CN114405500A - V-Al nano fiber catalyst and preparation method and application thereof - Google Patents

V-Al nano fiber catalyst and preparation method and application thereof Download PDF

Info

Publication number
CN114405500A
CN114405500A CN202210059099.7A CN202210059099A CN114405500A CN 114405500 A CN114405500 A CN 114405500A CN 202210059099 A CN202210059099 A CN 202210059099A CN 114405500 A CN114405500 A CN 114405500A
Authority
CN
China
Prior art keywords
methyl formate
methanol
catalyst
oxygen
inert gas
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.)
Pending
Application number
CN202210059099.7A
Other languages
Chinese (zh)
Inventor
孙予罕
王慧
马春辉
陈佳煜
阚显
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.)
Shanghai Cluster Rui Low Carbon Energy Technology Co ltd
Original Assignee
Shanghai Cluster Rui Low Carbon Energy Technology Co ltd
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 Shanghai Cluster Rui Low Carbon Energy Technology Co ltd filed Critical Shanghai Cluster Rui Low Carbon Energy Technology Co ltd
Priority to CN202210059099.7A priority Critical patent/CN114405500A/en
Publication of CN114405500A publication Critical patent/CN114405500A/en
Pending legal-status Critical Current

Links

Images

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
    • B01J35/58—Fabrics or filaments
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/002—Mixed oxides other than spinels, e.g. perovskite
    • 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
    • B01J23/22—Vanadium
    • 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
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/40—Catalysts, in general, characterised by their form or physical properties characterised by dimensions, e.g. grain size
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C07C67/39—Preparation of carboxylic acid esters by oxidation of groups which are precursors for the acid moiety of the ester

Landscapes

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

Abstract

The invention provides a V-Al nano-fiber catalyst and a preparation method and application thereof. The V-Al nanofiber catalyst comprises V2O5And Al2O3The mass ratio is 2: 98-80: 20, the catalyst is in the form of nanofibers. The preparation method comprises the following steps: carrying out electrostatic spinning and roasting on a mixed solution containing a V source and an Al source; the mixed solution also contains a high molecular polymer and a solvent. The application of the catalyst in preparing methyl formate by oxidizing methanol. Methanol and oxygen-containing inert gas react in the presence of a catalyst to obtain methyl formate. The V-Al sodium saltThe rice fiber catalyst has the advantages of large specific surface area, high porosity, uniform nanometer size and good sintering resistance, and the space velocity is 600-60000 ml.g in the reaction of preparing methyl formate by oxidizing methanol‑1·h‑1During the process, the conversion rate of the methanol is 60-99%, the selectivity of the methyl formate is 75-99%, and the one-way service life of the catalyst is more than 1000 h.

