002822 niobium compounds Chemical class 0.000 description 1
- 229910000484 niobium oxide Inorganic materials 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- FJKROLUGYXJWQN-UHFFFAOYSA-N papa-hydroxy-benzoic acid Natural products OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 229960004889 salicylic acid Drugs 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 238000002798 spectrophotometry method Methods 0.000 description 1
- 239000012086 standard solution Substances 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 238000002211 ultraviolet spectrum Methods 0.000 description 1
- 239000011345 viscous material Substances 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
- 229910000166 zirconium phosphate Inorganic materials 0.000 description 1
- LEHFSLREWWMLPU-UHFFFAOYSA-B zirconium(4+);tetraphosphate Chemical compound [Zr+4].[Zr+4].[Zr+4].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O LEHFSLREWWMLPU-UHFFFAOYSA-B 0.000 description 1
Images
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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/186—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J27/195—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with vanadium, niobium or tantalum
-
- 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
- C07D307/38—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 substituted hydrocarbon radicals attached to ring carbon atoms
- C07D307/40—Radicals substituted by oxygen atoms
- C07D307/46—Doubly bound oxygen atoms, or two oxygen atoms singly bound to the same carbon atom
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Catalysts (AREA)
Abstract
本发明涉及一种Ag@SiO2负载介孔磷酸铌催化剂的合成方法及其在制备5‑羟甲基糠醛中的应用，以磷酸氧铌为固体酸源，利用纳米银与磷酸氧铌的协同作用和SiO2与NbOPO4键合作用，将NbOPO4与核壳量子点Ag@SiO2反应，制备出介孔型固体酸催化剂Ag@SiO2‑NbOPO4；并在此基础上以可再生生物资葡萄糖为原料，采用水/γ‑戊内酯双相体系，在最佳制备工艺为：反应温度160℃，反应时间120min，催化剂为Ag@SiO2负载介孔磷酸铌其用量为0.06g、水和戊内酯体积比为5:95及葡萄糖用量0.36mg，该条件下可实现5‑羟甲基糠醛88.23%的收率，效果显著。
The invention relates to a method for synthesizing an Ag@SiO 2 supported mesoporous niobium phosphate catalyst and its application in the preparation of 5-hydroxymethyl furfural. Niobium oxyphosphate is used as a solid acid source, and the synergy of nano silver and niobium oxyphosphate is utilized. and SiO 2 and NbOPO 4 bonding, NbOPO 4 reacts with core-shell quantum dots Ag@SiO 2 to prepare a mesoporous solid acid catalyst Ag@SiO 2 ‑NbOPO 4 ; The material glucose is used as the raw material, and the water/γ-valerolactone biphasic system is used. The optimal preparation process is as follows: the reaction temperature is 160 ° C, the reaction time is 120 min, the catalyst is Ag@SiO 2 supported mesoporous niobium phosphate, and the dosage is 0.06 g, The volume ratio of water and valerolactone is 5:95 and the amount of glucose is 0.36 mg. Under this condition, a yield of 88.23% of 5-hydroxymethylfurfural can be achieved, and the effect is remarkable.
Description
Technical Field
The invention relates to Ag @ SiO2A synthetic method of a loaded mesoporous niobium phosphate catalyst and application thereof in preparation of 5-hydroxymethylfurfural.
Background
5-hydroxymethylfurfural (5-HMF) as an important platform compound can be widely used for preparing various chemical products with high added values and related derivatives through reactions such as oxidation, hydrogenation, condensation and the like of aldehyde groups of convertible functional groups, hydroxyl groups or furan rings of conjugated dienes in molecules. The 5-hydroxymethyl furfural and its derivatives can be used for replacing petroleum fuel, manufacturing various high molecular materials, synthesizing medicines and pesticides, producing resin plastics, etc. Most researchers at present usually prepare 5-hydroxymethylfurfural by dehydrating monosaccharides (including fructose and glucose) and carbohydrates such as cellulose catalyzed by various types of acids. In view of the advantages of low price and rich raw material sources of 5-hydroxymethylfurfural, wide market of partial products and high added value, the research on the synthesis of 5-hydroxymethylfurfural is a hot spot at present.
At present, the raw materials for preparing 5-hydroxymethylfurfural mainly comprise fructose and glucose, and research shows that the fructose can be used for efficiently preparing 5-hydroxymethylfurfural, the yield is up to more than 95%, and the synthesis process is relatively mild and easy to implement; in comparison, the glucose has wider sources, low cost and wider application prospect, but the yield of the target product in the preparation of the 5-hydroxymethylfurfural is generally relatively low, about 50 percent, so that the development of a novel catalyst for preparing the high-yield 5-hydroxymethylfurfural by taking the glucose as a raw material has important theoretical and practical significance. The existing catalytic system for preparing 5-hydroxymethylfurfural mainly comprises inorganic acid (hydrochloric acid, sulfuric acid, nitric acid and the like), organic acid (acetic acid, salicylic acid, formic acid and the like) and salt compound (TiO)2、ZrOCl2Zirconium phosphate, etc.), Lewis acids (CrCl)3、ZnCl2、SnCl4Etc.) and solid acids. Eminov et al chromium salts CrCl3·H2O as catalyst in CrCl3·H2Under the condition that the molar ratio of O to glucose is 24:1, 90% of yield of 5-hydroxymethylfurfural is realized in an ionic liquid reaction system, which is a research report in the prior literature that the highest yield of 5-HMF is realized by taking glucose as a raw material. Secondly, Wang et al already ZrO2And SO4 2-/ TiO2-SiO2As a mixed catalyst in the reaction system H2The yield of 5-hydroxymethylfurfural in O/DMSO is 85 percent. It can be seen that this can be achieved by modifying the catalyst and optimizing the catalytic systemThe 5-hydroxymethylfurfural with high yield is synthesized by taking glucose as a raw material.
