CN113926447B - Niobium-loaded carbon nano tube solid acid catalyst and preparation method and application thereof - Google Patents

Niobium-loaded carbon nano tube solid acid catalyst and preparation method and application thereof Download PDF

Info

Publication number
CN113926447B
CN113926447B CN202111213494.8A CN202111213494A CN113926447B CN 113926447 B CN113926447 B CN 113926447B CN 202111213494 A CN202111213494 A CN 202111213494A CN 113926447 B CN113926447 B CN 113926447B
Authority
CN
China
Prior art keywords
niobium
solid acid
acid catalyst
nano tube
carbon nano
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
Application number
CN202111213494.8A
Other languages
Chinese (zh)
Other versions
CN113926447A (en
Inventor
叶俊
蒋剑春
赵剑
徐俊明
谭卫红
王奎
李静
夏海虹
陆海龙
王瑞珍
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Institute of Chemical Industry of Forest Products of CAF
Original Assignee
Institute of Chemical Industry of Forest Products of CAF
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Institute of Chemical Industry of Forest Products of CAF filed Critical Institute of Chemical Industry of Forest Products of CAF
Priority to CN202111213494.8A priority Critical patent/CN113926447B/en
Publication of CN113926447A publication Critical patent/CN113926447A/en
Application granted granted Critical
Publication of CN113926447B publication Critical patent/CN113926447B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/16—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
    • 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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/584—Recycling of catalysts

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Catalysts (AREA)
  • Carbon And Carbon Compounds (AREA)

Abstract

The invention discloses a niobium-loaded carbon nano tube 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 aqueous solution, and fully stirring; (3) Pouring the solution into a high-pressure reaction kettle, covering a kettle cover tightly, and raising the temperature of the reaction kettle to perform reaction; (4) Cooling and opening the reaction kettle after the reaction is finished, filtering and drying; (5) And (3) placing the obtained solid in a tubular reactor for calcination, and cooling to obtain the niobium-loaded carbon nano tube solid acid catalyst. The preparation method prepares the novel niobium-loaded carbon nano tube solid acid catalyst by hydrothermal and calcining loading of the niobium precursor and the carbon nano tube in a reaction kettle. 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 industrialized popularization.

