CN113926447A - Niobium-supported carbon nanotube solid acid catalyst and preparation method and application thereof - Google Patents
Niobium-supported carbon nanotube solid acid catalyst and preparation method and application thereof Download PDFInfo
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 95
- 239000002041 carbon nanotube Substances 0.000 title claims abstract description 94
- 229910021393 carbon nanotube Inorganic materials 0.000 title claims abstract description 93
- 239000003054 catalyst Substances 0.000 title claims abstract description 85
- 239000011973 solid acid Substances 0.000 title claims abstract description 81
- 238000002360 preparation method Methods 0.000 title claims abstract description 42
- HYBBIBNJHNGZAN-UHFFFAOYSA-N furfural Chemical compound O=CC1=CC=CO1 HYBBIBNJHNGZAN-UHFFFAOYSA-N 0.000 claims abstract description 94
- 238000006243 chemical reaction Methods 0.000 claims abstract description 70
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 38
- 229910052758 niobium Inorganic materials 0.000 claims abstract description 30
- 239000010955 niobium Substances 0.000 claims abstract description 30
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 claims abstract description 30
- 238000001354 calcination Methods 0.000 claims abstract description 27
- 239000002243 precursor Substances 0.000 claims abstract description 18
- 238000001035 drying Methods 0.000 claims abstract description 16
- 238000001816 cooling Methods 0.000 claims abstract description 15
- 238000001914 filtration Methods 0.000 claims abstract description 12
- 238000000034 method Methods 0.000 claims abstract description 12
- 239000007787 solid Substances 0.000 claims abstract description 3
- 238000003756 stirring Methods 0.000 claims abstract description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 72
- SRBFZHDQGSBBOR-IOVATXLUSA-N D-xylopyranose Chemical compound O[C@@H]1COC(O)[C@H](O)[C@H]1O SRBFZHDQGSBBOR-IOVATXLUSA-N 0.000 claims description 58
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 56
- PYMYPHUHKUWMLA-UHFFFAOYSA-N arabinose Natural products OCC(O)C(O)C(O)C=O PYMYPHUHKUWMLA-UHFFFAOYSA-N 0.000 claims description 29
- SRBFZHDQGSBBOR-UHFFFAOYSA-N beta-D-Pyranose-Lyxose Natural products OC1COC(O)C(O)C1O SRBFZHDQGSBBOR-UHFFFAOYSA-N 0.000 claims description 29
- 229910052757 nitrogen Inorganic materials 0.000 claims description 28
- 229920001221 xylan Polymers 0.000 claims description 16
- 150000004823 xylans Chemical class 0.000 claims description 16
- GAGSVOVTFFOFFX-UHFFFAOYSA-D [Nb+5].[Nb+5].OC(C(O)C([O-])=O)C([O-])=O.OC(C(O)C([O-])=O)C([O-])=O.OC(C(O)C([O-])=O)C([O-])=O.OC(C(O)C([O-])=O)C([O-])=O.OC(C(O)C([O-])=O)C([O-])=O Chemical compound [Nb+5].[Nb+5].OC(C(O)C([O-])=O)C([O-])=O.OC(C(O)C([O-])=O)C([O-])=O.OC(C(O)C([O-])=O)C([O-])=O.OC(C(O)C([O-])=O)C([O-])=O.OC(C(O)C([O-])=O)C([O-])=O GAGSVOVTFFOFFX-UHFFFAOYSA-D 0.000 claims description 15
- 239000000243 solution Substances 0.000 claims description 11
- 239000007864 aqueous solution Substances 0.000 claims description 10
- 239000002048 multi walled nanotube Substances 0.000 claims description 9
- ZTILUDNICMILKJ-UHFFFAOYSA-N niobium(v) ethoxide Chemical compound CCO[Nb](OCC)(OCC)(OCC)OCC ZTILUDNICMILKJ-UHFFFAOYSA-N 0.000 claims description 8
- 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 claims description 5
- XFHGGMBZPXFEOU-UHFFFAOYSA-I azanium;niobium(5+);oxalate Chemical compound [NH4+].[Nb+5].[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O XFHGGMBZPXFEOU-UHFFFAOYSA-I 0.000 claims description 4
- 239000002079 double walled nanotube Substances 0.000 claims description 4
- 239000002109 single walled nanotube Substances 0.000 claims description 4
- 238000006555 catalytic reaction Methods 0.000 abstract description 4
- 238000004519 manufacturing process Methods 0.000 abstract description 4
- 239000012071 phase Substances 0.000 description 11
- 239000002253 acid Substances 0.000 description 9
- 239000008346 aqueous phase Substances 0.000 description 8
- 239000007791 liquid phase Substances 0.000 description 8
- 238000004445 quantitative analysis Methods 0.000 description 8
- 230000035484 reaction time Effects 0.000 description 7