Although the metal salt catalyst and the Lewis acid have good application performance, the metal salt catalyst and the Lewis acid have the defects of high toxicity, difficulty in later-stage treatment of samples, difficulty in catalyst recovery and the like. As a novel solid acid catalyst, compared with a homogeneous acid catalyst, the solid acid catalyst not only is easy to separate from a product, can be recycled again, has better high-temperature resistance and stability, but also is convenient to operate and has less environmental pollution. Compared with metal solid acid catalysts such as Ti, Al, Zr and the like, the niobium compound has obvious application advantages in catalysis, and compared with niobium oxide, niobium phosphate shows better acidity, thermal stability and catalytic activity in the acid catalysis process.
In order to realize efficient and economic conversion of glucose into 5-HMF, a load technology is studied to further modify a niobium phosphate catalyst so as to realize efficient catalysis of glucose to prepare 5-HMF; meanwhile, a green renewable solvent system water/gamma-valerolactone is adopted, and a two-phase system is utilized to effectively reduce the decomposition of 5-HMF, so that the 5-HMF is synthesized with high yield.
Disclosure of Invention
The technical problem to be solved by the invention is as follows: provides Ag @ SiO2Synthesis method of supported mesoporous niobium phosphate catalyst, application of supported mesoporous niobium phosphate catalyst in preparation of 5-hydroxymethylfurfural, and Ag @ SiO prepared by utilizing supporting technology2Supported niobium phosphate (Ag @ SiO)2-NbOPO4) The solid acid catalyst has more advantages in the aspects of specific surface area, aperture uniformity, thermal stability and the like, realizes efficient acidification and hydrolysis of grapes by utilizing the mutual synergistic effect of the solid acid catalyst, and can effectively improve the yield of 5-hydroxymethylfurfural.
The technical scheme for solving the technical problems is as follows: ag @ SiO2The synthesis method of the loaded mesoporous niobium phosphate catalyst comprises the following steps:
（1）Ag@SiO2 and (3) synthesis of nanoparticles: weighing AgNO3Placing in secondary water, dissolving at 20-25 deg.C, adding PEG 200, stirring for 15-25min to obtain solution I, AgNO in solution I3The ratio of water to PEG 200 is (0.8-0.9) g to 200mL (78-82) mL, then sodium borohydride and PEGThe ratio of water is (1.1-1.2) g:200 mL, sodium borohydride is put into secondary water to be fully dissolved to obtain sodium borohydride solution, the sodium borohydride solution is slowly dripped into the solution I while stirring, and the dripping amount of the sodium borohydride solution is AgNO3The weight ratio of the nano silver to the sodium borohydride is (0.8-0.9): 1.135, the sodium borohydride solution is quickly stirred after the sodium borohydride solution is dripped, when the pH value of the solution is 9.5-9.7, the nano silver aqueous solution is obtained according to AgNO3The ratio of the Ag to the TEOS is (0.8-0.9) g: 60mL, the TEOS is slowly dripped into the nano-silver aqueous solution, and then the solution is stirred for 1.8-2.2 h at 47-52 ℃ to obtain Ag @ SiO2 Sealing and standing the aqueous solution at room temperature for later use;
(2) preparation of niobium phosphate solution: according to the material amount of 1 (3.9-4.1) and 2.0-2.4), the amounts of niobium pentoxide hydrate, tartaric acid and ammonium dihydrogen phosphate are extracted, the obtained tartaric acid is added into secondary water to be completely dissolved, then the niobium pentoxide hydrate is added, and the mixture is fully stirred in a constant-temperature water bath until the niobium pentoxide hydrate is completely dissolved; adding ammonium dihydrogen phosphate into the secondary water for dissolving completely, and mixing the two prepared solutions uniformly to obtain a niobium phosphate solution;
(3) preparing a niobium phosphate composite solution: measuring secondary water in a plastic bottle according to the proportion of the water to the hexadecyl trimethyl ammonium bromide: (10-15) 1.0g of hexadecyl trimethyl ammonium bromide is added, then the mixture is placed in a constant-temperature water bath kettle at the temperature of 32-38 ℃ to be fully stirred, the fresh niobium phosphate solution prepared in the step (2) is dropwise added into the hexadecyl trimethyl ammonium bromide solution according to the mass ratio of the consumption of the hydrated niobium pentoxide to the hexadecyl trimethyl ammonium bromide in the step (2) of 1.3-1.4:1, and the stirring is continuously carried out for 0.8-1.2 hours, so as to obtain a niobium phosphate composite solution;
(4) synthesizing a catalyst: according to the formula niobium phosphate and Ag @ SiO2The mass ratio of the substances is 1 (0.4-1), the niobium phosphate composite solution prepared in the step (3) and the Ag @ SiO prepared in the step (1) are counted2Placing the aqueous solution in a stainless steel crystallization kettle with a polytetrafluoroethylene lining, aging at the temperature of 125-plus 135 ℃ for 23-25h, naturally cooling, taking out, washing with deionized water, drying at the temperature of 48-53 ℃ overnight, and roasting in a muffle furnace at the temperature of 580-plus 620 ℃ for 4-6h to obtain Ag @ SiO2Mesoporous supported niobium phosphateA catalyst.
