CN113441163A - Preparation method and application of novel nitrogen-doped hydrothermal carbon-supported copper catalyst - Google Patents
Preparation method and application of novel nitrogen-doped hydrothermal carbon-supported copper catalyst Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 48
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 42
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 42
- 239000010949 copper Substances 0.000 title claims abstract description 42
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 238000006243 chemical reaction Methods 0.000 claims abstract description 33
- HYBBIBNJHNGZAN-UHFFFAOYSA-N furfural Chemical compound O=CC1=CC=CO1 HYBBIBNJHNGZAN-UHFFFAOYSA-N 0.000 claims abstract description 30
- 239000007790 solid phase Substances 0.000 claims abstract description 17
- 229910052751 metal Inorganic materials 0.000 claims abstract description 16
- 239000002184 metal Substances 0.000 claims abstract description 16
- 238000003763 carbonization Methods 0.000 claims abstract description 14
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229910052921 ammonium sulfate Inorganic materials 0.000 claims abstract description 13
- 235000011130 ammonium sulphate Nutrition 0.000 claims abstract description 13
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000000203 mixture Substances 0.000 claims abstract description 9
- 239000002028 Biomass Substances 0.000 claims abstract description 8
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 8
- 239000002699 waste material Substances 0.000 claims abstract description 6
- 238000005470 impregnation Methods 0.000 claims abstract description 4
- 239000002243 precursor Substances 0.000 claims abstract description 3
- 238000001035 drying Methods 0.000 claims description 22
- 239000000047 product Substances 0.000 claims description 17
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 13
- 229910052739 hydrogen Inorganic materials 0.000 claims description 13
- 239000001257 hydrogen Substances 0.000 claims description 13
- 235000005824 Zea mays ssp. parviglumis Nutrition 0.000 claims description 11
- 235000002017 Zea mays subsp mays Nutrition 0.000 claims description 11
- 235000005822 corn Nutrition 0.000 claims description 11
- 239000010902 straw Substances 0.000 claims description 10
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- 238000002156 mixing Methods 0.000 claims description 8
- 238000001291 vacuum drying Methods 0.000 claims description 8
- 238000001354 calcination Methods 0.000 claims description 6
- 239000012265 solid product Substances 0.000 claims description 4
- 239000012071 phase Substances 0.000 claims description 2
- 239000000243 solution Substances 0.000 claims 4
- 241000209149 Zea Species 0.000 claims 2
- 239000007864 aqueous solution Substances 0.000 claims 2
- 230000035484 reaction time Effects 0.000 claims 1
- XPFVYQJUAUNWIW-UHFFFAOYSA-N furfuryl alcohol Chemical compound OCC1=CC=CO1 XPFVYQJUAUNWIW-UHFFFAOYSA-N 0.000 abstract description 27
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 7
- 229910052799 carbon Inorganic materials 0.000 abstract description 7
- 230000000694 effects Effects 0.000 abstract description 7
- 238000000034 method Methods 0.000 abstract description 6
- 239000008346 aqueous phase Substances 0.000 abstract description 4
- 238000003837 high-temperature calcination Methods 0.000 abstract description 2
- 239000010970 precious metal Substances 0.000 abstract description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 12
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 12
- 238000010438 heat treatment Methods 0.000 description 12
- 239000007787 solid Substances 0.000 description 12
- 240000008042 Zea mays Species 0.000 description 9
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- 238000002791 soaking Methods 0.000 description 6
- 239000006228 supernatant Substances 0.000 description 6
- 239000000725 suspension Substances 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- YLQBMQCUIZJEEH-UHFFFAOYSA-N Furan Chemical compound C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 5
- 229910000510 noble metal Inorganic materials 0.000 description 3
- VQKFNUFAXTZWDK-UHFFFAOYSA-N 2-Methylfuran Chemical compound CC1=CC=CO1 VQKFNUFAXTZWDK-UHFFFAOYSA-N 0.000 description 2
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 229910052681 coesite Inorganic materials 0.000 description 2
- 229910052906 cristobalite Inorganic materials 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 238000010335 hydrothermal treatment Methods 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 229910052682 stishovite Inorganic materials 0.000 description 2