- 230000003197 catalytic effect Effects 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 238000011068 loading method Methods 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 3
- 239000002028 Biomass Substances 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-N acetic acid Substances CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 2
- 238000004939 coking Methods 0.000 description 2
- GAEKPEKOJKCEMS-UHFFFAOYSA-N gamma-valerolactone Chemical compound CC1CCC(=O)O1 GAEKPEKOJKCEMS-UHFFFAOYSA-N 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 238000000197 pyrolysis Methods 0.000 description 2
- 238000007670 refining Methods 0.000 description 2
- 238000002411 thermogravimetry Methods 0.000 description 2
- 230000004580 weight loss Effects 0.000 description 2
- 239000011592 zinc chloride Substances 0.000 description 2
- 229920002488 Hemicellulose Polymers 0.000 description 1
- 239000002841 Lewis acid Substances 0.000 description 1
- 229910019792 NbO4 Inorganic materials 0.000 description 1
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 1
- 229920002522 Wood fibre Polymers 0.000 description 1
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 1
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000013064 chemical raw material Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 229910000360 iron(III) sulfate Inorganic materials 0.000 description 1
- 230000002045 lasting effect Effects 0.000 description 1
- 150000007517 lewis acids Chemical class 0.000 description 1
- 239000002029 lignocellulosic biomass Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L magnesium chloride Substances [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 1
- 229910001629 magnesium chloride Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- -1 nanotechnology Substances 0.000 description 1
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 1
- ZKATWMILCYLAPD-UHFFFAOYSA-N niobium pentoxide Inorganic materials O=[Nb](=O)O[Nb](=O)=O ZKATWMILCYLAPD-UHFFFAOYSA-N 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000002390 rotary evaporation Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 239000002025 wood fiber Substances 0.000 description 1
- 235000005074 zinc chloride Nutrition 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/20—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
- C07D307/48—Furfural
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- 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
- C07D307/48—Furfural
- C07D307/50—Preparation from natural products
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
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- Y02P20/584—Recycling of catalysts
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Abstract
The invention discloses a niobium-supported carbon nanotube solid acid catalyst, and a preparation method and application thereof, and belongs to the technical field of furfural production. The preparation method comprises the following steps: (1) dissolving a niobium precursor in water; (2) adding the carbon nano tube into the niobium precursor water solution, and fully stirring; (3) pouring the solution into a high-pressure reaction kettle, covering the kettle cover tightly, and raising the temperature of the reaction kettle for reaction; (4) cooling and opening the reaction kettle after the reaction is finished, filtering and drying; (5) and calcining the obtained solid in a tubular reactor, and cooling to obtain the niobium-supported carbon nanotube solid acid catalyst. The preparation method prepares the novel niobium-supported carbon nanotube solid acid catalyst by carrying niobium precursor and carbon nanotubes in a reaction kettle through hydrothermal and calcination. Meanwhile, the niobium-loaded carbon nanotube solid acid has the advantages of good thermal stability, high catalytic reaction efficiency, high reuse efficiency, simple process and easy realization of industrial popularization.
Description
Technical Field
The invention belongs to the technical field of furfural production, and particularly relates to a niobium-supported carbon nanotube solid acid catalyst and a preparation method and application thereof.