The other technical scheme of the invention is as follows: ag @ SiO as defined above2The application of the loaded mesoporous niobium phosphate catalyst in the preparation of 5-hydroxymethylfurfural comprises the following steps of: 0.04g (15-25) mL of glucose is weighed and added into water for complete ultrasonic dissolution, gamma-valerolactone and glucose solution are added into a container according to the volume ratio of water to gamma-valerolactone (4-6):95, and after being uniformly stirred, Ag @ SiO is added2The mesoporous niobium phosphate supported catalyst comprises the following components in percentage by mass: (0.03-0.06) g, 0.36mg, placing the container in a heater at the temperature of 150 ℃ and 170 ℃, installing a condensation reflux device, carrying out heating reflux reaction for 115 min and 125min, carrying out suction filtration when the reaction is finished, and taking the liquid obtained by suction filtration, namely the 5-hydroxymethylfurfural solution.
The supported catalyst is a catalyst in which an active component and a cocatalyst are uniformly dispersed and supported on a specially selected carrier. After the noble metal catalyst is prepared into a load type, the dispersity (the ratio of the atomic number of the metal exposed on the surface of the crystal grain to the total atomic number of the metal) of the noble metal catalyst can be improved, and the using amount can be reduced. The nano-scale silicon dioxide has the advantages of small size, more micropores, good surface permeability, large specific surface area, high thermal stability and the like. The core-shell type nano material has the characteristics of good stability, easy regulation and control, excellent dispersibility and capability of designing a core-shell structure. Niobium phosphate (NbOPO) as a novel solid acid catalyst at present4) And the analogues thereof have obvious advantages in the application of catalyzing glucose and fructose to prepare 5-hydroxymethylfurfural. The invention prepares Ag @ SiO based on the previous research2Supported niobium phosphate solid acid catalyst (Ag @ SiO)2- NbOPO4) And the synergistic effect of the two components is utilized to realize better catalysis of glucose to prepare 5-hydroxymethylfurfural. The invention takes mesoporous niobium phosphate as a carrier, and the mesoporous niobium phosphate is mixed with Ag @ SiO2Loading to obtain the catalyst with good catalytic activity in hydrolysis reaction of glucose. Meanwhile, in view of a reaction mechanism of preparing 5-hydroxymethylfurfural from glucose, in order to reduce side reactions in the reaction, a water gamma-valerolactone biphasic system is adopted in a reaction system, so that high-efficiency preparation of 5-hydroxymethylfurfural is realized.
The invention is provided withThe yield of the 5-hydroxymethylfurfural is used as an optimization index, the accurate determination of the 5-HMF is realized by adopting an ultraviolet spectrophotometry, and a standard curve equation for calculating the content of the 5-HMF is established according to the result: y =51.8x + 0.1204; and with niobium phosphate (NbOPO)4) Is a solid acid source, utilizes the synergistic effect of nano silver and niobium phosphate and SiO2And NbOPO4Bonding NbOPO4And core-shell quantum dot Ag @ SiO2Reacting to prepare a solid acid catalyst Ag @ SiO2-NbOPO4(ii) a On the basis, renewable biological resource glucose is used as a raw material, a water/gamma-valerolactone two-phase system is adopted, the influence of factors such as reaction temperature, reaction time, catalyst dosage and the like on the yield of the 5-HMF is explored by single factors, and the result shows that the optimal preparation process of the 5-HMF is as follows: the reaction temperature is 160 ℃, the reaction time is 120min, and the catalyst is Ag @ SiO2The using amount of the loaded mesoporous niobium phosphate is 0.06g, the volume ratio of water to valerolactone is 5:95, and the using amount of glucose is 0.36mg, under the condition, the yield of 5-hydroxymethylfurfural 88.23% can be realized, and the effect is obvious.
Drawings
FIG. 1 is a linear regression plot of absorbance versus mass concentration of 5-HMF.
FIG. 2 is a graph showing the effect of reaction time on the yield of 5-hydroxymethylfurfural.
FIG. 3 is a graph showing the effect of catalyst amount on the yield of 5-hydroxymethylfurfural.
FIG. 4 is a graph showing the effect of glucose dosage on the yield of 5-hydroxymethylfurfural.
FIG. 5 is a graph of the effect of water volume on 5-hydroxymethylfurfural yield.
FIG. 6 is a graph showing the effect of reaction temperature on the yield of 5-hydroxymethylfurfural.
FIG. 7 is a UV spectrum of the product obtained under the optimal reaction conditions.
Detailed Description
Example 1: a synthesis method of an Ag @ SiO2 supported mesoporous niobium phosphate catalyst comprises the following steps:
（1）Ag@SiO2 and (3) synthesis of nanoparticles: 0.85 g (0.005 mol) of AgNO was weighed3Putting the mixture into 200mL of secondary water, and dissolving the mixture in a water bath kettle at 23 DEG CAfter the solution is uniformly mixed, 80mL of PEG 200 is added and stirred for 20min, then 1.135g of sodium borohydride is placed in 200mL of secondary water to be fully dissolved, the solution is slowly added dropwise while stirring, after the sodium borohydride solution is added dropwise, the stirring speed is rapidly adjusted to 400r/min, the solution is stirred vigorously for 15 min, and when the solution is changed from dark gray to light gray and the pH value is about 9.6, naked nano-silver particles are generated. Then slowly dripping 60mL of TEOS into the nano-silver aqueous solution, regulating the temperature of a water bath kettle to 50 ℃, and stirring for 2h to obtain Ag @ SiO2 Sealing and standing the aqueous solution at room temperature for later use.