Description

V-Al nano fiber catalyst and preparation method and application thereof
Technical Field
The invention relates to the technical field of methyl formate preparation by methanol oxidation, in particular to a V-Al nanofiber catalyst and a preparation method and application thereof.
Background
Methyl Formate (MF) is an important intermediate in carbon-one chemistry, has wide application, can be used as a raw material for organic synthesis, and can be used for preparing formic acid, formamide and the like; can be used for producing products such as insecticide, military poison gas and solvent; can be used as cellulose nitrate, cellulose acetate solvent, fumigation insecticide and bactericide; can be used as bactericide, fumigant, and tobacco treatment. The existing industrial production methods of methyl formate mainly comprise a methanol dehydrogenation method, a formic acid esterification method, a methanol liquid phase hydroxylation method, a method for directly synthesizing methyl formate by using synthesis gas and the like. The formic acid esterification method has high cost and serious corrosion to equipment; the methanol dehydrogenation method has low yield and poor product selectivity; the direct synthesis method of the synthesis gas has low efficiency and high equipment requirement; the methanol carbonylation process requires the use of relatively expensive anhydrous methanol and high concentrations of CO greater than 80%. The methyl formate prepared by one-step oxidation of methanol overcomes the defects of the method, can be developed into a green and economic method for preparing methyl formate, and has very wide application prospect. Catalyst S-V used for preparing methyl formate by one-step oxidation of methanol2O5/TiO2(VTS) has excellent reaction performance, but the catalyst has low specific surface area and low space velocity, so that the productivity is low, and the S component in the catalyst is easy to pollute the environment.
Chinese patent CN101327444A adopts V2O5/TiO2The catalyst is used for synthesizing methylal and methyl formate, but the preparation process of the catalyst is complex and generates a large amount of waste water. The catalyst has the advantages of low specific surface area, small reaction space velocity and low productivity.
Disclosure of Invention
In view of the disadvantages of the prior art, the present invention aims to provide a V-Al fiber catalyst for preparing methyl formate by oxidizing methanol, a preparation method and a use thereof, which overcome the problem of low productivity due to low reaction space velocity.
To achieve the above and other related objects, the present invention provides, in a first aspect, a V-Al nanofiber catalyst comprising V2O5And Al2O3，V2O5And Al2O3The mass ratio of (A) to (B) is 2: 98-80: 20, as shown in 2: 98-20: 80. 20: 80-30: 70. 30: 70-50: 50. 50: 50-60: 40. 60: 40-70: 30 or 70: 30-80: 20, the V-Al nano fiber catalyst is in a nano fiber shape.
Preferably, the fiber diameter of the V-Al nanofiber catalyst is 50-200 nm.
The second aspect of the present invention provides a method for preparing the above V-Al nanofiber catalyst, comprising the steps of:
1) carrying out electrostatic spinning on a mixed solution containing a V source and an Al source to obtain V-Al nano fibers;
2) roasting the V-Al nano-fiber to obtain a V-Al nano-fiber catalyst;
wherein the mixed solution further contains a high molecular polymer and a solvent.
The mixed solution containing the V source and the Al source can be obtained by the following steps: mixing the V source, the Al source, the high molecular polymer and the solvent, and uniformly stirring. Specifically, the stirring speed may be 300-2000 rpm, such as 300-400 rpm, 400-500 rpm, 500-600 rpm or 600-2000 rpm.
Preferably, at least one of the following technical features is also included:
1a) in the step 1), the solvent is water or an organic solvent;
1b) in the step 1), the mass ratio of the solvent to the high molecular polymer is 85: 15-95: 5, such as 85: 15-87: 13. 87: 13-88: 12. 88: 12-90: 10. 90: 10-91: 9. 91: 9-92: 8 or 92: 8-95: 5;
1c) in step 1), the V source is selected from V2O5、VOSO4、NH4VO3And vanadyl acetylacetonate;
1d) in the step 1), the Al source is at least one selected from aluminum chloride, aluminum sulfate and sodium metaaluminate;
1e) in the step 1), the high molecular polymer is selected from at least one of polyvinyl alcohol, polyethylene glycol and polyvinylpyrrolidone;
1f) in the step 1), V in the mixed solution accounts for 0.1-5% of the total mass of the solvent and the high molecular polymer, such as 0.1-1%, 1-2.5%, 2.5-3%, 3-3.5%, 3.5-4% or 4-5%;
1g) in the step 1), Al in the mixed solution accounts for 0.73-6.62% of the total mass of the solvent and the high molecular polymer, such as 0.73-1.18%, 1.18-1.42%, 1.42-2.36%, 2.36-2.52%, 2.52-6.06% or 6.06-6.62%;
1h) in the step 1), electrostatic spinning is carried out under the condition that the relative humidity is 15-70%, such as 15-40%, 40-42%, 42-45% or 45-70%;
1i) in the step 1), electrostatic spinning is carried out at the temperature of 15-70 ℃, such as 15-25 ℃, 25-28 ℃, 28-30 ℃ or 30-70 ℃;