Description

Niobium-loaded carbon nano tube solid acid catalyst and preparation method and application thereof
Technical Field
The invention belongs to the technical field of furfural production, and particularly relates to a niobium-loaded carbon nano tube 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 currently obtained by refining agricultural and forestry waste. Furfural can be converted into fuel and chemicals, and is widely applied to industries such as oil refining, plastics, pharmacy, agrochemicals 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 dilute acid (H) 2 SO 4 、HCl、H 3 PO 4 Acetic acid) and continuously synthesizing furfural under the catalysis of the catalyst. The preparation of the furfural by solvent liquefaction is usually carried out in a two-phase solvent, such as gamma-valerolactone/water, tetrahydrofuran/water and the like, and solid acid and metal salt are used as catalysts. Other solid acid catalysts such as SC-CaCt-700, H-ZSM-5, amorphous Nb 2 O 5 Etc. In the aspect of preparing furfural by pyrolysis, zinc chloride is mainly used as a catalyst, and other catalysts such as: h 2 SO 4 、H 3 PO 4 、H 3 BO 3 、(NH 4 ) 2 SO 4 、ZnCl 2 、NiCl 2 、MgCl 2 Etc., wherein Fe 2 (SO 4 ) 3 The best performance is achieved, and the furfural yield reaches 10wt%.
At present, a plurality of 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 oxidation energy, is a unique water-resistant solid acid with an acid strength of about (hc= -5.6-8.2) provided by surface-OH functionalityAcid position and NbO 4 Tetrahedra provide Lewis acid sites, and niobic acid exhibits high acid strength, thermal stability and sustained effective catalytic activity in reactions involving water (e.g., hydration, dehydration, hydrolysis, etc.). Carbon Nanotubes (CNTs) are a type of nanomaterial consisting of a two-dimensional hexagonal lattice of Carbon atoms that 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 such as electronics, optics, composite materials, nano technology, material science and the like. Research shows that carbon nanotubes have the advantages of improving mass transfer rate, reducing side reaction and target product selectivity in an organic phase in the hydrothermal conversion process of lignocellulose biomass. In view of the efficient catalytic performance and hydrothermal stability of the niobic acid, the carbon nano tube has good mass transfer efficiency and product selectivity, and the preparation of the novel solid acid catalyst by the niobic acid loaded carbon nano tube has very important significance for the existing chemical catalytic industry.
Disclosure of Invention
Aiming at the problems in the prior art, the technical problem to be solved by the invention is to provide a preparation method of a niobium-loaded carbon nano tube solid acid catalyst. The invention aims to provide a niobium-supported carbon nano tube solid acid catalyst. The invention also aims to provide an application of the niobium-loaded carbon nano tube solid acid catalyst in preparing furfural. The preparation method of the catalyst prepares the novel niobium-loaded carbon nano tube solid acid catalyst by hydrothermal and calcining loading of the niobium precursor and the carbon nano tube in a reaction kettle. 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 industrialized popularization.
In order to solve the problems, the technical scheme adopted by the invention is as follows:
the preparation method of the niobium-loaded carbon nano tube 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 lower than 1:1;
(2) Adding the carbon nano tube into the 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 a kettle cover, 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, drying at 30-200 ℃ for 0.5-72 h;
(5) Calcining the obtained solid in a tubular reactor at 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-loaded carbon nano tube 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 flow rate of the nitrogen is not lower than 1mL/min.
The preparation method of the niobium-loaded carbon nanotube solid acid catalyst comprises the step of preparing a niobium precursor, wherein the niobium precursor is any one of niobium ethoxide, niobium oxalate, niobium ammonium oxalate or niobium tartrate; the carbon nanotube is any one of a single-wall carbon nanotube, a double-wall carbon nanotube or a multi-wall carbon nanotube; the outer diameter of the carbon nano tube is 5-100 nm, and the mass ratio of the niobium precursor to the carbon nano tube is 0.01:1-0.8:1.
The mass ratio of the niobium precursor to water is 1:1-1:3000.
In the preparation method of the niobium-loaded carbon nano tube solid acid catalyst, the temperature of the reaction kettle is increased to 150-300 ℃ and the temperature is kept for 2-12 h.
The preparation method of the niobium-loaded carbon nano tube solid acid catalyst comprises the steps of drying at 50-150 ℃ for 2-24 hours.
The preparation method of the niobium-loaded carbon nano tube solid acid catalyst comprises the steps of calcining at 150-350 ℃ in air and at 150-900 ℃ in nitrogen; the calcination time is 0.5-6 hours.
The niobium-loaded carbon nano tube solid acid catalyst prepared by the method.
The application of the niobium-loaded carbon nano tube solid acid catalyst in preparing furfural.
The application of the niobium-loaded carbon nano tube solid acid catalyst in preparing furfural comprises the steps of adding the niobium-loaded carbon nano tube solid acid catalyst, xylose or xylan, water and toluene into a reaction kettle, increasing the temperature of the reaction kettle to 130-250 ℃, and reacting at constant temperature for 0.1-10 h under nitrogen pressure of 0.5-5 MPa; 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 solid acid catalyst is applied to preparing furfural, 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.
The beneficial effects are 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-loaded carbon nano tube solid acid catalyst is prepared by adopting a hydrothermal-calcining combined loading technology, so that the solid acid catalyst with high hydrothermal stability and high reaction activity is obtained.