Background
Lignocellulosic biomass is considered as a potential alternative resource for the production of high value-added chemicals. Furfural, one of the 12 most valuable products listed by the U.S. department of energy, is the only chemical raw material obtained by refining agricultural and forestry waste completely at present. The furfural can be converted into fuels and chemicals and is widely applied to industries such as oil refining, plastics, pharmacy, agriculture and the like. Currently, furfural production and research methods include industrial continuous processes, solvent liquefaction and pyrolysis. The industrial production process of furfural mainly uses lignocellulose biomass hemicellulose as raw material and uses diluted acid (H)2SO4、HCl、H3PO4Acetic acid) under the catalysis of the furfural. The furfural solvent liquefaction preparation is generally carried out in a two-phase solvent, such as gamma-valerolactone/water and tetrahydrofuran/water, and a solid acid and a metal salt are adopted as catalysts. Other solid acid catalysts such as SC-CaCt-700, H-ZSM-5, amorphous Nb2O5And the like. In the aspect of preparing furfural by pyrolysis, zinc chloride is mainly used as a catalyst, and other catalysts such as: h2SO4、H3PO4、H3BO3、(NH4)2SO4、ZnCl2、NiCl2、MgCl2Etc. of Fe2(SO4)3The expression is optimal, and the furfural yield reaches 10 wt%.
Currently, many problems exist in the industrial preparation and research process of furfural, wherein liquid acid is adopted as a catalyst in the industrial production process, so that equipment is corroded; the conventional solid acid catalyst has the problems of low catalytic efficiency, poor hydrothermal stability of the catalyst, low reuse efficiency and the like. Niobic acid, also known as aqueous oxidative energy, is a unique water-resistant solid acid, having an acid strength of about (Hc ═ 5.6 to 8.2), provided by surface-OH functional groups
Acid sites and NbO4The tetrahedron provides Lewis acid site, and the niobic acid shows high acid strength, high thermal stability and lasting effective catalytic activity in the reaction with water (such as hydration, dehydration, hydrolysis and the like). Carbon Nanotubes (CNTs) are a class of nanomaterials consisting of a two-dimensional hexagonal lattice of Carbon atoms, which are bent in one direction and combined to form a hollow cylinder. The carbon nano tube has certain chemical stability, high electrical conductivity, excellent thermal conductivity, mechanical rigidity and tensile strength, and has higher application value in the fields of electronics, optics, composite materials, nanotechnology, material science and the like. Research shows that in the process of hydrothermal conversion of the wood fiber biomass, the carbon nano tube has the advantages of improving mass transfer rate, reducing side reaction and selectivity of target products in an organic phase. In view of the high-efficiency catalytic performance and hydrothermal stability of the niobic acid and the good mass transfer efficiency and product selectivity of the carbon nano tube, the preparation of the novel solid acid catalyst by the niobic acid loaded carbon nano tube has very important significance for the existing chemical catalysis industry.
Disclosure of Invention
Aiming at the problems in the prior art, the invention aims to provide a preparation method of a niobium-supported carbon nanotube solid acid catalyst. Another technical problem to be solved by the present invention is to provide a niobium-supported carbon nanotube solid acid catalyst. The invention also aims to solve the technical problem of providing an application of the niobium-supported carbon nanotube solid acid catalyst in preparation of furfural. The preparation method of the catalyst comprises the steps of carrying out hydrothermal and calcination loading on a niobium precursor and a carbon nano tube in a reaction kettle to prepare the novel niobium-loaded carbon nano tube solid acid catalyst. Meanwhile, the niobium-loaded carbon nanotube solid acid has the advantages of good thermal stability, high catalytic reaction efficiency, high reuse efficiency, simple process and easy realization of industrial popularization.
In order to solve the problems, the technical scheme adopted by the invention is as follows:
a preparation method of a niobium-supported carbon nanotube solid acid catalyst comprises the following specific steps:
(1) dissolving a niobium precursor in water, wherein the mass ratio of the niobium precursor to the water is not less than 1: 1;
(2) adding a carbon nano tube into a niobium precursor aqueous solution, fully stirring, wherein the outer diameter of the carbon nano tube is not higher than 100nm, and the mass ratio of the niobium precursor to the carbon nano tube is not higher than 1: 1;
(3) pouring the solution into a high-pressure reaction kettle, covering the kettle cover tightly, raising the temperature of the reaction kettle to 30-350 ℃, and keeping the temperature for 0.5-48 h;
(4) cooling and opening the reaction kettle, filtering, and drying at the drying temperature of 30-200 ℃ for 0.5-72 h;
(5) calcining the obtained solid in a tubular reactor at the temperature of 150-1000 ℃, and introducing air or nitrogen in the calcining process; calcining for not less than 0.5 hour, and cooling to obtain the niobium-supported carbon nanotube solid acid catalyst; when air is introduced, the air flow is not lower than 1mL/min, and the calcining temperature is 150-600 ℃; when nitrogen is introduced, the nitrogen flow rate is not lower than 1 mL/min.