1j) in the step 1), the positive voltage of electrostatic spinning is 10-60 kV, such as 10-12 kV, 12-20 kV, 20-30 kV, 30-45 kV, 45-55 kV and 55-60 kV;
1k) in the step 1), the negative voltage of electrostatic spinning is 10-60 kV, such as 10-12 kV, 12-20 kV, 20-30 kV, 30-45 kV, 45-55 kV and 55-60 kV;
1l) in the step 1), the distance of electrostatic spinning is 5-50 cm, such as 5-10 cm, 10-15 cm, 15-20 cm, 20-30 cm or 30-50 cm;
2a) in step 2), the roasting temperature is 300-600 ℃, such as 300-400 ℃, 400-450 ℃, 450-500 ℃ or 500-600 ℃;
2b) in the step 2), the roasting time is 1-20 hours, such as 1-2 hours, 2-3 hours, 3-4 hours, 4-5 hours, 5-10 hours or 10-20 hours.
More preferably, at least one of the following technical characteristics is also included:
1a1) in the feature 1a), the organic substance is at least one selected from the group consisting of tetrahydrofuran, benzene, toluene, N-methylpyrrolidone, and N, N-dimethylformamide;
1f1) in the characteristic 1f), V in the mixed solution accounts for 0.5-2.5% of the total mass of the solvent and the high molecular polymer;
1g1) the preparation method is characterized in that in 1g), Al in the mixed solution accounts for 0.73-5% of the total mass of the solvent and the high molecular polymer;
2b1) in the step 2b), the roasting time is 2-10 h.
The third aspect of the invention provides the application of the V-Al nanofiber catalyst in preparing methyl formate by oxidizing methanol.
Preferably, at least one of the following technical features is also included:
a1) before being used for preparing methyl formate by oxidizing methanol, activating the catalyst;
a2) the reaction temperature for preparing methyl formate by methanol oxidation is 100-200 ℃, such as 100-135 ℃, 135-140 ℃, 140-150 ℃ or 150-200 ℃;
a3) the reaction pressure for preparing methyl formate by methanol oxidation is 0.1-2.0 Mpa, such as 0.1-0.5 Mpa, 0.5-1 Mpa or 1-2.0 Mpa;
a4) the reaction space velocity for preparing methyl formate by oxidizing methanol is 600-60000 ml-g-1·h-1E.g. 600-2400 ml g-1·h-1、2400～3000ml·g-1·h-1、3000～8000ml·g-1·h-1、8000～12000ml·g-1·h-1、12000～24000ml·g-1·h-1Or 24000 to 60000 ml/g-1·h-1；
a5) When methyl formate is prepared by oxidizing methanol, the flow rate of the methanol is 0.002-0.020 mL/min, such as 0.002-0.004 mL/min, 0.004-0.005 mL/min or 0.005-0.020 mL/min;
a6) when methyl formate is prepared by methanol oxidation, the oxygen content in the oxygen-containing inert gas is 10-40 v%, such as 10-15 v%, 15-20 v% or 20-40 v%; the inert gas can be nitrogen, argon and the like;
a7) when methyl formate is prepared by methanol oxidation, the flow rate of the oxygen-containing inert gas is 8.8-100 mL/min, such as 8.8-10 mL/min, 10-16.6 mL/min, 16.6-24.9 mL/min, 24.9-33.2 mL/min or 33.2-100 mL/min.
More preferably, in the feature a1), at least one of the following technical features is further included:
a11) introducing inert gas containing 10-40 v% of oxygen during activation, such as 10-20 v%, 20-30 v% or 30-40 v%;
a12) the flow rate of the oxygen-containing inert gas introduced during activation is 10-100 mL/min, such as 10-15 mL/min, 15-20 mL/min, 20-30 mL/min, 30-50 mL/min or 50-100 mL/min; the inert gas can be nitrogen, argon and the like;
a13) the activation temperature is 200-600 ℃, such as 200-300 ℃, 300-350 ℃, 350-400 ℃ or 400-600 ℃;
a14) the activation time is 0.5-6 h, such as 0.5-2 h or 2-6 h.
In the fourth aspect of the invention, methanol and oxygen-containing inert gas react in the presence of the V-Al nanofiber catalyst to obtain methyl formate.
Preferably, at least one of the following technical features is also included:
b1) before being used for preparing methyl formate by oxidizing methanol, activating the catalyst;
b2) the reaction temperature for preparing methyl formate by methanol oxidation is 100-200 ℃, such as 100-135 ℃, 135-140 ℃, 140-150 ℃ or 150-200 ℃;
b3) the reaction pressure for preparing methyl formate by methanol oxidation is 0.1-2.0 Mpa, such as 0.1-0.5 Mpa, 0.5-1 Mpa or 1-2.0 Mpa;
b4) the reaction space velocity for preparing methyl formate by oxidizing methanol is 600-60000 ml-g-1·h-1E.g. 600-2400 ml g-1·h-1、2400～3000ml·g-1·h-1、3000～8000ml·g-1·h-1、8000～12000ml·g-1·h-1、12000～24000ml·g-1·h-1Or 24000 to 60000 ml/g-1·h-1；
b5) When methyl formate is prepared by oxidizing methanol, the flow rate of the methanol is 0.002-0.020 mL/min, such as 0.002-0.004 mL/min, 0.004-0.005 mL/min or 0.005-0.020 mL/min;
b6) when methyl formate is prepared by methanol oxidation, the oxygen content in the oxygen-containing inert gas is 10-40 v%, such as 10-15 v%, 15-20 v% or 20-40 v%;
b7) when methyl formate is prepared by methanol oxidation, the flow rate of the oxygen-containing inert gas is 8.8-100 mL/min, such as 8.8-10 mL/min, 10-16.6 mL/min, 16.6-24.9 mL/min, 24.9-33.2 mL/min or 33.2-100 mL/min.
More preferably, in the feature b1), at least one of the following technical features is further included:
b11) introducing inert gas containing 10-40 v% of oxygen during activation, such as 10-20 v%, 20-30 v% or 30-40 v%;
b12) the flow rate of the oxygen-containing inert gas introduced during activation is 10-100 mL/min, such as 10-15 mL/min, 15-20 mL/min, 20-30 mL/min, 30-50 mL/min or 50-100 mL/min;
b13) the activation temperature is 200-600 ℃, such as 200-300 ℃, 300-350 ℃, 350-400 ℃ or 400-600 ℃;