(2) Aiming at the problems of low reuse efficiency and the like caused by easy polymerization, coking and the like of the existing solid acid catalyst and liquefied products, the carbon nano tube is innovatively adopted as a carrier to load, the selectivity and the yield of the liquefied products 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 graph of the thermogravimetric profile of a carbon nanotube, example 2, and example 6 solid acid catalyst.
Detailed Description
In order that the above-recited objects, features and advantages of the present invention will become more apparent, a more particular description of the invention will be rendered by reference to specific embodiments thereof. The calculation formula of xylose or xylan conversion and furfural yield in the examples is shown below:
wherein M is the mass, g and M of furfural in the aqueous phase 0 Xylose mass, g.
Wherein M is the mass, g and M of furfural in the aqueous phase 0 Xylan mass, g.
Example 1
The preparation method of the niobium-loaded carbon nano tube solid acid catalyst specifically comprises the following steps:
taking niobium ethoxide and a multiwall carbon nanotube 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 the niobium ethoxide to water is 1:3000) and the carbon nanotube into a reaction kettle. Setting the temperature at 150 ℃ for 6 hours, filtering after the reaction is cooled, and drying at 105 ℃ for 12 hours. And (3) calcining for 4 hours at the calcining temperature of 300 ℃ and under the nitrogen flow of 20mL/min, and cooling to obtain the niobium-loaded carbon nano tube solid acid catalyst.
The solid acid catalyst of the niobium-loaded carbon nano tube is used for preparing furfural by catalysis, and specifically comprises the following steps:
taking the niobium-loaded carbon nano tube solid acid catalyst, xylose, water and toluene according to the mass ratio of 0.5:1, and adding the mixture into a reaction kettle in a volume of 20mL (volume ratio of 1:3). The reaction temperature was set at 150℃for 6 hours and the nitrogen pressure was 1.5MPa, and the aqueous phase and toluene phase were taken out and quantitatively analyzed for xylose and furfural in the high performance liquid phase, respectively, and the xylose conversion and furfural yield were calculated, and the results were shown in Table 1.
Example 2
The preparation method of the niobium-loaded carbon nano tube solid acid catalyst specifically comprises the following steps:
taking niobium ethoxide and a multiwall carbon nanotube 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 the niobium ethoxide to water is 1:2000) and the carbon nanotube into a reaction kettle. Setting the temperature to 180 ℃ for 5 hours, filtering after the reaction is cooled, and drying at 105 ℃ for 12 hours. Calcination was carried out at 400℃for 4 hours under a nitrogen flow of 20 mL/min. Thermogravimetric analysis was performed on multi-walled carbon nanotubes and niobium-supported carbon nanotube solid acid catalysts, and the results are shown in fig. 1.
The solid acid catalyst of the niobium-loaded carbon nano tube is used for preparing furfural by catalysis, and specifically comprises the following steps:
taking the niobium-loaded carbon nano tube solid acid catalyst, xylose, water and toluene according to the mass ratio of 0.5:1, and adding the mixture into a reaction kettle in a volume of 20mL (volume ratio of 1:3). The reaction temperature was set at 150℃for 6 hours and the nitrogen pressure was 1.5MPa, and the aqueous phase and toluene phase were taken out and quantitatively analyzed for xylose and furfural in the high performance liquid phase, respectively, and the xylose conversion and furfural yield were calculated, and the results were shown in Table 1.
Example 3
The preparation method of the niobium-loaded carbon nano tube solid acid catalyst specifically comprises the following steps:
taking niobium tartrate and a multiwall carbon nanotube with the outer diameter of 10-20nm according to the mass ratio of 2:100, and adding a niobium tartrate aqueous solution (the mass ratio of niobium tartrate to water is 1:2500) and the carbon nanotube into a reaction kettle. Setting the temperature to 200 ℃ for 12 hours, filtering after the reaction is cooled, and drying at 105 ℃ for 12 hours. Calcination was carried out at 550℃for 4 hours under a nitrogen flow of 20 mL/min.
The solid acid catalyst of the niobium-loaded carbon nano tube is used for preparing furfural by catalysis, and specifically comprises the following steps:
taking the niobium-loaded carbon nano tube solid acid catalyst, xylose, water and toluene according to the mass ratio of 0.5:1, and adding the mixture into a reaction kettle in a volume of 20mL (volume ratio of 1:3). The reaction temperature was set at 170℃for 3 hours and the nitrogen pressure was 1.8MPa, and the aqueous phase and toluene phase were quantitatively analyzed for xylose and furfural in the high performance liquid phase, respectively, and the xylose conversion and furfural yield were calculated, and the results are shown in Table 1.
Example 4
The preparation method of the niobium-loaded carbon nano tube solid acid catalyst specifically comprises the following steps:
taking niobium tartrate and a multiwall carbon nanotube with the outer diameter of 20-40nm according to the mass ratio of 3:100, and adding a niobium tartrate aqueous solution (the mass ratio of niobium tartrate to water is 1:1500) and the carbon nanotube into a reaction kettle. Setting the temperature to 240 ℃ for 5 hours, filtering after the reaction is cooled, and drying at 105 ℃ for 12 hours. Calcination was carried out at 450℃for 4 hours under a nitrogen flow of 20 mL/min.
The solid acid catalyst of the niobium-loaded carbon nano tube is used for preparing furfural by catalysis, and specifically comprises the following steps:
taking the niobium-loaded carbon nano tube solid acid catalyst, xylose, water and toluene according to the mass ratio of 0.5:1, and adding the mixture into a reaction kettle in a volume of 20mL (volume ratio of 1:3). The reaction temperature was set at 170℃for 3 hours and the nitrogen pressure was 1.8MPa, and the aqueous phase and toluene phase were quantitatively analyzed for xylose and furfural in the high performance liquid phase, respectively, and the xylose conversion and furfural yield were calculated, and the results are shown in Table 1.