(2) Preparation of niobium phosphate solution: according to the amount of the substances of 1:4, 0.005mol of niobium pentoxide hydrate and 0.02mol of tartaric acid are taken, the obtained tartaric acid is taken out and added into water to be completely dissolved, then the niobium pentoxide hydrate is added, and the mixture is fully stirred in a constant-temperature water bath until the niobium pentoxide hydrate and the tartaric acid are completely dissolved. 1.31g of ammonium dihydrogen phosphate is added into the secondary water to be dissolved completely. Mixing the above two solutions.
(3) Preparing a niobium phosphate composite solution: measuring 13mL of secondary water in a plastic (PP) bottle, adding 1.0g of hexadecyl trimethyl ammonium bromide, then placing the bottle in a constant-temperature water bath kettle at 35 ℃ for fully stirring, taking all the prepared fresh niobium phosphate solution, dropwise adding the fresh niobium phosphate solution into the hexadecyl trimethyl ammonium bromide solution, and continuously stirring for 1h to obtain the niobium phosphate composite solution.
(4) Synthesizing a catalyst: half of the fresh niobium phosphate composite solution (equivalent to 0.005moL niobium phosphate) and all Ag @ SiO2Aqueous solution (equivalent to 0.005moL Ag @ SiO)2) Placing in a stainless steel crystallization kettle with a polytetrafluoroethylene lining, aging at 130 ℃ for 24h, naturally cooling, taking out, washing with deionized water, drying at 50 ℃ overnight, and roasting in a muffle furnace at 600 ℃ for 5h to obtain Ag @ SiO2A mesoporous niobium phosphate supported catalyst.
The hydrated niobium pentoxide employed in this example may be purchased directly from the market, or may be prepared in the following conventional manner: adding a certain amount of niobium oxalate into water to dissolve completely, adding ethylene glycol according to the volume ratio of the niobium oxalate solution to the ethylene glycol of 1:2, stirring uniformly, adding ammonia water to regulate the pH value to be about 9, sealing a beaker, putting the beaker into a constant-temperature water bath kettle at 65 ℃ for stirring, generating white precipitate at the moment, taking out the beaker after the reaction is completely finished, separating the beaker by using a centrifugal machine to obtain white solid, washing the white solid by using deionized water, and drying the white solid in a proper amount.
Example 2: ag @ SiO solid as described in example 12The application of the loaded mesoporous niobium phosphate catalyst in the preparation of 5-hydroxymethylfurfural is characterized by weighing 0.04g of glucose, placing the glucose in a 50mL beaker, adding 20mL of water, carrying out ultrasonic dissolution completely, adding gamma-valerolactone and glucose solution into the round-bottom beaker according to the volume ratio of the water to the gamma-valerolactone of 5:95, stirring uniformly, and adding crushed Ag @ SiO2The mesoporous niobium phosphate supported catalyst comprises the following components in percentage by mass: 60:0.36, then placing the round-bottom flask in a heater at the temperature of 160 ℃, loading a condensation reflux device and introducing tap water, carrying out heating reflux reaction for 120min, taking out the reaction flask after the reaction is finished, carrying out suction filtration by using a suction filtration bottle while the reaction flask is hot, taking the liquid obtained by suction filtration, namely the 5-hydroxymethylfurfural solution, wherein the yield is 88.23%.
The detection of the product 5-hydroxymethylfurfural and the calculation of the yield are as follows:
generally, two methods are used for measuring 5-hydroxymethylfurfural in the product, wherein the first method is high performance liquid chromatography, a chromatographic column and an ultraviolet detector at 280 nm. The second method is a UV detection method which requires a UV-visible spectrophotometer to detect its absorbance at 284nm, and the second method is a UV detection method used in the present invention.
5-HMF standard solution preparation and standard curve establishment: taking 0.1g of 5-hydroxymethyl furfural standard (Nanjing Dulai biotechnology, Inc.), titrating with secondary water to 10mL to prepare mother liquor, diluting the mother liquor according to the required test mass concentration, measuring the absorbance of the mother liquor at 284nm by using an ultraviolet spectrophotometer, and establishing a standard curve of the absorbance (y) and the 5-HMF mass concentration (x), wherein the standard curve is obtained by using the absorbance (y) and the 5-HMF mass concentration (x)R 2It is required to be 0.95 or more.
Determination of absorbance of sample and calculation of 5-HMF yield: opening an ultraviolet-visible spectrophotometer, preheating for about 30min, taking 4mL of gamma-valerolactone in a sample measuring tube, and taking a base line within the range of 200nm-400 nm; and taking 4mL of the test sample obtained by the experiment, measuring the absorbance at 284nm, diluting the sample until the sample is in the reasonable value range of the standard curve when the sample concentration is too high and the absorbance deviates from the range of the standard curve, and recording the total volume after dilution so as to calculate the yield of the 5-HMF.
The standard curve equation for absorbance (y) versus mass concentration (x) is: y =51.8x +0.1204
Calculating the concentration of the 5-hydroxymethylfurfural and the yield of the 5-hydroxymethylfurfural of the product as follows:
the development process of the invention is as follows:
1. influence of reaction time on the yield of 5-hydroxymethylfurfural.