b14) the activation time is 0.5-6 h, such as 0.5-2 h or 2-6 h.
As described above, the invention has at least one of the following advantageous effects:
1) the V-Al nanofiber catalyst is in a nanofiber shape, the specific fiber diameter is 50-200 nm, the specific surface area is large, the porosity is high, the nanometer size is uniform, and the sintering resistance is good.
2) The V-Al nanofiber catalyst is applied to the reaction of preparing methyl formate by oxidizing methanol, and the airspeed is 600-60000 ml.g-1·h-1In the process, the conversion rate of the methanol is 60-99%, the selectivity of the methyl formate is 75-99%, and the one-way service life of the catalyst is more than 1000 h.
3) The V-Al nanofiber catalyst is applied to the reaction of preparing methyl formate by oxidizing methanol, and has more excellent reaction performance than a VTS catalyst prepared by the traditional method; at a space velocity of 12000ml g-1·h-1And at the reaction temperature of 140 ℃, the conversion rate of the methanol is 99 percent, and the selectivity of the methyl formate is 99 percent.
Drawings
FIG. 1 is an XRD spectrum of the V-Al nanofiber catalyst of example 5.
FIG. 2 is an SEM image of the V-Al nanofiber catalyst of example 5.
FIG. 3 is a TEM spectrum of the V-Al nanofiber catalyst of example 5.
FIG. 4 is N of the V-Al nanofiber catalyst of example 52Adsorption pattern.
Detailed Description
The invention is further illustrated by the following examples. It should be understood that these examples are only for illustrating the present invention, and are not to be construed as limiting the scope of the present invention. The experimental methods and reagents of the formulations not specified in the following examples were carried out or configured according to the conventional conditions or the conditions recommended by the manufacturers.
Example 1
Step (1), preparing a V-Al solution: 0.58g vanadyl acetylacetonate and 25.63g aluminum chloride in 95.20g water/16.80 g polyvinylpyrrolidone solution were mixed at room temperature and stirred uniformly at a stirring speed of 300rpm, wherein the V and Al are V2O5And Al2O3The mass ratio is 2: 98, respectively;
step (2), electrostatic spinning: carrying out electrostatic spinning on the V-Al mixed solution prepared in the step (1) under the conditions that the relative humidity is 15% and the temperature is 15 ℃, wherein the positive voltage of the electrostatic spinning is 10kV, the negative voltage of the electrostatic spinning is 10kV, and the distance of the electrostatic spinning is 5cm, so as to obtain V-Al nano fibers;
and (3) roasting the V-Al nano fibers: roasting the V-Al nano-fiber obtained in the step (2) at 300 ℃ for 2h to obtain a V-Al nano-fiber catalyst comprising V2O5And Al2O3，V2O5And Al2O3The mass ratio of (A) to (B) is 2: 98, the diameter of the fiber is 50-200 nm, and the nano size is uniform.
0.1g of the prepared V-Al nano-fiber catalyst is filled into the reactionIn the vessel, an oxygen-containing (10%) inert gas (nitrogen, the same as in the examples below) was first introduced at a flow rate of 10mL/min and activated at 200 ℃ for 0.5 h. After activation, the reactor temperature was lowered to 100 ℃ and methanol was fed at a flow rate of 0.002mL/min, an oxygen-containing (10%) inert gas (nitrogen, the same as in the examples below) was fed at a flow rate of 100mL/min, the pressure was 0.1MPa, and the space velocity of the reaction was 60000mL g-1·h-1. The reactivity is shown in Table 1.
Example 2
Step (1), preparing a V-Al solution: a solution of 23.31g vanadyl acetylacetonate and 6.71g aluminium sulphate in 85.09g water/4.45 g polyvinylpyrrolidone was mixed and stirred at 2000rpm at room temperature, wherein the V and Al were V2O5And Al2O3The mass ratio is 80: 20;
step (2), electrostatic spinning: carrying out electrostatic spinning on the V-Al mixed solution prepared in the step (1) under the conditions that the relative humidity is 70% and the temperature is 70 ℃, wherein the positive voltage of the electrostatic spinning is 60kV, the negative voltage of the electrostatic spinning is 60kV, and the distance of the electrostatic spinning is 30cm, so as to obtain V-Al nano fibers;
and (3) roasting the V-Al nano fibers: roasting the V-Al nano-fiber obtained in the step (2) at 600 ℃ for 10 hours to obtain a V-Al nano-fiber catalyst comprising V2O5And Al2O3，V2O5And Al2O3The mass ratio of (A) to (B) is 80: 20, the diameter of the fiber is 50-200 nm, and the nano size is uniform.
1g of the prepared V-Al nanofiber catalyst is filled into a reactor, oxygen-containing (40%) mixed gas is firstly introduced at the speed of 100mL/min, and the V-Al nanofiber catalyst is activated for 6 hours at the temperature of 600 ℃. After activation, the reactor temperature was reduced to 200 ℃ and methanol was fed at a flow rate of 0.020mL/min, an oxygen-containing (40%) inert gas was fed at a flow rate of 10mL/min, the pressure was 2.0MPa, and the reaction space velocity was 600mL g-1·h-1. The reactivity is shown in Table 1.
Example 3