- 229910052905 tridymite Inorganic materials 0.000 description 2
- 229910017813 Cu—Cr Inorganic materials 0.000 description 1
- ZZZCUOFIHGPKAK-UHFFFAOYSA-N D-erythro-ascorbic acid Natural products OCC1OC(=O)C(O)=C1O ZZZCUOFIHGPKAK-UHFFFAOYSA-N 0.000 description 1
- 229920002488 Hemicellulose Polymers 0.000 description 1
- KDXKERNSBIXSRK-UHFFFAOYSA-N Lysine Natural products NCCCCC(N)C(O)=O KDXKERNSBIXSRK-UHFFFAOYSA-N 0.000 description 1
- 239000004472 Lysine Substances 0.000 description 1
- 229930003268 Vitamin C Natural products 0.000 description 1
- 239000001089 [(2R)-oxolan-2-yl]methanol Substances 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 238000006114 decarboxylation reaction Methods 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- HDNHWROHHSBKJG-UHFFFAOYSA-N formaldehyde;furan-2-ylmethanol Chemical compound O=C.OCC1=CC=CO1 HDNHWROHHSBKJG-UHFFFAOYSA-N 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 231100000086 high toxicity Toxicity 0.000 description 1
- 238000007327 hydrogenolysis reaction Methods 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229910052702 rhenium Inorganic materials 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- BSYVTEYKTMYBMK-UHFFFAOYSA-N tetrahydrofurfuryl alcohol Chemical compound OCC1CCCO1 BSYVTEYKTMYBMK-UHFFFAOYSA-N 0.000 description 1
- 235000019154 vitamin C Nutrition 0.000 description 1
- 239000011718 vitamin C Substances 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
- B01J37/084—Decomposition of carbon-containing compounds into carbon
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/10—Heat treatment in the presence of water, e.g. steam
-
- 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
- C07D307/42—Singly bound oxygen atoms
- C07D307/44—Furfuryl alcohol
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- Chemical Kinetics & Catalysis (AREA)
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- Thermal Sciences (AREA)
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Abstract
本发明提供一种新型氮掺杂水热碳负载铜催化剂的制备方法及其应用，涉及氮掺杂水热碳和铜基催化剂的制备和应用技术领域。本发明的氮掺杂水热碳负载铜金属催化剂以生物质废弃物为前驱体，与一定浓度的硫酸铵，钨酸铵混合，将混合物至于高压反应釜中进行水热炭化处理，反应后离心分离固相产物，即可得到氮掺杂水热碳。继而通过浸渍法负载铜，高温煅烧后即可得到氮掺杂的铜基催化剂，应用于水相催化糠醛加氢制备糠醇。该催化剂在水相反应中具有较高的活性，选择性和稳定性，且为非贵金属催化剂，具有成本低廉的优势。
The invention provides a preparation method and application of a novel nitrogen-doped hydrothermal carbon-supported copper catalyst, and relates to the technical field of preparation and application of nitrogen-doped hydrothermal carbon and copper-based catalysts. The nitrogen-doped hydrothermal carbon-supported copper metal catalyst of the present invention uses biomass waste as a precursor, is mixed with a certain concentration of ammonium sulfate and ammonium tungstate, and the mixture is placed in a high-pressure reactor for hydrothermal carbonization treatment, and centrifuged after the reaction. The nitrogen-doped hydrothermal carbon can be obtained by separating the solid-phase product. Then, copper is supported by impregnation method, and after high temperature calcination, a nitrogen-doped copper-based catalyst can be obtained, which is applied to the hydrogenation of furfural in aqueous phase to prepare furfuryl alcohol. The catalyst has high activity, selectivity and stability in the aqueous phase reaction, is a non-precious metal catalyst, and has the advantage of low cost.
Description
Technical Field
The invention provides a preparation method and application of a novel nitrogen-doped hydrothermal carbon-loaded copper metal catalyst, and relates to the technical field of preparation and application of nitrogen-doped hydrothermal carbon and copper-based catalysts.
Background
The design of a high-efficiency and high-selectivity catalytic process for efficiently converting biomass into fine chemicals and liquid fuels has important scientific significance. A number of researchers have reported that biomass-based cellulose and hemicellulose can be converted to furfural through hydrolysis-isomerization-dehydration processes. Furfuryl alcohol can be synthesized by taking furfural as a raw material and further adopting a catalytic hydrogenation means. Such products are widely used as intermediates in the synthesis of furan-based resins, furan-based fibers, lubricants, pharmaceuticals such as lysine and vitamin C. Therefore, starting from the furfural of a bio-based source, a non-petroleum route of preparing furfuryl alcohol by hydrogenation is selected, and the method has important research background and application prospect.