1.5mL of glucose with the concentration of 2mg/mL and 8.5mL of gamma-valerolactone are taken to be stirred and mixed evenly, and the prepared Ag @ SiO20.06g of mesoporous niobium phosphate supported catalyst. Then placing the round bottom beaker in a magnetic stirring pan of oil bath heated to 140 ℃, filling tap water in a condensing reflux device, and starting timing for 60min, 80min, 100min, 120min and 140min respectively. From the collected product, the color of the solution was colorless and pale yellow regardless of the product concentration from the viewpoint of appearance, and the absorbance A of the product at 284nm under an ultraviolet-visible photometer was measured and recorded in order and converted into the conversion of glucose and the yield of 5-hydroxymethylfurfural, and Table 1 and FIG. 2 were prepared in terms of the time of reaction and the yield of 5-hydroxymethyl group. As can be seen from table 1 and fig. 2, the optimal yield of 5-hydroxymethylfurfural was 120min, the absorbance was the highest, and the yield was 53.58% with other variables being controlled. This is because the reaction temperature is too low to sufficiently activate the solid acid hydrolysis acidification of glucose5-hydroxymethyl furfural is formed; along with the reaction temperature, the acid catalysis speed of the catalyst is accelerated, and the yield of the 5-hydroxymethylfurfural is increased; too high a reaction temperature also accelerates the decomposition rate of 5-HMF, which in turn leads to a decrease in the yield of 5-HMF.
TABLE 1 Effect of reaction time on 5-hydroxymethylfurfural yield
2.Ag@SiO2Influence of the amount of the supported mesoporous niobium phosphate catalyst on the yield of 5-hydroxymethylfurfural.
The optimal reaction time in the time variables is selected to be 120min, other conditions of the experiment are not changed, and the content of the 5-hydroxymethylfurfural in the product is respectively considered when the catalyst dosage is respectively 0.02 g, 0.04g, 0.06g, 0.08g and 0.1 g. It was observed that the severity of the reaction gradually decreased during the course of the reaction as the amount of catalyst was increased. The product was collected and its absorbance a at 284nm in an ultraviolet-visible spectrophotometer was measured, and from this, the yield of 5-hydroxymethylfurfural was calculated, as shown in table 2 and fig. 3.
TABLE 2 influence of catalyst dosage on 5-hydroxymethylfurfural yield
Table 2, fig. 3 show that the amount of different catalysts has a significant effect on the yield of 5-hydroxymethylfurfural. When the amount of the catalyst is increased between 0.02 and 0.06g, the yield of the 5-hydroxymethylfurfural is simultaneously increased, and when the amount of the catalyst is 0.06g, the yield of the 5-HMF reaches the maximum value of 53.58 percent; with increasing amounts of catalyst, the yield of 5-HMF showed a significant decrease. The reason is that the yield of the product is increased by properly increasing the dosage of the catalyst, which is beneficial to catalyzing the reaction active site for converting the glucose into the 5-HMF; when the catalyst is used in an excessive amount, the rate of side reactions such as polymerization and decomposition of 5-HMF in the reaction system is increased, and the yield of the target product is reduced. The optimum amount of catalyst used was 0.06g for this experiment.
3. Influence of the amount of glucose on the yield of 5-hydroxymethylfurfural.
The reaction conditions were selected for the optimum yield, and the amounts of glucose used in the reactions were changed to 0.24mg, 0.36mg, 0.48mg, 0.6mg, and 0.72mg, respectively, by adjusting the amounts of glucose used in the reactions. After the reaction is finished, the product is collected and measured, and the absorbance A of the product at 284nm under an ultraviolet-visible photometer is measured, and the influence of the glucose dosage on the yield of the 5-hydroxymethylfurfural is shown in table 3 and figure 4. From the experimental results it can be obtained: when the other conditions are not changed, the single variable of the dosage of the glucose is changed, the best yield of the 5-hydroxymethylfurfural is the highest absorbance when the dosage of the glucose is 0.36mg, and the highest yield is 53.58%.
TABLE 3 influence of the amount of glucose used on the yield of 5-hydroxymethylfurfural
As shown in table 3 and fig. 4, the yield of 5-hydroxymethylfurfural increased and then decreased with the increase of the amount of glucose, and when the amount of glucose was 0.36mg, the yield was 53.58% at the highest, and when the amount of glucose was increased, the amount of 5-hydroxymethylfurfural measured in the product was continuously decreased to only 2.06% at the lowest, so that the reaction effect was the best when the amount of glucose used in the experiment was 0.36 mg.
4. Effect of water and gamma valerolactone volume ratio on yield of 5-hydroxymethylfurfural.
And under the experimental conditions of optimal reaction time, catalyst dosage and glucose dosage, the influence of the volume ratios of different water and gamma-valerolactone on the experimental result is examined. The previous procedure was repeated to collect the resultant product and record its absorbance a at 284nm measured under a uv-vis spectrophotometer, converted into conversion rate of glucose and yield of 5-hydroxymethylfurfural, and the following table 4 and fig. 5 were prepared in terms of volume of water and yield of 5-hydroxymethyl group (total volume of solvent is 10mL, wherein the solvent is water and valerolactone).
TABLE 4 Effect of Water volume on 5-hydroxymethylfurfural yield
As shown in the graphs 4 and 5, the yield of 5-hydroxymethylfurfural in the product decreases significantly as the volume of water increases. This is because when the volume of water is small, the 5-hydroxymethylfurfural produced by the reaction can be extracted by gamma-valerolactone in time without being decomposed; when the water content is increased, 5-hydroxymethylfurfural is easy to decompose at high temperature, so that a large part of products are decomposed by water in the reaction process, the reduction of the using amount of water in the reaction system is beneficial to improving the product yield under the condition of fully dissolving the reaction raw material glucose, and the yield is 74.34 percent at most when the volume of water is 0.5mL, namely the volume ratio of water to gamma-valerolactone is 5:95, so that the best effect is achieved.