According to the preparation method of the niobium-supported carbon nanotube solid acid catalyst, the niobium precursor is any one of niobium ethoxide, niobium oxalate, ammonium niobium oxalate or niobium tartrate; the carbon nano tube is any one of a single-wall carbon nano tube, a double-wall carbon nano tube or a multi-wall carbon nano tube; the carbon nanotube has an outer diameter of 5 to 100nm, and the mass ratio of the niobium precursor to the carbon nanotube is 0.01:1 to 0.8: 1.
According to the preparation method of the niobium-supported carbon nanotube solid acid catalyst, the mass ratio of the niobium precursor to water is 1: 1-1: 3000.
According to the preparation method of the niobium-supported carbon nanotube solid acid catalyst, the temperature of a reaction kettle is raised to 150-300 ℃, and the temperature is kept for 2-12 hours.
According to the preparation method of the niobium-supported carbon nanotube solid acid catalyst, the drying temperature is 50-150 ℃, and the temperature is kept for 2-24 hours.
According to the preparation method of the niobium-supported carbon nanotube solid acid catalyst, the air calcination temperature is 150-350 ℃, and the nitrogen calcination temperature is 150-900 ℃; the calcination time is 0.5-6 hours.
The niobium-supported carbon nanotube solid acid catalyst prepared by the method.
The niobium-supported carbon nanotube solid acid catalyst is applied to preparation of furfural.
The application of the niobium-supported carbon nanotube solid acid catalyst in preparation of furfural is characterized by adding the niobium-supported carbon nanotube solid acid catalyst, xylose or xylan, water and toluene into a reaction kettle, raising the temperature of the reaction kettle to 130-250 ℃, keeping the nitrogen pressure at 0.5-5 MPa, and carrying out constant-temperature reaction for 0.1-10 h; the mass ratio of the solid acid catalyst to xylose or xylan is 0.1: 1-2: 1, and the volume ratio of water to toluene is 1: 0.5-1: 10.
The application of the niobium-supported carbon nanotube solid acid catalyst in preparation of furfural is characterized in that the mass ratio of the solid acid catalyst to xylose or xylan is 0.25: 1-1: 1, the volume ratio of water to toluene is 1: 0.5-1: 4, the temperature of a reaction kettle is 150-200 ℃, the pressure of nitrogen is 1-3 MPa, and the temperature is kept for 3-6 hours.
Has the advantages that: compared with the prior art, the invention has the advantages that:
(1) aiming at the problems of poor hydrothermal stability and low catalytic efficiency of the existing solid acid catalyst, the niobium-supported carbon nanotube solid acid catalyst is prepared by adopting a hydrothermal-calcination combined loading technology to obtain the solid acid catalyst with high hydrothermal stability and high reaction activity.
(2) Aiming at the problems that the existing solid acid catalyst is easy to polymerize with a liquefied product, coking is easy to cause low reuse efficiency and the like, a carbon nano tube is innovatively adopted as a carrier loading form, so that the selectivity and the yield of the liquefied product are improved, the problems of polymerization, coking and the like are reduced, and the reuse efficiency of the catalyst is improved.
Drawings
Fig. 1 is a thermogravimetric plot of carbon nanotubes, example 2 and example 6 solid acid catalysts.
Detailed Description
In order to make the aforementioned objects, features and advantages of the present invention comprehensible, embodiments accompanied with examples are described in detail below. The calculation formulas of xylose or xylan conversion and furfural yield in the examples are as follows:
wherein M is the mass of furfural in the water phase, g, M0Is the mass of xylose, g.