Example 5
The preparation method of the niobium-loaded carbon nano tube solid acid catalyst specifically comprises the following steps:
taking niobium tartrate and a multiwall carbon nanotube with the outer diameter of 30-80nm according to the mass ratio of 5:100, and adding a niobium tartrate aqueous solution (the mass ratio of niobium tartrate to water is 1:1000) and the carbon nanotube into a reaction kettle. Setting the temperature to 280 ℃ for 3 hours, filtering after the reaction is cooled, and drying at 105 ℃ for 12 hours. Calcination was carried out at 350℃for 4 hours under a nitrogen flow of 20 mL/min.
The solid acid catalyst of the niobium-loaded carbon nano tube is used for preparing furfural by catalysis, and specifically comprises the following steps:
taking the niobium-loaded carbon nano tube solid acid catalyst, xylan and water according to the mass ratio of 0.5:1, and adding 20mL (volume ratio of 1:3) of toluene into a reaction kettle. The reaction temperature of 170 ℃ and the time of 3 hours are set, the nitrogen pressure is 1.8MPa, the solution is taken out, the xylan and the furfural in the water phase and the toluene phase are respectively quantitatively analyzed by adopting a high-efficiency liquid phase, the xylose conversion rate and the furfural yield are calculated, and the results are shown in Table 1.
Example 6
The preparation method of the niobium-loaded carbon nano tube solid acid catalyst specifically comprises the following steps:
taking ammonium niobium oxalate and a multiwall carbon nanotube 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 nanotube into a reaction kettle. Setting the temperature to 200 ℃ for 10 hours, filtering after the reaction is cooled, and drying at 105 ℃ for 12 hours. Calcination was carried out at 600℃for 4 hours under a nitrogen flow of 20 mL/min.
Taking the niobium-loaded carbon nano tube solid acid catalyst, xylose, water and toluene according to the mass ratio of 0.5:1, and adding the mixture into a reaction kettle in a volume of 20mL (volume ratio of 1:3). Setting the reaction temperature to 170 ℃ for 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 furfural. And repeating 19 times, taking the niobium-loaded carbon nano tube solid acid catalyst, xylose and water according to the mass ratio of 0.5:1, and adding 20mL (volume ratio of 1:3) of toluene into the reaction kettle. Taking out the solution, respectively quantitatively analyzing xylose and furfural in the water phase and the toluene phase by adopting a high-efficiency liquid phase, and calculating xylose conversion rate and furfural yield, wherein the results are shown in Table 1. Thermogravimetric analysis of the catalyst reused multiple times was performed and the results are shown in figure 1.
FIG. 1 is a graph of thermal weight of carbon nanotubes, solid acid catalyst of examples 2 and 6, wherein the upper graph of the graph shows the increase in mass loss rate versus temperature (or time) versus weight change for carbon nanotubes, solid acid catalyst of example 2 and solid acid catalyst of example 6, and the graph of DTG shows the change rate of mass (dm/dt) versus temperature (or time). It can be seen from fig. 1 that both the carbon nanotubes and the solid acid catalyst have high thermal stability, and the weight loss is within 2% at room temperature to 800 ℃.
Example 7
The preparation method of the niobium-loaded carbon nano tube solid acid catalyst specifically comprises the following steps:
and (3) taking ammonium niobium oxalate and single-walled carbon nanotubes with the outer diameter of 1-2nm according to the mass ratio of 5:100, and adding a niobium tartrate aqueous solution (the mass ratio of niobium tartrate to water is 1:2500) and the single-walled carbon nanotubes into a reaction kettle. Setting the temperature to 200 ℃ for 4 hours, filtering after the reaction is cooled, and drying at 105 ℃ for 12 hours. Calcination was carried out at 550℃for 4 hours under a nitrogen flow of 20 mL/min.
The solid acid catalyst of the niobium-loaded carbon nano tube is used for preparing furfural by catalysis, and specifically comprises the following steps:
taking the niobium-loaded carbon nano tube solid acid catalyst, xylan and water according to the mass ratio of 0.5:1, and adding 20mL (volume ratio of 1:3) of toluene into a reaction kettle. The reaction temperature of 170 ℃ and the time of 3 hours are set, the nitrogen pressure is 1.8MPa, the solution is taken out, the xylan and the furfural in the water phase and the toluene phase are respectively quantitatively analyzed by adopting a high-efficiency liquid phase, the xylose conversion rate and the furfural yield are calculated, and the results are shown in Table 1.
Example 8
The preparation method of the niobium-loaded carbon nano tube solid acid catalyst specifically comprises the following steps:
adding a niobium oxalate aqueous solution (the mass ratio of niobium oxalate to water is 1:2500) and the double-wall carbon nano tube into a reaction kettle according to the mass ratio of 5:100, wherein the external diameter of the double-wall carbon nano tube is 2-4 nm. Setting the temperature to 200 ℃ for 8 hours, filtering after the reaction is cooled, and drying at 105 ℃ for 12 hours. Calcination was carried out at 550℃for 4 hours under a nitrogen flow of 20 mL/min.
The solid acid catalyst of the niobium-loaded carbon nano tube is used for preparing furfural by catalysis, and specifically comprises the following steps:
taking the niobium-loaded carbon nano tube solid acid catalyst, xylan and water according to the mass ratio of 0.5:1, and adding 20mL (volume ratio of 1:3) of toluene into a reaction kettle. Setting the reaction temperature to 170 ℃, setting the time to 3 hours, setting the nitrogen pressure to 1.8MPa, taking out the solution, respectively carrying out quantitative analysis on xylan and furfural in a high-efficiency liquid phase on a water phase and a toluene 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 different 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 (8)

1. The application of the niobium-loaded carbon nano tube solid acid catalyst in preparing furfural is characterized in that the preparation method of the niobium-loaded carbon nano tube 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 lower than 1:1;
(2) Adding the carbon nano tube into the 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 a kettle cover, 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, drying, wherein the drying temperature is 30-200 ℃ and the drying time is 0.5-72 h;
(5) Calcining the obtained solid in a tubular reactor at 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-loaded carbon nano tube solid acid catalyst; when air is introduced, the air flow is not lower than 1mL/min, and the calcination temperature is 150-600 ℃; when nitrogen is introduced, the flow rate of the nitrogen is not lower than 1mL/min.
2. The use of a niobium-supported carbon nanotube solid acid catalyst as claimed in claim 1 in the preparation of furfural, wherein the niobium precursor is any one of niobium ethoxide, niobium oxalate, niobium ammonium oxalate or niobium tartrate; the carbon nanotube is any one of a single-wall carbon nanotube, a double-wall carbon nanotube or a multi-wall carbon nanotube; the outer diameter of the carbon nano tube is 5-100 nm, and the mass ratio of the niobium precursor to the carbon nano tube is 0.01:1-0.8:1.
3. The application of the niobium-supported carbon nanotube solid acid catalyst according to claim 1 or 2 in preparing furfural, wherein the mass ratio of the niobium precursor to water is 1:1-1:3000.
4. The application of the niobium-supported carbon nanotube solid acid catalyst according to claim 1 or 2 in preparing furfural, wherein the temperature of the reaction kettle is raised to 150-300 ℃ and the reaction kettle is kept at the constant temperature for 2-12 h.
5. The application of the niobium-supported carbon nanotube solid acid catalyst according to claim 1 or 2 in preparing furfural, wherein the drying temperature is 50-150 ℃ and the constant temperature is 2-24 hours.
6. The application of the niobium-supported carbon nanotube solid acid catalyst according to claim 1 or 2 in preparing furfural, wherein the air calcination temperature is 150-350 ℃ and the nitrogen calcination temperature is 150-900 ℃; the calcination time is 0.5-6 hours.
7. The application of the niobium-supported carbon nanotube solid acid catalyst in preparing furfural, which 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 constant temperature reaction is carried out 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.
8. The application of the niobium-supported carbon nanotube solid acid catalyst in preparing 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 nitrogen pressure is 1-3 MPa, and the temperature is kept constant for 3-6 hours.
CN202111213494.8A 2021-10-19 2021-10-19 Niobium-loaded carbon nano tube solid acid catalyst and preparation method and application thereof Active CN113926447B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202111213494.8A CN113926447B (en) 2021-10-19 2021-10-19 Niobium-loaded carbon nano tube solid acid catalyst and preparation method and application thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202111213494.8A CN113926447B (en) 2021-10-19 2021-10-19 Niobium-loaded carbon nano tube solid acid catalyst and preparation method and application thereof

Publications (2)

Publication Number Publication Date
CN113926447A CN113926447A (en) 2022-01-14
CN113926447B true CN113926447B (en) 2023-12-05

Family

ID=79280435

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202111213494.8A Active CN113926447B (en) 2021-10-19 2021-10-19 Niobium-loaded carbon nano tube solid acid catalyst and preparation method and application thereof

Country Status (1)

Country Link
CN (1) CN113926447B (en)

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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
CN106732673A (en) * 2016-11-10 2017-05-31 常州大学 A kind of construction method of the solid acid catalyst with montmorillonite as carrier

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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
CN106732673A (en) * 2016-11-10 2017-05-31 常州大学 A kind of construction method of the solid acid catalyst with montmorillonite as carrier

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
"Comparison of impregnation and deposition precipitation for the synthesis of hydrothermally stable niobia/carbon";Haifeng Xiong等;《Applied Catalysis A: General》;第471卷;第165-174页 *
"Preparation and electrochemical properties of nanocable-like Nb2O5/surface-modified carbon nanotubes composites for anode materials in lithium ion batteries";Chongfu Shi等;《Electrochimica Acta》;第246卷;第1088-1096页 *

Also Published As

Publication number Publication date
CN113926447A (en) 2022-01-14

Similar Documents

Publication Publication Date Title
Hajipour et al. Multi walled carbon nanotubes supported N-heterocyclic carbene–cobalt (ΙΙ) as a novel, efficient and inexpensive catalyst for the Mizoroki–Heck reaction
CN102675072B (en) Method for producing acetophenone through catalytic oxidation of ethylbenzene
CN108455592B (en) Preparation method of nitrogen-doped porous carbon/carbon nanotube composite with interpenetrating network structure
CN111468121B (en) Preparation and application of MXene modified biomass carbon nano metal catalyst
CN102744102B (en) Metal modified SAPO-34 zeolite catalyst, preparation method thereof and use method thereof
CN105498817A (en) Catalyst for production of trimellitic anhydride and preparation method and application of catalyst
Wang et al. An efficient, soluble, and recyclable multiwalled carbon nanotubes-supported TEMPO for oxidation of alcohols
CN101239713A (en) Method of preparing multi-wall carbon nano-tube by using polymer as raw material
CN113926447B (en) Niobium-loaded carbon nano tube solid acid catalyst and preparation method and application thereof
CN111686730B (en) Preparation method and application of catalyst for synthesizing 2-phenylimidazole by Debus method
Nie et al. Preparation of Pd nanoparticles deposited on a polyaniline/multiwall carbon nanotubes nanocomposite and their application in the Heck reaction
CN105498801A (en) Preparation method of sulfated carbonized corn cob catalyst and method for preparing furfural from xylose in presence of catalyst
CN111644201A (en) L-proline/MWCNTs high-load catalyst and preparation method and application thereof
CN109879741B (en) Green and efficient method for producing benzaldehyde by catalytic oxidation of benzyl alcohol
CN101759596A (en) Method for preparing 3,4-dichloro-cyanobenzene
CN110759818A (en) Method for preparing acetophenone by catalytic oxidation of ethylbenzene by nitrogen-doped carbon nano tube
CN104069885A (en) Fe-CNx nano composite catalyst as well as preparation method and application thereof
CN103130748B (en) Cyclohexene oxidizing method
Yang et al. Attapulgite-anchored Pd complex catalyst: a highly active and reusable catalyst for C–C coupling reactions
CN114904531B (en) Supported non-noble metal monoatomic catalyst for oxidative dehydrogenation coupling reaction, and preparation method and application thereof
CN113813991B (en) Preparation method and application of phosphonic acid modified ruthenium metal loaded niobium-based oxide catalyst
CN104399507A (en) Vanadium catalyst and method utilizing vanadium catalyst to synthesize 2,3,5-trimethylbenzoquinone
CN104610014A (en) Method for preparing m-dichlorobenzene by catalyzing isomerization of p-dichlorobenzene by using nano ZSM-12 molecular sieve
CN102850169A (en) Method for manufacturing isobutene through isobutane dehydrogenation
CN103360251B (en) Method for catalytically synthesizing mono-butyl itaconate at high selectivity

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