5. Influence of the reaction temperature on the yield of 5-hydroxymethylfurfural.
The influence of the reaction temperature on the experimental results was examined under experimental conditions of optimum reaction time, catalyst amount, glucose amount, water and gamma-valerolactone volume ratio of 5: 95. The resultant product was collected by repeating the previous steps and then measured for absorbance a at 284nm under an ultraviolet-visible photometer, and the conversion rate into glucose and the yield of 5-hydroxymethylfurfural were recorded, and table 5 and fig. 6 were prepared according to the reaction temperature and the yield of 5-hydroxymethyl group.
TABLE 5 Effect of reaction temperature on 5-hydroxymethylfurfural yield
As shown in Table 5 and FIG. 6, the yield of 5-hydroxymethylfurfural in the product was 88.23% at the maximum at a temperature variation of 160 ℃ as the reaction temperature increased. The experimental reaction temperature is thus optimal. This is because a suitable increase in the reaction temperature is advantageous for increasing the rate of conversion of glucose to 5-hydroxymethylfurfural; when the temperature is too high, 5-HMF is further decomposed into byproducts such as acetoacetic acid and the like under high temperature and acidic conditions, so that the product yield of a reaction system is reduced.
6. Non-mesoporous niobium phosphate-Ag @ SiO2Influence on the yield of 5-hydroxymethylfurfural.
Non-mesoporous niobium phosphate-Ag @ SiO2The preparation method comprises the following steps: putting a fresh niobium phosphate solution (prepared in the step (2) of the embodiment 1 of the invention, wherein the niobium phosphate solution does not contain hexadecyl trimethyl ammonium bromide) into a constant-temperature water bath kettle at 80 ℃ to be stirred for 8-10h to ensure that the reaction is completely carried out to generate niobium phosphate, and adding Ag @ SiO2The core-shell quantum dots (prepared in step (1) of example 1 of the invention) and niobium phosphate are placed in a constant-temperature water bath kettle at 50 ℃ for reaction for 3 hours. Placing the obtained solution in a stainless steel crystallization kettle with a polytetrafluoroethylene lining, aging at 130 ℃ for 24h, naturally cooling to normal temperature, taking out, centrifuging the aged product by a centrifuge to obtain a semi-viscous substance, drying at 80 ℃ to obtain off-white powder, placing the off-white powder in a muffle furnace at 500 ℃ to calcine for 5h to obtain an off-white product, namely the niobium phosphate-Ag @ SiO2The catalyst was ground in a mortar for further use.
Under all the above-mentioned optimum reaction conditions, the catalyst is made up by using Ag @ SiO2Replacing mesoporous niobium phosphate into non-mesoporous niobium phosphate-Ag @ SiO2. Repeating the previous steps, classifying and collecting the products after the reaction, measuring the absorbance A at 284nm under an ultraviolet-visible photometer, recording the absorbance A, converting the absorbance A into the conversion rate of glucose and the yield of the 5-hydroxymethylfurfural, wherein the yield of the 5-hydroxymethylfurfural is 53.6 percent which is much lower than the optimal yield. So that it is possible to obtain: ag @ SiO under the same loading condition when other conditions are not changed2The effect of the supported mesoporous niobium phosphate solid catalyst is better than that of Ag @ SiO2A supported non-mesoporous niobium phosphate solid catalyst.
Claims (2)
1. Ag @ SiO2The synthesis method of the loaded mesoporous niobium phosphate catalyst is characterized by comprising the following steps: the method comprises the following steps:
（1）Ag@SiO2 and (3) synthesis of nanoparticles: weighing AgNO3Placing in secondary water at 20-25 deg.CDissolving uniformly, adding PEG 200, stirring for 15-25min to obtain solution I, AgNO in the solution I3The ratio of water to PEG 200 is (0.8-0.9) g:200 mL (78-82) mL, then sodium borohydride is put into secondary water according to the ratio of sodium borohydride to water is (1.1-1.2) g:200 mL to be fully dissolved to obtain sodium borohydride solution, the sodium borohydride solution is slowly dripped into the solution I while stirring, and the dripping amount of the sodium borohydride solution is AgNO3The weight ratio of the nano silver to the sodium borohydride is (0.8-0.9): 1.135, the sodium borohydride solution is quickly stirred after the sodium borohydride solution is dripped, when the pH value of the solution is 9.5-9.7, the nano silver aqueous solution is obtained according to AgNO3The ratio of the Ag to the TEOS is (0.8-0.9) g: 60mL, the TEOS is slowly dripped into the nano-silver aqueous solution, and then the solution is stirred for 1.8-2.2 h at 47-52 ℃ to obtain Ag @ SiO2 Sealing and standing the aqueous solution at room temperature for later use;
(2) preparation of niobium phosphate solution: according to the material amount of 1 (3.9-4.1) and 2.0-2.4), the amounts of niobium pentoxide hydrate, tartaric acid and ammonium dihydrogen phosphate are extracted, the obtained tartaric acid is added into secondary water to be completely dissolved, then the niobium pentoxide hydrate is added, and the mixture is fully stirred in a constant-temperature water bath until the niobium pentoxide hydrate is completely dissolved; adding ammonium dihydrogen phosphate into the secondary water for dissolving completely, and mixing the two prepared solutions uniformly to obtain a niobium phosphate solution;
(3) preparing a niobium phosphate composite solution: measuring secondary water in a plastic bottle according to the proportion of the water to the hexadecyl trimethyl ammonium bromide: (10-15) 1.0g of hexadecyl trimethyl ammonium bromide is added, then the mixture is placed in a constant-temperature water bath kettle at the temperature of 32-38 ℃ to be fully stirred, the fresh niobium phosphate solution prepared in the step (2) is dropwise added into the hexadecyl trimethyl ammonium bromide solution according to the mass ratio of the consumption of the hydrated niobium pentoxide to the hexadecyl trimethyl ammonium bromide in the step (2) of 1.3-1.4:1, and the stirring is continuously carried out for 0.8-1.2 hours, so as to obtain a niobium phosphate composite solution;
(4) synthesizing a catalyst: according to the formula niobium phosphate and Ag @ SiO2The mass ratio of the substances is 1 (0.4-1), the niobium phosphate composite solution prepared in the step (3) and the Ag @ SiO prepared in the step (1) are counted2The aqueous solution is placed in a stainless steel crystallization kettle with a polytetrafluoroethylene lining and aged for 23-25h at the temperature of 125-135 ℃,naturally cooling, taking out, washing with deionized water, drying at 48-53 ℃ overnight, and roasting in a muffle furnace at 580-620 ℃ for 4-6h to obtain Ag @ SiO2A mesoporous niobium phosphate supported catalyst.