Wherein M is the mass of furfural in the water phase, g, M0Is the xylan mass, g.
Example 1
The preparation method of the niobium-loaded carbon nanotube solid acid catalyst specifically comprises the following steps:
taking niobium ethoxide and a multi-wall carbon nano tube with the outer diameter of 5-15nm according to the mass ratio of 0.5:100, and adding a niobium ethoxide aqueous solution (the mass ratio of niobium ethoxide to water is 1:3000) and the carbon nano tube into a reaction kettle. Setting the temperature at 150 ℃ for 6 hours, cooling the reaction, filtering, and drying at 105 ℃ for 12 hours. And calcining for 4 hours at the calcining temperature of 300 ℃ and under the nitrogen flow of 20mL/min after drying, and cooling to obtain the niobium-supported carbon nanotube solid acid catalyst.
The preparation of furfural by using the niobium-supported carbon nanotube solid acid catalyst comprises the following specific steps:
adding niobium-supported carbon nanotube solid acid catalyst, xylose, water and toluene in a volume of 20mL (in a volume ratio of 1:3) into a reaction kettle according to a mass ratio of 0.5: 1. Setting the reaction temperature at 150 ℃, the reaction time at 6 hours and the nitrogen pressure at 1.5MPa, taking out the solution, carrying out quantitative analysis on the aqueous phase and the toluene phase by adopting xylose and furfural in the high-efficiency liquid phase respectively, and calculating the xylose conversion rate and the furfural yield, wherein the results are shown in Table 1.
Example 2
The preparation method of the niobium-loaded carbon nanotube solid acid catalyst specifically comprises the following steps:
taking niobium ethoxide and a multi-walled carbon nano tube with the outer diameter of 10-20nm according to the mass ratio of 1:100, and adding a niobium ethoxide aqueous solution (the mass ratio of niobium ethoxide to water is 1:2000) and the carbon nano tube into a reaction kettle. Setting the temperature at 180 ℃ for 5 hours, cooling the reaction, filtering, and drying at 105 ℃ for 12 hours. The calcination was carried out at 400 ℃ under a nitrogen flow of 20mL/min for 4 hours. Thermogravimetric analysis was performed on the multi-walled carbon nanotubes and the niobium-supported carbon nanotube solid acid catalyst, and the results are shown in fig. 1.
The preparation of furfural by using the niobium-supported carbon nanotube solid acid catalyst comprises the following specific steps:
adding niobium-supported carbon nanotube solid acid catalyst, xylose, water and toluene in a volume of 20mL (in a volume ratio of 1:3) into a reaction kettle according to a mass ratio of 0.5: 1. Setting the reaction temperature at 150 ℃, the reaction time at 6 hours and the nitrogen pressure at 1.5MPa, taking out the solution, carrying out quantitative analysis on the aqueous phase and the toluene phase by adopting xylose and furfural in the high-efficiency liquid phase respectively, and calculating the xylose conversion rate and the furfural yield, wherein the results are shown in Table 1.
Example 3
The preparation method of the niobium-loaded carbon nanotube solid acid catalyst specifically comprises the following steps:
according to the mass ratio of 2:100, taking niobium tartrate and a multi-wall carbon nano tube with the outer diameter of 10-20nm, and adding a niobium tartrate aqueous solution (the mass ratio of niobium tartrate to water is 1:2500) and the carbon nano tube into a reaction kettle. Setting the temperature at 200 ℃ for 12 hours, cooling the reaction, filtering, and drying at 105 ℃ for 12 hours. The calcination was carried out at 550 ℃ under a nitrogen flow of 20mL/min for 4 hours.
The preparation of furfural by using the niobium-supported carbon nanotube solid acid catalyst comprises the following specific steps:
adding niobium-supported carbon nanotube solid acid catalyst, xylose, water and toluene in a volume of 20mL (in a volume ratio of 1:3) into a reaction kettle according to a mass ratio of 0.5: 1. Setting the reaction temperature to be 170 ℃, the reaction time to be 3 hours and the nitrogen pressure to be 1.8MPa, taking out the solution, respectively carrying out quantitative analysis on the aqueous phase and the toluene phase by adopting xylose and furfural in the high-efficiency liquid phase, and calculating the xylose conversion rate and the furfural yield, wherein the results are shown in Table 1.