Step (1), preparing a V-Al solution: 8.96g of vanadyl sulfate and 8.04g of sodium metaaluminate are mixed at room temperature100.76g N, N-2-methylformamide/11.20 g polyethylene glycol solution, and stirring uniformly at 500rpm, wherein the V and Al are V2O5And Al2O3The mass ratio is 50: 50;
step (2), electrostatic spinning: carrying out electrostatic spinning on the V-Al mixed solution prepared in the step (1) under the conditions that the relative humidity is 42% and the temperature is 25 ℃, wherein the positive voltage of the electrostatic spinning is 55kV, the negative voltage of the electrostatic spinning is 55kV, and the distance of the electrostatic spinning is 5cm, so as to obtain V-Al nano fibers;
and (3) roasting the V-Al nano fibers: roasting the V-Al nano-fiber obtained in the step (2) for 5 hours at 500 ℃ to obtain a V-Al nano-fiber catalyst comprising V2O5And Al2O3，V2O5And Al2O3In a mass ratio of 50: 50, the diameter of the fiber is 50-200 nm, and the nano size is uniform.
0.5g of the prepared V-Al nanofiber catalyst is filled into a reactor, and oxygen-containing (10%) inert gas is firstly introduced at the speed of 30mL/min, and the catalyst is activated for 2 hours at 400 ℃. After activation, the reactor temperature was reduced to 135 ℃ and methanol was fed at a flow rate of 0.002mL/min, an oxygen-containing (20%) inert gas was fed at a flow rate of 16.6mL/min, the pressure was 0.5MPa, and the reaction space velocity was 2400mL g-1·h-1. The reactivity is shown in Table 1.
Example 4
Step (1), preparing a V-Al solution: a solution of 7.71g ammonium vanadate and 13.42g aluminium sulphate in 77.25g water/6.72 g polyvinyl alcohol was mixed at room temperature and stirred uniformly at 300rpm, wherein V and Al are V2O5And Al2O3The mass ratio is 60: 40;
step (2), electrostatic spinning: carrying out electrostatic spinning on the V-Al mixed solution prepared in the step (1) under the conditions that the relative humidity is 45% and the temperature is 28 ℃, wherein the positive voltage of the electrostatic spinning is 45kV, the negative voltage of the electrostatic spinning is 45kV, and the distance of the electrostatic spinning is 15cm, so as to obtain V-Al nano fibers;
step (3), roasting of V-Al nano-fiber: roasting the V-Al nano-fiber obtained in the step (2) for 4 hours at the temperature of 450 ℃ to obtain a V-Al nano-fiber catalyst comprising V2O5And Al2O3，V2O5And Al2O3The mass ratio of (A) to (B) is 60: 40, the diameter of the fiber is 50-200 nm, and the nano size is uniform.
0.2g of the prepared V-Al nanofiber catalyst is filled into a reactor, firstly, inert gas containing oxygen (10%) is introduced at the speed of 15mL/min, and the catalyst is activated for 2 hours at 400 ℃. After activation, the temperature of the reactor is reduced to 140 ℃, methanol is introduced at the flow rate of 0.004mL/min, inert gas containing oxygen (15%) is introduced at the flow rate of 8.8mL/min, the pressure is 1.0MPa, and the reaction space velocity is 3000 ml.g-1·h-1. The reactivity is shown in Table 1.
Example 5
Step (1), preparing a V-Al solution: a solution of 3.85g of ammonium vanadate and 18.30g of aluminum chloride in 49.26g of tetrahydrofuran/6.72 g of polyvinyl alcohol is mixed at room temperature and stirred uniformly at a stirring speed of 300rpm, wherein the V and Al are represented by V2O5And Al2O3The mass ratio is 30: 70;
step (2), electrostatic spinning: carrying out electrostatic spinning on the V-Al mixed solution prepared in the step (1) under the conditions that the relative humidity is 40% and the temperature is 25 ℃, wherein the positive voltage of the electrostatic spinning is 20kV, the negative voltage of the electrostatic spinning is 20kV, and the distance of the electrostatic spinning is 50cm, so as to obtain V-Al nano fibers;
and (3) roasting the V-Al nano fibers: roasting the V-Al nano-fiber obtained in the step (2) at 300 ℃ for 4h to obtain a V-Al nano-fiber catalyst comprising V2O5And Al2O3，V2O5And Al2O3The mass ratio of (A) to (B) is 30: 70, the fiber diameter is 50-200 nm, the nano size is uniform, an XRD spectrogram is shown in figure 1, an SEM spectrogram is shown in figure 2, a TEM spectrogram is shown in figure 3, and N is2The adsorption pattern is shown in FIG. 4.
0.2g of the prepared V-Al nanofiber catalyst is filled into a reactor, and oxygen-containing (20%) inert gas is firstly introduced at the speed of 50mL/min, and the catalyst is activated for 2 hours at 400 ℃. Is activated completelyAfter the reaction, the temperature of the reactor is reduced to 140 ℃, methanol is introduced at the flow rate of 0.002mL/min, oxygen-containing (10%) inert gas is introduced at the flow rate of 33.2mL/min, the working pressure is 1.0MPa, and the reaction space velocity is 12000 mL/g-1·h-1. The reactivity is shown in Table 1.
The prepared V-Al nanofiber catalyst has stable service life, can stably run for more than 1000 hours, and has reaction stability shown in Table 2.
Example 6
Step (1), preparing a V-Al solution: mixing 0.58g vanadyl acetylacetonate and 2.68g aluminum sulfate solution of 50.7g water/7.57 g polyvinyl alcohol at room temperature, and stirring uniformly at 600rpm, wherein the V and Al are V2O5And Al2O3The mass ratio is 20: 80;
step (2), electrostatic spinning: carrying out electrostatic spinning on the V-Al mixed solution prepared in the step (1) under the conditions that the relative humidity is 45% and the temperature is 30 ℃, wherein the positive voltage of the electrostatic spinning is 12kV, the negative voltage of the electrostatic spinning is 12kV, and the distance of the electrostatic spinning is 10cm, so as to obtain V-Al nano fibers;
and (3) roasting the V-Al nano fibers: roasting the V-Al nano-fiber obtained in the step (2) for 3 hours at the temperature of 600 ℃ to obtain a V-Al nano-fiber catalyst comprising V2O5And Al2O3，V2O5And Al2O3The mass ratio of (A) to (B) is 20: 80, the diameter of the fiber is 50-200 nm, and the nano size is uniform.
0.3g of the prepared V-Al nanofiber catalyst is filled into a reactor, and oxygen-containing (30%) inert gas is firstly introduced at the speed of 20mL/min, and the catalyst is activated for 2 hours at 350 ℃. After activation, the temperature of the reactor is reduced to 150 ℃, methanol is introduced at the flow rate of 0.005mL/min, oxygen-containing (20%) inert gas is introduced at the flow rate of 24.9mL/min, the working pressure is 1.0MPa, and the reaction space velocity is 8000 mL/g-1·h-1. The reactivity is shown in Table 1.
Example 7
Step (1), preparing a V-Al solution: 8.99g of ammonium vanadate and 4.82g of sodium metaaluminate in 101.88g of tetrahydro are added at room temperatureThe solution of furan/10.08 g polyvinyl alcohol was mixed and stirred uniformly at 400rpm, wherein the V and Al are represented by V2O5And Al2O3The mass ratio is 70: 30, of a nitrogen-containing gas;
step (2), electrostatic spinning: carrying out electrostatic spinning on the V-Al mixed solution prepared in the step (1) under the conditions that the relative humidity is 40% and the temperature is 25 ℃, wherein the positive voltage of the electrostatic spinning is 30kV, the negative voltage of the electrostatic spinning is 30kV, and the distance of the electrostatic spinning is 20cm, so as to obtain V-Al nano fibers;
and (3) roasting the V-Al nano fibers: roasting the V-Al nano-fiber obtained in the step (2) for 4 hours at 400 ℃ to obtain a V-Al nano-fiber catalyst comprising V2O5And Al2O3，V2O5And Al2O3The mass ratio of (A) to (B) is 70: 30, the diameter of the fiber is 50-200 nm, and the nano size is uniform.
0.1g of the prepared V-Al nanofiber catalyst is filled into a reactor, and oxygen-containing (20%) inert gas is firstly introduced at the speed of 30mL/min, and the catalyst is activated for 2 hours at 300 ℃. After activation, the temperature of the reactor is reduced to 140 ℃, methanol is introduced at the flow rate of 0.002mL/min, oxygen-containing (10%) inert gas is introduced at the flow rate of 33.2mL/min, the working pressure is 1.0MPa, and the reaction space velocity is 24000 ml.g-1·h-1. The reactivity is shown in Table 1.
Comparative example
Taking 1.5g of vanadyl sulfate, 16.3g of aluminum sulfate and 5g of sulfuric acid, ultrasonically dissolving in 400ml of deionized water to obtain a solution A, and taking 50ml of ammonia water (25%) and adding 300ml of water to prepare a solution B. Solution a was added dropwise to solution B at a rate of 2ml/min under vigorous stirring in an ice-water bath until pH 7.5 to give a slurry containing a tan precipitate. Aging at room temperature for 2h, washing with 200ml of water for 2 times to obtain a tan solid, dissolving the obtained tan solid in 20ml of water, adding 1ml of n-butyl alcohol, stirring for 6h, removing water by using a rotary evaporator, drying at 80 ℃ for 12h, and roasting at 400 ℃ for 6h to obtain the V-Al catalyst.
1g of the obtained catalyst was charged into a fixed bed reactor, and oxygen (20 mL/min) was first introduced thereinto at a rate of 30mL/min%) of an inert gas, activated at 300 ℃ for 2 h. After the activation is finished, the temperature of the reactor is reduced to 140 ℃, methanol is introduced at the flow rate of 0.002mL/min, oxygen-containing (10%) inert gas is introduced at the flow rate of 16.6mL/min, the working pressure is 0.1MPa, and the reaction space velocity is 1200 ml.g-1·h-1. The reaction properties are shown in Table 1.
TABLE 1 Properties of V-Al nanofiber catalysts prepared in examples 1 to 7 for preparing methyl formate by methanol oxidation
Figure BDA0003477387280000091
TABLE 2 evaluation of Life of V-Al nanofiber catalyst prepared in example 5 for methyl formate preparation by methanol Oxidation
Figure BDA0003477387280000101
The above examples are intended to illustrate the disclosed embodiments of the invention and are not to be construed as limiting the invention. In addition, various modifications of the methods and compositions set forth herein, as well as variations of the methods and compositions of the present invention, will be apparent to those skilled in the art without departing from the scope and spirit of the invention. While the invention has been specifically described in connection with various specific preferred embodiments thereof, it should be understood that the invention should not be unduly limited to such specific embodiments. Indeed, various modifications of the above-described embodiments which are obvious to those skilled in the art to which the invention pertains are intended to be covered by the scope of the present invention.

Claims (11)

1. The V-Al nano-fiber catalyst is characterized by comprising V2O5And Al2O3，V2O5And Al2O3The mass ratio of (A) to (B) is 2: 98-80: 20, the V-Al nano fiber catalyst is in a nano fiber shape.
2. The V-Al nanofiber catalyst according to claim 1, wherein the fiber diameter of the V-Al nanofiber catalyst is 50 to 200 nm.
3. The method of preparing a V-Al nanofiber catalyst according to claim 1 or 2, comprising the steps of:
1) carrying out electrostatic spinning on a mixed solution containing a V source and an Al source to obtain V-Al nano fibers;
2) roasting the V-Al nano-fiber to obtain a V-Al nano-fiber catalyst;
wherein the mixed solution further contains a high molecular polymer and a solvent.
4. The method of claim 3, further comprising at least one of the following technical features:
1a) in the step 1), the solvent is water or an organic solvent;
1b) in the step 1), the mass ratio of the solvent to the high molecular polymer is 85: 15-95: 5;
1c) in step 1), the V source is selected from V2O5、VOSO4、NH4VO3And vanadyl acetylacetonate;
1d) in the step 1), the Al source is at least one selected from aluminum chloride, aluminum sulfate and sodium metaaluminate;
1e) in the step 1), the high molecular polymer is selected from at least one of polyvinyl alcohol, polyethylene glycol and polyvinylpyrrolidone;
1f) in the step 1), V in the mixed solution accounts for 0.1-5% of the total mass of the solvent and the high molecular polymer;
1g) in the step 1), Al in the mixed solution accounts for 0.73-6.62% of the total mass of the solvent and the high molecular polymer;
1h) in the step 1), electrostatic spinning is carried out under the condition that the relative humidity is 15-70%;
1i) in the step 1), electrostatic spinning is carried out at the temperature of 15-70 ℃;
1j) in the step 1), the positive voltage of electrostatic spinning is 10-60 kV;
1k) in the step 1), the negative voltage of electrostatic spinning is 10-60 kV;
1l) in the step 1), the distance of electrostatic spinning is 5-50 cm;
2a) in the step 2), the roasting temperature is 300-600 ℃;
2b) in the step 2), the roasting time is 1-20 h.
5. The method of claim 4, further comprising at least one of the following technical features:
1a1) in the feature 1a), the organic substance is at least one selected from the group consisting of tetrahydrofuran, benzene, toluene, N-methylpyrrolidone, and N, N-dimethylformamide;
1f1) in the characteristic 1f), V in the mixed solution accounts for 0.5-2.5% of the total mass of the solvent and the high molecular polymer;
1g1) the preparation method is characterized in that in 1g), Al in the mixed solution accounts for 0.73-5% of the total mass of the solvent and the high molecular polymer;
2b1) in the step 2b), the roasting time is 2-10 h.
6. Use of the V-Al nanofiber catalyst of claim 1 or 2 in the oxidation of methanol to methyl formate.
7. Use of a V-Al nanofiber catalyst according to claim 6, characterized by further comprising at least one of the following technical features:
a1) before being used for preparing methyl formate by oxidizing methanol, activating the catalyst;
a2) the reaction temperature for preparing methyl formate by oxidizing methanol is 100-200 ℃;
a3) the reaction pressure for preparing methyl formate by oxidizing methanol is 0.1-2.0 Mpa;
a4) the reaction space velocity for preparing methyl formate by oxidizing methanol is 600-60000 ml-g-1·h-1；
a5) When methyl formate is prepared by oxidizing methanol, the flow rate of the methanol is 0.002-0.020 mL/min;
a6) when methyl formate is prepared by methanol oxidation, the oxygen content in the oxygen-containing inert gas is 10-40 v%;
a7) when methyl formate is prepared by methanol oxidation, the flow rate of the oxygen-containing inert gas is 8.8-100 mL/min.
8. Use of a V-Al nanofiber catalyst according to claim 7, characterized in that in characteristic a1), at least one of the following technical characteristics is also included:
a11) introducing inert gas containing 10-40 v% of oxygen during activation;
a12) the flow rate of the oxygen-containing inert gas introduced during activation is 10-100 mL/min;
a13) the activation temperature is 200-600 ℃;
a14) the activation time is 0.5-6 h.
9. A method for preparing methyl formate by oxidizing methanol, which is characterized in that methanol and oxygen-containing inert gas react in the presence of the V-Al nanofiber catalyst as claimed in claim 1 or 2 to obtain methyl formate.
10. The method for preparing methyl formate by oxidizing methanol according to claim 9, further comprising at least one of the following technical features:
b1) before being used for preparing methyl formate by oxidizing methanol, activating the catalyst;
b2) the reaction temperature for preparing methyl formate by oxidizing methanol is 100-200 ℃;
b3) the reaction pressure for preparing methyl formate by oxidizing methanol is 0.1-2.0 Mpa;
b4) the reaction space velocity for preparing methyl formate by oxidizing methanol is 600-60000 ml-g-1·h-1；
b5) When methyl formate is prepared by oxidizing methanol, the flow rate of the methanol is 0.002-0.020 mL/min;
b6) when methyl formate is prepared by methanol oxidation, the oxygen content in the oxygen-containing inert gas is 10-40 v%;
b7) when methyl formate is prepared by methanol oxidation, the flow rate of the oxygen-containing inert gas is 8.8-100 mL/min.
11. The method for preparing methyl formate by oxidizing methanol according to claim 10, wherein the characteristic b1) further comprises at least one of the following technical characteristics:
b11) introducing inert gas containing 10-40 v% of oxygen during activation;
b12) the flow rate of the oxygen-containing inert gas introduced during activation is 10-100 mL/min;
b13) the activation temperature is 200-600 ℃;
b14) the activation time is 0.5-6 h.
CN202210059099.7A 2022-01-19 2022-01-19 V-Al nano fiber catalyst and preparation method and application thereof Pending CN114405500A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202210059099.7A CN114405500A (en) 2022-01-19 2022-01-19 V-Al nano fiber catalyst and preparation method and application thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202210059099.7A CN114405500A (en) 2022-01-19 2022-01-19 V-Al nano fiber catalyst and preparation method and application thereof

Publications (1)

Publication Number Publication Date
CN114405500A true CN114405500A (en) 2022-04-29

Family

ID=81272893

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202210059099.7A Pending CN114405500A (en) 2022-01-19 2022-01-19 V-Al nano fiber catalyst and preparation method and application thereof

Country Status (1)

Country Link
CN (1) CN114405500A (en)

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101757906A (en) * 2008-12-23 2010-06-30 南京大学 Preparation method for V-Ti-Al-O composite catalyst for methylal synthesis through methanol oxidation
WO2010122049A1 (en) * 2009-04-21 2010-10-28 Basf Se Water-based production of metal-oxide and metal nanofibers
CN102553566A (en) * 2011-12-14 2012-07-11 中国科学院山西煤炭化学研究所 Catalyst for preparing methyl formate by oxidizing dimethyl ether at low temperature, and preparation method and application of catalyst
CN105903484A (en) * 2016-05-17 2016-08-31 中国科学院上海高等研究院 Nano-catalyst for preparing methyl formate by oxidizing methyl alcohol at one step and preparation method thereof
CN107020077A (en) * 2016-02-01 2017-08-08 中国科学院上海高等研究院 A kind of methanol aoxidizes nano-fiber catalyst of methyl formate processed and preparation method thereof

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101757906A (en) * 2008-12-23 2010-06-30 南京大学 Preparation method for V-Ti-Al-O composite catalyst for methylal synthesis through methanol oxidation
WO2010122049A1 (en) * 2009-04-21 2010-10-28 Basf Se Water-based production of metal-oxide and metal nanofibers
CN102553566A (en) * 2011-12-14 2012-07-11 中国科学院山西煤炭化学研究所 Catalyst for preparing methyl formate by oxidizing dimethyl ether at low temperature, and preparation method and application of catalyst
CN107020077A (en) * 2016-02-01 2017-08-08 中国科学院上海高等研究院 A kind of methanol aoxidizes nano-fiber catalyst of methyl formate processed and preparation method thereof
CN105903484A (en) * 2016-05-17 2016-08-31 中国科学院上海高等研究院 Nano-catalyst for preparing methyl formate by oxidizing methyl alcohol at one step and preparation method thereof

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
徐兵: "双功能氧化物催化剂的制备及甲醇催化反应性能研究" *

Similar Documents

Publication Publication Date Title
CN110433864B (en) Preparation and application of MOF (Metal organic framework) supported bimetallic catalyst
DE2811115A1 (en) CARRIER CATALYST FOR THE PRODUCTION OF VINYL ACETATE FROM ETHYLENE, ACETIC ACID AND OXYGEN IN THE GAS PHASE
DE3803900A1 (en) METHOD FOR PRODUCING VINYL ACETATE
CN1921939A (en) Oxidation process with in-situ h2o2 generation and polymer-encapsulated catalysts therefor
CN114829004B (en) Method for preparing Ni-X-based oxide catalyst and application of Ni-X-based oxide catalyst in transfer hydrogenation
CN108404987B (en) Method for improving catalytic efficiency of nanoparticle @ MOFs material
CN114573435B (en) Preparation method of cyclopropyl methyl ketone
CN114054061A (en) Nitrogen-doped carbon-supported palladium catalyst and preparation method and application thereof
CN114029053B (en) Preparation method of supported catalyst and application of supported catalyst in preparation of methyl glycolate from ethylene glycol
CN114405500A (en) V-Al nano fiber catalyst and preparation method and application thereof
CN88101657A (en) Produce the method for amine
CN110586094A (en) Copper-based nanoflower catalyst for producing methanol and ethylene glycol by ethylene carbonate hydrogenation and preparation method thereof
CN108250331B (en) Composition, preparation method and application of olefin polymerization catalyst carrier
JPH05186393A (en) Catalyst and preparation of vinyl acetate
US5977350A (en) Process for the oxidation of di-, tri-, oligo- and polysaccharides into polyhydroxycarboxylic acids
CN115445601A (en) Load type SiO 2 @M x O y -TiO 2 Catalyst, preparation method and application thereof
CN112973663B (en) Solid acid catalyst for catalyzing esterification reaction of pentaerythritol and stearic acid and preparation method thereof
CN106902818B (en) The preparation method and its application in catalysis benzoic acid hydrogenation reaction that TiO2-C loads Ru composite catalyst
CN110813364B (en) Preparation method of bimetallic nano-catalyst and application of bimetallic nano-catalyst in preparation of pyruvic acid and hydroxyacetone by catalytic oxidation of 1, 2-propylene glycol
CN111589461A (en) Preparation method and application of V-Ti-P nano catalyst for preparing methyl formate by oxidizing methanol
CN114349973A (en) Lanthanum-manganese bimetal quasi-organic framework material and preparation method and application thereof
JP4069242B2 (en) Metal particle carrier and method for producing carboxylic acid ester
CN114289012B (en) Vanadium-titanium catalyst and preparation method and application thereof
CN1189437C (en) Improvement of a colour index of multivalent alcohols by hydrogenation
TWI268943B (en) Preparation of polytetrahydrofuran having a low color number

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
RJ01 Rejection of invention patent application after publication

Application publication date: 20220429