2. Ag @ SiO prepared by the method of claim 12The application of the loaded mesoporous niobium phosphate catalyst in the preparation of 5-hydroxymethylfurfural is characterized in that: the proportion of glucose to water is as follows: 0.04g (15-25) mL of glucose is weighed and added into water for complete ultrasonic dissolution, gamma-valerolactone and glucose solution are added into a container according to the volume ratio of water to gamma-valerolactone (4-6):95, and after being uniformly stirred, Ag @ SiO is added2The mesoporous niobium phosphate supported catalyst comprises the following components in percentage by mass: (0.03-0.06) g, 0.36mg, placing the container in a heater at the temperature of 150 ℃ and 170 ℃, installing a condensation reflux device, carrying out heating reflux reaction for 115 min and 125min, carrying out suction filtration when the reaction is finished, and taking the liquid obtained by suction filtration, namely the 5-hydroxymethylfurfural solution.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910536794.6A CN110302815B (en) | 2019-06-20 | 2019-06-20 | Ag @ SiO2Synthesis method of supported mesoporous niobium phosphate catalyst and application of supported mesoporous niobium phosphate catalyst in preparation of 5-hydroxymethylfurfural |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910536794.6A CN110302815B (en) | 2019-06-20 | 2019-06-20 | Ag @ SiO2Synthesis method of supported mesoporous niobium phosphate catalyst and application of supported mesoporous niobium phosphate catalyst in preparation of 5-hydroxymethylfurfural |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN110302815A CN110302815A (en) | 2019-10-08 |
| CN110302815B true CN110302815B (en) | 2021-11-09 |
Family
ID=68076755
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910536794.6A Active CN110302815B (en) | 2019-06-20 | 2019-06-20 | Ag @ SiO2Synthesis method of supported mesoporous niobium phosphate catalyst and application of supported mesoporous niobium phosphate catalyst in preparation of 5-hydroxymethylfurfural |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110302815B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114054056B (en) * | 2020-07-30 | 2023-12-22 | 中国石油化工股份有限公司 | Hydroisomerization bifunctional catalyst, and preparation method and application thereof |
| CN115041201B (en) * | 2022-04-21 | 2024-05-10 | 浙江恒逸石化研究院有限公司 | A highly selective metal-modified hollow niobium phosphate catalyst and its preparation method, and its application in the synthesis of 5-hydroxymethylfurfural |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2007146636A1 (en) * | 2006-06-06 | 2007-12-21 | Wisconsin Alumni Research Foundation | Catalytic process for producing furan derivatives from carbohydrates in a biphasic reactor |
| CN102101851A (en) * | 2009-12-18 | 2011-06-22 | 中国科学院大连化学物理研究所 | Method for catalytic preparation of 5-hydroxymethyl furfural from carbohydrates |
| CN103977796A (en) * | 2014-05-18 | 2014-08-13 | 华东理工大学 | Catalyst used in preparation of long-chain alkane through catalytic hydrodeoxygenation of biomass |
| CN104039441A (en) * | 2011-11-07 | 2014-09-10 | 索尔维公司 | Catalysts for direct synthesis of hydrogen peroxide |
| CN108796135A (en) * | 2017-05-03 | 2018-11-13 | 中国科学院大连化学物理研究所 | A method of promoting the polysaccharide hydrolysis containing glycosidic bond under light and heat condition |
| WO2019000069A1 (en) * | 2017-06-29 | 2019-01-03 | The University Of Western Ontario | Bi-phasic continuous-flow tubular reactor and heterogeneous catalysts preparation method for production of 5-hydroxymethyl furfural |
| JP2019048249A (en) * | 2017-09-07 | 2019-03-28 | 国立研究開発法人宇宙航空研究開発機構 | Catalyst for hydrogen reduction of carbon dioxide and method for producing the same, hydrogen reduction method for carbon dioxide and hydrogen reduction apparatus for carbon dioxide |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8741258B2 (en) * | 2008-09-18 | 2014-06-03 | University Of Massachusetts | Production of hydrogen, liquid fuels, and chemicals from catalytic processing of bio-oils |
-
2019
- 2019-06-20 CN CN201910536794.6A patent/CN110302815B/en active Active
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2007146636A1 (en) * | 2006-06-06 | 2007-12-21 | Wisconsin Alumni Research Foundation | Catalytic process for producing furan derivatives from carbohydrates in a biphasic reactor |
| CN102101851A (en) * | 2009-12-18 | 2011-06-22 | 中国科学院大连化学物理研究所 | Method for catalytic preparation of 5-hydroxymethyl furfural from carbohydrates |