However, in the reaction for producing furfuryl alcohol by selective hydrogenation of furfural, side reactions such as hydrogenation of furan rings (to give tetrahydrofurfuryl alcohol), hydrogenolysis of furfuryl alcohol (to give 2-methylfuran), decarboxylation of furfuryl alcohol (to give furan) are always accompanied, and these significantly affect the selectivity of the reaction. The Cu-Cr system was the first system to be applied to this reaction, however, the high toxicity of Cr causes environmental pollution, which is a serious problem. A range of precious and non-precious metal systems have been developed. The noble metal has too high hydrogenation activity and no strict requirement on reaction conditions, but usually a second component is added to weaken the activity, such as Ir/SiO2And Pt/SiO2After the Re or Ti component is added, the selectivity of the furfuryl alcohol is respectively improved by 30 percent and 80 percent. From the viewpoint of cost and reserves, the cheap metal has the advantages of moderate activity and relatively controllable selectivity. However, due to the moderate activity of inexpensive catalysts, the reaction system is generally required to perform well at high temperature. But furfural furfuryl in high temperature aqueous solutionThe alcohols are very susceptible to polymerization, so these inexpensive metal systems are essentially carried out in organic solvents to avoid polymerization side reactions, and the harsh conditions are accompanied by agglomeration or loss of the inexpensive metal. In contrast, water is a green and environment-friendly solvent, and the problem to be solved is still how to design a high-efficiency and high-stability cheap metal catalyst, and how to synthesize furfuryl alcohol by selective hydrogenation of furfural under the catalysis of a water phase.
In order to achieve the purpose, the invention adopts the following technical scheme: a preparation method and application of a novel nitrogen-doped hydrothermal carbon-loaded copper metal catalyst are characterized by being prepared by the following steps: step (1): mixing biomass waste corn straws serving as a precursor with ammonium sulfate and ammonium tungstate solution with certain concentration, and placing the mixture in a high-pressure reaction kettle for hydrothermal carbonization treatment at the carbonization temperature of 200-250 ℃ for 0.5-6 h; step (2): centrifuging the solid-phase product after reaction, and drying the solid-phase product in a vacuum drying oven to constant weight; and (3): impregnating the obtained solid product with a copper nitrate solution with a certain concentration, and drying to constant weight; and (4): and placing the solid product in a muffle furnace, and calcining at a high temperature to obtain the nitrogen-doped copper-based catalyst, wherein the calcining temperature is 400-.
The invention has the beneficial effects that: the method comprises the steps of co-hydrothermal treatment of waste biomass corn straws and an ammonium sulfate solution to obtain nitrogen-doped hydrothermal carbon rich in acidic active sites, dipping copper metal, and calcining at high temperature to obtain the nitrogen-doped copper-based catalyst. The catalyst has high activity, selectivity and stability in aqueous phase reaction, is a non-noble metal catalyst, and has the advantage of low cost.
Drawings
FIG. 1 is a flow chart used in example 1;
FIG. 2 is the conversion of furfural and the selectivity of furfuryl alcohol for examples 1-6.
Detailed Description
The embodiments of the present invention will be described more fully hereinafter with reference to the accompanying drawings, in which some, but not all embodiments of the invention are shown. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
(1) Mixing 10g of corn straws, 10g of ammonium sulfate solution and ammonium tungstate solution with the concentration of 0.1 mol/L, placing the mixture in a high-pressure reaction kettle, and carrying out hydrothermal carbonization treatment for 1 h at 200 ℃;
(2) centrifuging the solid-phase product after reaction, and drying the solid-phase product in a vacuum drying oven to constant weight;
(3) soaking the solid and 1mol/L copper nitrate solution in the same volume, drying in shade at room temperature for 12 h, and then placing in an oven at 80 ℃ for drying to constant weight;
(4) putting the solid in a muffle furnace, heating to 600 ℃ at the heating rate of 20 ℃/min, and preserving heat for 1 h to obtain a nitrogen-doped copper-based catalyst;
(5) reducing the nitrogen-doped copper-based catalyst for 1 h at 600 ℃ in a hydrogen atmosphere under the protection of nitrogen;
(6) adding 0.1g of furfural, 5.0g of water and 20mg of nitrogen-doped copper-based catalyst into a reaction kettle, reacting at 100 ℃ under the hydrogen pressure of 1MPa for 2 h, taking out the suspension, centrifuging, taking the supernatant, adding acetone to dilute by 10 times, and testing by GC-MS.
Example 2
(1) Mixing 10g of corn straws, 10g of ammonium sulfate solution and ammonium tungstate solution with the concentration of 0.1 mol/L, placing the mixture in a high-pressure reaction kettle, and carrying out hydrothermal carbonization treatment for 3 hours at 200 ℃;
(2) centrifuging the solid-phase product after reaction, and drying the solid-phase product in a vacuum drying oven to constant weight;
(3) soaking the solid and 1mol/L copper nitrate solution in the same volume, drying in shade at room temperature for 12 h, and then drying in an oven at 80 ℃ to constant weight;
(4) putting the solid in a muffle furnace, heating to 600 ℃ at the heating rate of 20 ℃/min, and preserving heat for 1 h to obtain a nitrogen-doped copper-based catalyst;
(5) reducing the nitrogen-doped copper-based catalyst for 1 h at 600 ℃ in a hydrogen atmosphere under the protection of nitrogen;
(6) adding 0.1g of furfural, 5.0g of water and 20mg of nitrogen-doped copper-based catalyst into a reaction kettle, reacting at 100 ℃ under the hydrogen pressure of 1MPa for 2 h, taking out the suspension, centrifuging, taking the supernatant, adding acetone to dilute by 10 times, and testing by GC-MS.
Example 3
(1) Mixing 10g of corn straws, 10g of ammonium sulfate solution and ammonium tungstate solution with the concentration of 0.1 mol/L, placing the mixture in a high-pressure reaction kettle, and carrying out hydrothermal carbonization treatment for 6 hours at 200 ℃;
(2) centrifuging the solid-phase product after reaction, and drying the solid-phase product in a vacuum drying oven to constant weight;
(3) soaking the solid and 1mol/L copper nitrate solution in the same volume, drying in shade at room temperature for 12 h, and then drying in an oven at 80 ℃ to constant weight;
(4) putting the solid in a muffle furnace, heating to 600 ℃ at the heating rate of 20 ℃/min, and preserving heat for 1 h to obtain a nitrogen-doped copper-based catalyst;
(5) reducing the nitrogen-doped copper-based catalyst for 1 h at 600 ℃ in a hydrogen atmosphere under the protection of nitrogen;
(6) adding 0.1g of furfural, 5.0g of water and 20mg of nitrogen-doped copper-based catalyst into a reaction kettle, reacting at 100 ℃ under the hydrogen pressure of 1MPa for 2 h, taking out the suspension, centrifuging, taking the supernatant, adding acetone to dilute by 10 times, and testing by GC-MS.
Example 4
(1) Mixing 10g of corn straws, 10g of ammonium sulfate solution and ammonium tungstate solution with the concentration of 0.1 mol/L, placing the mixture in a high-pressure reaction kettle, and carrying out hydrothermal carbonization treatment for 1 h at 250 ℃;
(2) centrifuging the solid-phase product after reaction, and drying the solid-phase product in a vacuum drying oven to constant weight;
(3) soaking the solid and 1mol/L copper nitrate solution in the same volume, drying in shade at room temperature for 12 h, and then drying in an oven at 80 ℃ to constant weight;
(4) putting the solid in a muffle furnace, heating to 600 ℃ at the heating rate of 20 ℃/min, and preserving heat for 1 h to obtain a nitrogen-doped copper-based catalyst;
(5) reducing the nitrogen-doped copper-based catalyst for 1 h at 600 ℃ in a hydrogen atmosphere under the protection of nitrogen;
(6) adding 0.1g of furfural, 5.0g of water and 20mg of nitrogen-doped copper-based catalyst into a reaction kettle, reacting at 100 ℃ under the hydrogen pressure of 1MPa for 2 h, taking out the suspension, centrifuging, taking the supernatant, adding acetone to dilute by 10 times, and testing by GC-MS.
Example 5
(1) Mixing 10g of corn straws, 10g of ammonium sulfate solution and ammonium tungstate solution with the concentration of 0.1 mol/L, placing the mixture in a high-pressure reaction kettle, and carrying out hydrothermal carbonization treatment for 3 hours at 250 ℃;
(2) centrifuging the solid-phase product after reaction, and drying the solid-phase product in a vacuum drying oven to constant weight;
(3) soaking the solid and 1mol/L copper nitrate solution in the same volume, drying in shade at room temperature for 12 h, and then drying in an oven at 80 ℃ to constant weight;
(4) putting the solid in a muffle furnace, heating to 600 ℃ at the heating rate of 20 ℃/min, and preserving heat for 1 h to obtain a nitrogen-doped copper-based catalyst;
(5) reducing the nitrogen-doped copper-based catalyst for 1 h at 600 ℃ in a hydrogen atmosphere under the protection of nitrogen;
(6) adding 0.1g of furfural, 5.0g of water and 20mg of nitrogen-doped copper-based catalyst into a reaction kettle, reacting at 100 ℃ under the hydrogen pressure of 1MPa for 2 h, taking out the suspension, centrifuging, taking the supernatant, adding acetone to dilute by 10 times, and testing by GC-MS.
Example 6
(1) Mixing 10g of corn straws, 10g of ammonium sulfate solution and ammonium tungstate solution with the concentration of 0.1 mol/L, placing the mixture in a high-pressure reaction kettle, and carrying out hydrothermal carbonization treatment for 6 hours at 250 ℃;
(2) centrifuging the solid-phase product after reaction, and drying the solid-phase product in a vacuum drying oven to constant weight;
(3) soaking the solid and 1mol/L copper nitrate solution in the same volume, drying in shade at room temperature for 12 h, and then drying in an oven at 80 ℃ to constant weight;
(4) putting the solid in a muffle furnace, heating to 600 ℃ at the heating rate of 20 ℃/min, and preserving heat for 1 h to obtain a nitrogen-doped copper-based catalyst;
(5) reducing the nitrogen-doped copper-based catalyst for 1 h at 600 ℃ in a hydrogen atmosphere under the protection of nitrogen;
(6) adding 0.1g of furfural, 5.0g of water and 20mg of nitrogen-doped copper-based catalyst into a reaction kettle, reacting at 100 ℃ under the hydrogen pressure of 1MPa for 2 h, taking out the suspension, centrifuging, taking the supernatant, adding acetone to dilute by 10 times, and testing by GC-MS.
The invention has the beneficial effects that: the method comprises the steps of co-hydrothermal treatment of waste biomass corn straws, ammonium sulfate and ammonium tungstate solution to obtain nitrogen-doped hydrothermal carbon rich in acidic active sites, impregnation of copper metal, and high-temperature calcination to obtain the nitrogen-doped copper-based catalyst. The catalyst has high activity, selectivity and stability in aqueous phase reaction, is a non-noble metal catalyst, and has the advantage of low cost.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, but rather as the subject matter of the invention is to cover all modifications, equivalents, and alternatives falling within the spirit and scope of the invention as defined by the appended claims.
Claims (9)
1. A preparation method and application of a novel nitrogen-doped hydrothermal carbon-supported copper catalyst are characterized by being prepared by the following steps:
step (1): mixing biomass waste corn straws serving as a precursor with ammonium sulfate and ammonium tungstate solution with certain concentration, and placing the mixture in a high-pressure reaction kettle for hydrothermal carbonization treatment at the carbonization temperature of 200-250 ℃ for 0.5-6 h;
step (2): centrifuging the solid-phase product after reaction, and drying the solid-phase product in a vacuum drying oven to constant weight;
and (3): impregnating the obtained solid product with a copper nitrate solution with a certain concentration, and drying to constant weight;
and (4): and placing the solid product in a muffle furnace, and calcining at high temperature to obtain the nitrogen-doped copper-based catalyst.
2. The calcination temperature is 400-.
3. The preparation method and the application of the novel nitrogen-doped hydrothermal carbon-supported copper metal catalyst according to claim 1, wherein the concentration of the ammonium sulfate solution in the step (1) is 0.01-1 mol/L, and the concentration of ammonium tungstate is 0.01-1 mol/L.
4. The preparation method and the application of the novel nitrogen-doped hydrothermal carbon-supported copper metal catalyst according to claim 1 are characterized in that the raw biomass waste corn stalks in the step (1) and an ammonium sulfate aqueous solution and an ammonium tungstate aqueous solution are subjected to hydrothermal carbonization reaction according to a ratio of 1:1: 1.
5. The preparation method and the application of the novel nitrogen-doped hydrothermal carbon-supported copper metal catalyst as claimed in claim 1, wherein the carbonization temperature in the step (1) is 200-250 ℃, and the carbonization time is 0.5-6 h.
6. The preparation method and the application of the novel nitrogen-doped hydrothermal carbon-supported copper metal catalyst according to claim 1, wherein the concentration of the copper nitrate solution in the step (3) is 0.5-1 mol/L.
7. The preparation method and the application of the novel nitrogen-doped hydrothermal carbon-supported copper metal catalyst according to claim 1, wherein the impregnation in the step (3) is carried out and then the impregnation is carried out for 6-24 h in the shade at room temperature.
8. The preparation method and the application of the novel nitrogen-doped hydrothermal carbon-supported copper metal catalyst as claimed in claim 1, wherein the calcination temperature in the step (4) is 400-.
9. The preparation method and the application of the novel nitrogen-doped hydrothermal carbon-supported copper metal catalyst according to claim 1 are characterized in that the catalyst is applied to a hydrogenation reaction of furfural in a water phase, wherein the hydrogenation reaction temperature is 30-100 ℃, the reaction time is 0.5-12 h, and the hydrogen pressure is 0.2-4 MPa.
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