Example 4
The preparation method of the niobium-loaded carbon nanotube solid acid catalyst specifically comprises the following steps:
according to the mass ratio of 3:100, taking niobium tartrate and a multi-wall carbon nano tube with the outer diameter of 20-40nm, and adding a niobium tartrate aqueous solution (the mass ratio of niobium tartrate to water is 1:1500) and the carbon nano tube into a reaction kettle. Setting the temperature at 240 ℃ for 5 hours, cooling the reaction, filtering, and drying at 105 ℃ for 12 hours. The calcination was carried out at 450 ℃ under a nitrogen flow of 20mL/min for 4 hours.
The preparation of furfural by using the niobium-supported carbon nanotube solid acid catalyst comprises the following specific steps:
adding niobium-supported carbon nanotube solid acid catalyst, xylose, water and toluene in a volume of 20mL (in a volume ratio of 1:3) into a reaction kettle according to a mass ratio of 0.5: 1. Setting the reaction temperature to be 170 ℃, the reaction time to be 3 hours and the nitrogen pressure to be 1.8MPa, taking out the solution, respectively carrying out quantitative analysis on the aqueous phase and the toluene phase by adopting xylose and furfural in the high-efficiency liquid phase, and calculating the xylose conversion rate and the furfural yield, wherein the results are shown in Table 1.
Example 5
The preparation method of the niobium-loaded carbon nanotube solid acid catalyst specifically comprises the following steps:
according to the mass ratio of 5:100, taking niobium tartrate and a multi-wall carbon nano tube with the outer diameter of 30-80nm, and adding a niobium tartrate aqueous solution (the mass ratio of niobium tartrate to water is 1:1000) and the carbon nano tube into a reaction kettle. Setting the temperature at 280 ℃ for 3 hours, cooling the reaction, filtering, and drying at 105 ℃ for 12 hours. The calcination was carried out at 350 ℃ under a nitrogen flow of 20mL/min for 4 hours.
The preparation of furfural by using the niobium-supported carbon nanotube solid acid catalyst comprises the following specific steps:
adding niobium-supported carbon nanotube solid acid catalyst, xylan, water and toluene in a volume of 20mL (in a volume ratio of 1:3) into a reaction kettle according to a mass ratio of 0.5: 1. Setting the reaction temperature at 170 ℃, the reaction time at 3 hours and the nitrogen pressure at 1.8MPa, taking out the solution, carrying out quantitative analysis on the aqueous phase and the toluene phase by adopting xylan and furfural in the high-efficiency liquid phase respectively, and calculating the xylose conversion rate and the furfural yield, wherein the results are shown in Table 1.
Example 6
The preparation method of the niobium-loaded carbon nanotube solid acid catalyst specifically comprises the following steps:
taking ammonium niobium oxalate and a multi-wall carbon nano tube with the outer diameter of 50-100nm according to the mass ratio of 2:100, and adding a niobium tartrate aqueous solution (the mass ratio of niobium tartrate to water is 1:500) and the carbon nano tube into a reaction kettle. Setting the temperature at 200 ℃ for 10 hours, cooling the reaction, filtering, and drying at 105 ℃ for 12 hours. The calcination was carried out at 600 ℃ under a nitrogen flow of 20mL/min for 4 hours.
Adding niobium-supported carbon nanotube solid acid catalyst, xylose, water and toluene in a volume of 20mL (in a volume ratio of 1:3) into a reaction kettle according to a mass ratio of 0.5: 1. Setting the reaction temperature to 170 ℃, the time to 3 hours and the nitrogen pressure to 1.8MPa, taking out the solution, filtering to obtain a solid acid catalyst, and performing rotary evaporation to obtain the furfural. And repeating the steps for 19 times, and adding the niobium-supported carbon nanotube solid acid catalyst, xylose, water and toluene into the reaction kettle according to the mass ratio of 0.5:1, wherein the volume of the water and the toluene is 20mL (the volume ratio is 1: 3). Taking out the solution, and carrying out quantitative analysis on the aqueous phase and the toluene phase by adopting xylose and furfural in the high-efficiency liquid phase respectively, and calculating the xylose conversion rate and the furfural yield, wherein the results are shown in table 1. Thermogravimetric analysis was performed on the catalyst repeatedly used several times, and the results are shown in fig. 1.
FIG. 1 is thermogravimetric plots of carbon nanotubes, solid acid catalysts of example 2 and example 6, in which the upper curves in the graphs are the weight change dependence of the mass weight loss rate of carbon nanotubes, solid acid catalysts of example 2 and solid acid catalysts of example 6 on temperature (or time), and the DTG curve represents the change in mass (dm/dt) as a function of temperature (or time). From fig. 1, it can be found that the carbon nanotubes and the solid acid catalyst both have high thermal stability, and the weight loss between room temperature and 800 ℃ is within 2%.
Example 7
The preparation method of the niobium-loaded carbon nanotube solid acid catalyst specifically comprises the following steps:
ammonium niobium oxalate and a single-walled carbon nanotube with the outer diameter of 1-2nm are taken according to the mass ratio of 5:100, and a niobium tartrate aqueous solution (the mass ratio of niobium tartrate to water is 1:2500) and the single-walled carbon nanotube are added into a reaction kettle. Setting the temperature at 200 ℃ for 4 hours, cooling the reaction, filtering, and drying at 105 ℃ for 12 hours. The calcination was carried out at 550 ℃ under a nitrogen flow of 20mL/min for 4 hours.
The preparation of furfural by using the niobium-supported carbon nanotube solid acid catalyst comprises the following specific steps:
adding niobium-supported carbon nanotube solid acid catalyst, xylan, water and toluene in a volume of 20mL (in a volume ratio of 1:3) into a reaction kettle according to a mass ratio of 0.5: 1. Setting the reaction temperature at 170 ℃, the reaction time at 3 hours and the nitrogen pressure at 1.8MPa, taking out the solution, carrying out quantitative analysis on the aqueous phase and the toluene phase by adopting xylan and furfural in the high-efficiency liquid phase respectively, and calculating the xylose conversion rate and the furfural yield, wherein the results are shown in Table 1.
Example 8
The preparation method of the niobium-loaded carbon nanotube solid acid catalyst specifically comprises the following steps:
according to the mass ratio of 5:100, taking niobium oxalate and a double-walled carbon nano tube with the outer diameter of 2-4nm, and adding a niobium oxalate aqueous solution (the mass ratio of niobium oxalate to water is 1:2500) and the double-walled carbon nano tube into a reaction kettle. Setting the temperature at 200 ℃ for 8 hours, cooling the reaction, filtering, and drying at 105 ℃ for 12 hours. The calcination was carried out at 550 ℃ under a nitrogen flow of 20mL/min for 4 hours.
The preparation of furfural by using the niobium-supported carbon nanotube solid acid catalyst comprises the following specific steps:
adding niobium-supported carbon nanotube solid acid catalyst, xylan, water and toluene in a volume of 20mL (in a volume ratio of 1:3) into a reaction kettle according to a mass ratio of 0.5: 1. Setting the reaction temperature to be 170 ℃, the reaction time to be 3 hours and the nitrogen pressure to be 1.8MPa, taking out the solution, respectively carrying out quantitative analysis on the aqueous phase and the toluene phase by adopting xylan and furfural in the high-efficiency liquid phase, and calculating the xylose conversion rate and the furfural yield. The results are shown in Table 1.
TABLE 1 xylose/xylan conversion and Furfural yield in various examples
| Examples | 1 | 2 | 3 | 4 | 5 | 6 | 7 | 8 |
| Xylose/xylan conversion% | 90.5 | 91.5 | 99.3 | 99.8 | 99.9 | 99.5 | 99.7 | 99.8 |
| Furfural yield/%) | 50.3 | 53.2 | 80.5 | 88.5 | 75.3 | 70.6 | 78.5 | 85.3 |
Claims (10)
1. A preparation method of a niobium-supported carbon nanotube solid acid catalyst is characterized by comprising the following specific steps:
(1) dissolving a niobium precursor in water, wherein the mass ratio of the niobium precursor to the water is not less than 1: 1;
(2) adding a carbon nano tube into a niobium precursor aqueous solution, fully stirring, wherein the outer diameter of the carbon nano tube is not higher than 100nm, and the mass ratio of the niobium precursor to the carbon nano tube is not higher than 1: 1;
(3) pouring the solution into a high-pressure reaction kettle, covering the kettle cover tightly, raising the temperature of the reaction kettle to 30-350 ℃, and keeping the temperature for 0.5-48 h;
(4) cooling and opening the reaction kettle, filtering, and drying at the drying temperature of 30-200 ℃ for 0.5-72 h;
(5) calcining the obtained solid in a tubular reactor at the temperature of 150-1000 ℃, and introducing air or nitrogen in the calcining process; calcining for not less than 0.5 hour, and cooling to obtain the niobium-supported carbon nanotube solid acid catalyst; when air is introduced, the air flow is not lower than 1mL/min, and the calcining temperature is 150-600 ℃; when nitrogen is introduced, the nitrogen flow rate is not lower than 1 mL/min.
2. The method for preparing the niobium-supported carbon nanotube solid acid catalyst according to claim 1, wherein the niobium precursor is any one of niobium ethoxide, niobium oxalate, ammonium niobium oxalate or niobium tartrate; the carbon nano tube is any one of a single-wall carbon nano tube, a double-wall carbon nano tube or a multi-wall carbon nano tube; the carbon nanotube has an outer diameter of 5 to 100nm, and the mass ratio of the niobium precursor to the carbon nanotube is 0.01:1 to 0.8: 1.
3. The method for preparing the niobium-supported carbon nanotube solid acid catalyst according to claim 1 or 2, wherein the mass ratio of the niobium precursor to water is 1:1 to 1: 3000.
4. The preparation method of the niobium-supported carbon nanotube solid acid catalyst according to claim 1 or 2, wherein the temperature of the reaction kettle is raised to 150-300 ℃ and kept constant for 2-12 hours.
5. The preparation method of the niobium-supported carbon nanotube solid acid catalyst according to claim 1 or 2, wherein the drying temperature is 50-150 ℃ and the temperature is kept constant for 2-24 hours.
6. The method for preparing the niobium-supported carbon nanotube solid acid catalyst according to claim 1 or 2, wherein the air calcination temperature is 150 to 350 ℃, and the nitrogen calcination temperature is 150 to 900 ℃; the calcination time is 0.5-6 hours.
7. The niobium-supported carbon nanotube solid acid catalyst prepared by the method of claim 1 or 2.
8. Use of the niobium supported carbon nanotube solid acid catalyst of claim 7 in the preparation of furfural.
9. The application of the niobium-supported carbon nanotube solid acid catalyst in preparation of furfural according to claim 8 is characterized in that the niobium-supported carbon nanotube solid acid catalyst, xylose or xylan, water and toluene are added into a reaction kettle, the temperature of the reaction kettle is increased to 130-250 ℃, the nitrogen pressure is 0.5-5 MPa, and the reaction is carried out at a constant temperature for 0.1-10 hours; the mass ratio of the solid acid catalyst to xylose or xylan is 0.1: 1-2: 1, and the volume ratio of water to toluene is 1: 0.5-1: 10.
10. The application of the niobium-supported carbon nanotube solid acid catalyst in preparation of furfural according to claim 9 is characterized in that the mass ratio of the solid acid catalyst to xylose or xylan is 0.25: 1-1: 1, the volume ratio of water to toluene is 1: 0.5-1: 4, the temperature of a reaction kettle is 150-200 ℃, the nitrogen pressure is 1-3 MPa, and the temperature is kept for 3-6 hours.
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| CN103193623A (en) * | 2013-04-03 | 2013-07-10 | 四川大学 | Method for catalytic preparation of acetylpropionic acid in one step by using waste residues obtained by producing xylose |
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| CN103193623A (en) * | 2013-04-03 | 2013-07-10 | 四川大学 | Method for catalytic preparation of acetylpropionic acid in one step by using waste residues obtained by producing xylose |
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