| CN104039441A (en) * | 2011-11-07 | 2014-09-10 | 索尔维公司 | Catalysts for direct synthesis of hydrogen peroxide |
| CN107754794A (en) * | 2011-11-07 | 2018-03-06 | 索尔维公司 | Catalyst for producing hydrogen peroxide by direct synthesis |
| CN103977796A (en) * | 2014-05-18 | 2014-08-13 | 华东理工大学 | Catalyst used in preparation of long-chain alkane through catalytic hydrodeoxygenation of biomass |
| CN108796135A (en) * | 2017-05-03 | 2018-11-13 | 中国科学院大连化学物理研究所 | A method of promoting the polysaccharide hydrolysis containing glycosidic bond under light and heat condition |
| WO2019000069A1 (en) * | 2017-06-29 | 2019-01-03 | The University Of Western Ontario | Bi-phasic continuous-flow tubular reactor and heterogeneous catalysts preparation method for production of 5-hydroxymethyl furfural |
| JP2019048249A (en) * | 2017-09-07 | 2019-03-28 | 国立研究開発法人宇宙航空研究開発機構 | Catalyst for hydrogen reduction of carbon dioxide and method for producing the same, hydrogen reduction method for carbon dioxide and hydrogen reduction apparatus for carbon dioxide |
Also Published As
| Publication number | Publication date |
|---|---|
| CN110302815A (en) | 2019-10-08 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN110302815B (en) | Ag @ SiO2Synthesis method of supported mesoporous niobium phosphate catalyst and application of supported mesoporous niobium phosphate catalyst in preparation of 5-hydroxymethylfurfural | |
| He et al. | The synthesis of 5-hydroxymethylfurfural from glucose in biphasic system by phosphotungstic acidified titanium–zirconium dioxide | |
| CN110407779B (en) | Method for preparing 5-Hydroxymethylfurfural with biomass as raw material | |
| CN110302816A (en) | Synthesis of ZnO@SiO2 Supported Mesoporous Niobium Phosphate Catalyst and Its Application in Preparation of 5-Hydroxymethylfurfural | |
| CN107282106B (en) | Preparation method and application of a weakly water-soluble loaded phosphotungstic heteropoly acid | |
| Cai et al. | Selective HMF synthesis from glucose via microwave-assisted metal chloride catalysis | |
| Zhai et al. | Efficient production of ethyl levulinate from furfuryl alcohol catalyzed by modified zirconium phosphate | |
| Mo et al. | Sustainable synthesis of 5-hydroxymethylfurfural from waste cotton stalk catalyzed by solid superacid-SO42-/ZrO2 | |
| CN106008415B (en) | A kind of method for preparing 2,5 furans dicarbaldehydes | |
| CN106582749A (en) | A kind of Cs-VPO/SiO2 catalyst and its preparation method and the application of catalyzing the condensation of acetic acid and paraformaldehyde to prepare acrylic acid | |
| Wang et al. | Syntheses of 5-Hydroxymethylfurfural Through Glucose Dehydration in Diphasic Solvent System on ZrO2 and SO42−/TiO2-SiO2 Catalyst | |
| CN104689810A (en) | Solid acid catalyst and application of solid acid catalyst in synthesis of reproducible diesel oil or aviation kerosene | |
| CN112827489A (en) | Supported photocatalyst and application thereof | |
| CN116284633B (en) | Porphyrin-containing covalent organic framework material and preparation method and application thereof | |
| CN103084162A (en) | Lanthanum-supported composite oxide solid catalyst as well as preparation method and applications of catalyst | |
| CN110882716A (en) | Preparation method of novel solid acid catalyst for one-pot multi-step catalytic conversion of biomass-derived furfural to γ-valerolactone | |
| CN106749130B (en) | A kind of method that 5 hydroxymethyl furfural prepares 2,5- furandicarboxylic acid | |
| CN117486838A (en) | Photocatalytic synthesis method of 2 (5H) -furanone compound | |
| CN102875458A (en) | Synthesis method of chromium 2-pyridylformate | |
| CN110437189B (en) | Preparation method of 5-formyl-2-furancarboxylic acid | |
| CN104761519A (en) | Method used for effective conversion of carbohydrate into 5-hydroxymethylfurfural in pure water | |
| CN107522612A (en) | A kind of catalyst acetate methanol condensation prepares acrylic acid（Ester）Method | |
| CN112657532A (en) | VO (volatile organic compound)2/g-C3N4Composite photocatalyst and preparation method and application thereof | |
| CN109400452A (en) | A kind of method that furan derivatives acid catalysis adds hydrogen 3- acetylpropyl alcohol and 1,4- pentanediol | |
| CN102500397B (en) | Preparation method for solid super acid catalyst for synthesis of levulinic acid and application of solid super acid catalyst |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |