CN106552622B - V-Ag-Si-O catalyst, preparation method and application thereof - Google Patents
V-Ag-Si-O catalyst, preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a V-Ag-Si-O catalyst, a preparation method and application thereof. The V-Ag-Si-O catalyst comprises 24-46% by mass of vanadium, 14-43% by mass of silver and 0.4-5.0% by mass of silicon, and the BET specific surface area of the V-Ag-Si-O catalyst is 20-130m2(ii) in terms of/g. Compared with the V-Ag-O metal oxide prepared by the prior art, the V-Ag-Si-O catalyst prepared by the method has larger surface area and can enhance the caking property with a carrier to be sprayed; the V-Ag-Si-O catalyst is used for catalytic oxidation synthesis of aldehyde, carboxylic acid and carboxylic anhydride and has the characteristics of high activity, stable reaction and the like.
Description
Technical Field
The invention relates to a V-Ag-Si-O catalyst, a preparation method and application thereof, belonging to the field of catalysts.
Background
the V-Ag-O metal oxide has good oxidation performance, and can be used for catalyzing and oxidizing methylbenzene to generate benzoic acid and benzaldehyde, oxidizing O-xylene to synthesize phthalic anhydride, oxidizing p-xylene to synthesize terephthalic acid, oxidizing methyl pyridine to synthesize picolinic acid and the like. For example, Delaigle et al doped Ag into VOx/TiO2In the catalyst, the synergistic effect between silver and vanadium is found to reduce the particle size of the catalyst, thereby improving the oxidation performance of the catalyst (Topics in Catalysis, vol 56 in 2013, page 18-20, 1867-1874). BASF corporation in CN200580009783.9, CN200480021531.3 and CN99813146.6 reported that V-Ag-O can be used for catalytic synthesis of aldehyde, carboxylic acid and carboxylic acid anhydride by using it as active component loaded on nonporous carrier after being modified by alkali metal, alkaline earth metal, Bi, Tl, Cu, Zn, Cd, Pb, Cr, Au, Al, Fe, Co, Ni, Mo, Nb, Ce, W, Mn, Ta, Pd, Pt, Ru and Rh. V-Ag-Ni-O and V-Ag-O catalysts prepared by Schlemongwei et al have good performance in synthesizing benzaldehyde and benzoic acid by selective oxidation of toluene (CN200710024880.6, Applied Catalysis A: General, Vol.330, No. 10, No. 117, page 126, Vol.2007, Applied Catalysis A: General, Vol.2010, No. 379, Vol.1-2, No. 7-14).
It is known that increasing the surface area of the active component of the catalyst, and increasing the thermal stability and mechanical strength of the catalyst are the goals pursued by cumin catalysis industry. The V-Ag-O prepared by adopting methods such as coprecipitation, sol-gel and the like has the defects of low surface area and difficult molding, is generally required to be loaded on a carrier in a spraying mode, but is weaker in combination with an inert carrier, and is easy to fall off from the surface of the carrier, so that the activity of the catalyst is reduced.
disclosure of Invention
In order to overcome the defects that the surface area of a V-Ag-O metal oxide is low, the V-Ag-O metal oxide is easy to fall off from the surface of a carrier and the like in the prior art, the invention provides a V-Ag-Si-O catalyst, a preparation method and application thereof.
in order to solve the technical problems, the technical scheme adopted by the invention is as follows:
The V-Ag-Si-O catalyst has vanadium 24-46 wt%, silver 14-43 wt% and silicon 0.4-5.0 wt%, and V-Ag-Si-O catalystThe BET specific surface area of the agent is 20-130m2/g。
The elemental composition of the V-Ag-Si-O catalyst is analyzed by X-ray fluorescence spectrum, and the surface area is determined by a nitrogen physical adsorption method.
The V-Ag-Si-O catalyst has the advantages of high activity, large specific surface area, strong mechanical property and the like.
the preparation method of the V-Ag-Si-O catalyst comprises the following steps of:
1) Fully contacting a precursor containing vanadium, silver and silicon to obtain a solution containing the precursor of vanadium, silver and silicon;
2) Forming gel from the solution of the precursor containing vanadium, silver and silicon obtained in the step 1) at the temperature of 40-70 ℃;
3) Adding C3-C6 alcohol into the gel obtained in the step 2), and sealing and crystallizing for 4-24 hours at the temperature of 40-90 ℃;
4) Drying the material obtained in the step 3) at 40-150 ℃ and roasting at 300-700 ℃ in sequence to obtain the V-Ag-Si-O catalyst.
The V-Ag-Si-O catalyst prepared by the preparation method effectively overcomes the defects that the V-Ag-O metal oxide has a lower surface area and is easy to fall off from the surface of the carrier and the like.
In order to ensure that the precursors of vanadium, silver and silicon are fully contacted, hydrogen peroxide, oxalic acid, citric acid, nitric acid or ammonia water can be added into the solution in the step 1) according to the requirement, wherein the mass ratio of the hydrogen peroxide, the oxalic acid, the citric acid, the nitric acid or the ammonia water to the vanadium (calculated by the simple substance of vanadium) is 0:1-35: 1.
the temperature for forming gel in the step 2) is preferably 60-70 ℃, and the time is preferably 5-8 h. The crystallization temperature in the step 3) is preferably 50-60 ℃, and the time is preferably 4-6 h. The drying temperature in the step 4) is preferably 90-110 ℃, the drying time is preferably 4-6h, the roasting temperature is preferably 550-650 ℃, and the roasting time is preferably 3-8 h.
In order to further improve the properties of the obtained catalyst, such as activity, specific surface area and mechanical strength, the vanadium precursor preferably comprises at least one of ammonium metavanadate, vanadyl oxalate, vanadyl sulfate or vanadium pentoxide. Further preferably, the precursor of vanadium comprises at least one of ammonium metavanadate, vanadyl oxalate or vanadium pentoxide.
in order to further improve the properties of the obtained catalyst, such as activity, specific surface area and mechanical strength, preferably, the silver precursor comprises at least one of silver nitrate or silver acetate; the precursor of silicon is ethyl silicate.
In order to further improve the performances of the obtained catalyst such as specific surface area, mechanical strength and the like, the C3-C6 alcohol is preferably at least one of n-propanol, isopropanol, n-butanol, isobutanol, n-pentanol, isoamyl alcohol, n-hexanol or cyclohexanol; the mass consumption of the C3-C6 alcohol is 80-300% of the mass of the roasted V-Ag-Si-O catalyst.
The catalyst obtained by the method can be directly used without being loaded on a carrier.
The V-Ag-Si-O catalyst can be used for preparing aldehyde, carboxylic acid or carboxylic anhydride by catalytic oxidation. The product analysis adopts gas chromatography and liquid chromatography.
The catalytic oxidation reaction of the V-Ag-Si-O catalyst is carried out on a fixed bed reactor, the reaction raw material is preheated and gasified at the temperature of 100 ℃ plus 250 ℃, and then enters the reactor with air, the reaction temperature is 300 ℃ plus 650 ℃, and the liquid airspeed is 1-10h-1The gas space velocity is 0.1-50000h-1。
The prior art is referred to in the art for techniques not mentioned in the present invention.
the V-Ag-Si-O catalyst prepared according to the method of the present invention not only has a large surface area, but also has a large surface area due to SiO, as compared to V-Ag-O metal oxides prepared in the prior art2The introduction of the coating enhances the adhesion with the carrier to be sprayed; the V-Ag-Si-O catalyst is used for catalytic oxidation synthesis of aldehyde, carboxylic acid and carboxylic anhydride and has the characteristics of high activity, stable reaction and the like.
Detailed Description
In order to better understand the present invention, the following examples are further provided to illustrate the present invention, but the present invention is not limited to the following examples.
In the examples, the elemental composition of the V-Ag-Si-O catalyst was analyzed by X-ray fluorescence spectroscopy, and the surface area was measured by nitrogen physical adsorption.
Example 1:
Weighing 1 part by mass of ammonium metavanadate and 0.3 part by mass of silver nitrate, mixing, adding 2.5 parts by mass of oxalic acid and 100 parts by mass of water to obtain a precursor solution of vanadium and silver, adding nitric acid to the precursor solution to adjust the pH to 1.5, then adding 0.03 part of ethyl silicate, heating at 60 ℃ for 8 hours to form gel, adding 0.9 part of isopropanol to the gel, sealing and crystallizing at 60 ℃ for 5 hours, finally drying the crystallized gel containing the isopropanol at 110 ℃ for 5 hours, roasting at 600 ℃ for 5 hours to obtain the V-Ag-Si-O catalyst A, wherein the mass percentage content of vanadium is 44%, the mass percentage content of silver is 19%, the mass percentage content of silicon is 0.4%, and the BET surface area is 23m2/g。
Comparative example 1:
Weighing 1 part by mass of ammonium metavanadate and 0.3 part by mass of silver nitrate, mixing, adding 2.5 parts by mass of oxalic acid and 100 parts by mass of water to obtain a precursor solution of vanadium and silver, adding nitric acid to the precursor solution to adjust the pH to 1.5, adding 0.03 part of ethyl silicate, heating at 60 ℃ for 8 hours to form gel, drying the gel at 110 ℃ for 5 hours, and roasting at 600 ℃ for 5 hours to obtain the V-Ag-Si-O catalyst B, wherein the vanadium content by mass is 44%, the silver content by mass is 19%, the silicon content by mass is 0.4%, and the BET surface area is 10m2/g。
Comparative example 2:
Weighing 1 part by mass of ammonium metavanadate and 0.3 part by mass of silver nitrate, mixing, adding 2.5 parts by mass of oxalic acid and 100 parts by mass of water to obtain a precursor solution of vanadium and silver, adding nitric acid to the precursor solution to adjust the pH to 1.5, heating at 60 ℃ for 8 hours to form gel, adding 0.9 part of isopropanol to the gel, sealing and crystallizing at 60 ℃ for 5 hours, drying the crystallized gel containing isopropanol at 110 ℃ for 5 hours, roasting at 600 ℃ for 5 hours to obtain a V-Ag-O catalyst C, and measuring the V-Ag-O catalyst C to obtain the V-Ag-O catalyst C, wherein the vanadium content is 44% by mass, the silver content is 19% by mass, and the BET surface area is 8m2/g。
Comparative example 3:
weighing 1 part by massMixing ammonium vanadate with 0.3 mass part of silver nitrate, adding 2.5 mass parts of oxalic acid and 100 mass parts of water to obtain a precursor solution of vanadium and silver, adding nitric acid to the precursor solution to adjust the pH to 1.5, heating at 60 ℃ for 8 hours to form gel, drying the gel at 110 ℃ for 5 hours, and roasting at 600 ℃ for 5 hours to obtain a V-Ag-O catalyst D, wherein the mass percent of vanadium is 44%, the mass percent of silver is 19%, and the BET surface area is 2m2/g。
example 2:
Weighing 1 part by mass of ammonium metavanadate and 0.3 part by mass of silver nitrate, mixing, adding 6 parts by mass of citric acid, 3 parts by mass of 28% hydrogen peroxide and 100 parts by mass of water to obtain a precursor solution of vanadium and silver, adding nitric acid to the precursor solution to adjust the pH to 1.5, adding 0.03 part of ethyl silicate, heating at 60 ℃ for 8 hours to form gel, adding 0.9 part of isopropanol to the gel, sealing and crystallizing at 50 ℃ for 5 hours, drying the crystallized gel containing isopropanol at 90 ℃ for 5 hours, and roasting at 550 ℃ for 8 hours to obtain a V-Ag-Si-O catalyst E, wherein the mass percentage of vanadium is 44%, the mass percentage of silver is 19%, the mass percentage of silicon is 0.4%, and the BET surface area is 43m2/g。
example 3:
Weighing 1 part by mass of vanadium pentoxide and 0.6 part by mass of silver nitrate, mixing, adding 10 parts by mass of 28% hydrogen peroxide and 100 parts by mass of water to obtain a precursor solution of vanadium and silver, adding nitric acid to the precursor solution to adjust the pH to 1.5, then adding 0.26 part by mass of ethyl silicate, heating at 60 ℃ for 8 hours to form a gel, adding 1.4 parts by mass of n-butyl alcohol to the gel, sealing and crystallizing at 50 ℃ for 5 hours, finally drying the crystallized gel containing the n-propyl alcohol at 90 ℃ for 5 hours, roasting at 550 ℃ for 8 hours to obtain the V-Ag-Si-O catalyst F, wherein the mass percentage content of vanadium is 37%, the mass percentage content of silver is 25%, the mass percentage content of silicon is 2.4%, and the BET surface area is 85m2/g。
Example 4:
Weighing 1 part by mass of vanadyl oxalate, mixing with 0.65 part by mass of silver nitrate, adding 3 parts by mass of citric acid and 100 parts by mass of water to obtain vanadium and silver precursorsAdding nitric acid into the precursor solution to adjust the pH value to 1.5, adding 0.31 part of ethyl silicate, heating at 60 ℃ for 8 hours to form gel, adding 2.5 parts of n-butyl alcohol into the gel, sealing and crystallizing at 50 ℃ for 5 hours, drying the crystallized gel containing the n-butyl alcohol at 90 ℃ for 5 hours, and roasting at 550 ℃ for 8 hours to obtain the V-Ag-Si-O catalyst G, wherein the V-Ag-Si-O catalyst G comprises 29 mass percent of vanadium, 37 mass percent of silver, 3.8 mass percent of silicon and 92m BET surface area2/g。
Example 5:
weighing 1 part by mass of vanadyl sulfate, mixing with 0.65 part by mass of silver nitrate, adding 3 parts by mass of citric acid and 100 parts by mass of water to obtain a precursor solution of vanadium and silver, adding nitric acid to the precursor solution to adjust the pH to 1.5, then adding 0.18 part of ethyl silicate, heating at 60 ℃ for 8 hours to form gel, adding 2.5 parts of n-amyl alcohol to the gel, sealing and crystallizing at 50 ℃ for 5 hours, finally drying the crystallized gel containing the n-amyl alcohol at 90 ℃ for 5 hours, roasting at 550 ℃ for 8 hours to obtain the V-Ag-Si-O catalyst H, wherein the vanadium content is 29% by mass, the silver content is 39% by mass, the silicon content is 2.3% by mass, and the BET surface area is 36m2/g。
Example 6:
weighing 1 part by mass of vanadyl oxalate, mixing with 0.6 part by mass of silver acetate, adding 3 parts by mass of citric acid and 100 parts by mass of water to obtain a precursor solution of vanadium and silver, adding nitric acid to the precursor solution to adjust the pH to 1.5, then adding 0.4 part of ethyl silicate, heating at 70 ℃ for 5 hours to form a gel, adding 3 parts of n-hexanol to the gel, sealing and crystallizing at 50 ℃ for 5 hours, finally drying the crystallized gel containing n-hexanol at 90 ℃ for 5 hours, roasting at 580 ℃ for 4 hours to obtain the V-Ag-Si-O catalyst I, wherein the vanadium content is 29% by mass, the silver content is 37% by mass, the siliceous content is 4.8% by mass, and the BET surface area is 102m2/g。
Example 7:
Weighing 1 part by mass of vanadyl oxalate, mixing with 0.6 part by mass of silver acetate, and adding 3 parts by mass of citric acid and 100 parts by mass of water to obtain vanadium and silver precursorsAdding nitric acid into the precursor solution to adjust the pH value to 1.5, then adding 0.4 part of ethyl silicate, heating at 70 ℃ for 5 hours to form gel, adding 3 parts of cyclohexanol into the gel, sealing and crystallizing at 50 ℃ for 5 hours, finally drying the crystallized gel containing cyclohexanol at 90 ℃ for 5 hours, and roasting at 650 ℃ for 3 hours to obtain the V-Ag-Si-O catalyst J, wherein the mass percent of vanadium is 29%, the mass percent of silver is 37%, the mass percent of silicon is 4.8%, and the BET surface area is 53m2/g。
example 8:
the catalysts of examples 1-7 and comparative examples 1-3 were charged into a fixed bed reactor, and the o-xylene feed weight space velocity was controlled to be 2 hours-1The reaction raw materials are preheated to 130 ℃, and the gas space velocity is 30000h-1The reaction temperature was 520 ℃ and the reaction results are shown in Table 1.
TABLE 1 reaction results of o-xylene oxidation to o-phthalaldehyde
Example 9:
the catalysts of examples 1-7 and comparative examples 1-3 were charged into a fixed bed reactor, and the weight space velocity of p-xylene feed was controlled to be 2 hours-1the reaction raw materials are preheated to 200 ℃, and the gas space velocity is 30000h-1The reaction temperature was 520 ℃ and the reaction results are shown in Table 2.
TABLE 2 reaction results of p-xylenoxy with terephthalaldehyde
Example 10:
The catalysts of examples 1-7 and comparative examples 1-3 were charged into a fixed bed reactor, and the toluene feed weight space velocity was controlled to 6 hours- 1Reaction raw material preparationHeating to 200 ℃, and the gas space velocity is 8000h- 1The reaction temperature was 340 ℃ and the reaction results are shown in Table 3.
TABLE 3 behaviour of toluene oxidation for benzaldehyde and benzoic acid synthesis
Claims (7)
1. a V-Ag-Si-O catalyst characterized by: 24 to 46 percent of vanadium, 14 to 43 percent of silver and 0.4 to 5.0 percent of silicon, and the BET specific surface area of the V-Ag-Si-O catalyst is 20 to 130m2(ii)/g; the preparation method comprises the following steps of:
1) fully contacting a precursor containing vanadium, silver and silicon to obtain a solution containing the precursor of vanadium, silver and silicon;
2) Forming gel from the solution of the precursor containing vanadium, silver and silicon obtained in the step 1) at the temperature of 60-70 ℃;
3) Adding C3-C6 alcohol into the gel obtained in the step 2), and sealing and crystallizing for 4-6h at the temperature of 50-60 ℃;
4) Drying the material obtained in the step 3) at 90-110 ℃ and roasting at 550-650 ℃ in sequence to obtain the V-Ag-Si-O catalyst;
In the step 2), the time for forming the gel is 5-8 h; in the step 4), the drying time is 4-6h, and the roasting time is 3-8 h;
The mass consumption of the C3-C6 alcohol is 80-300% of the mass of the roasted V-Ag-Si-O catalyst.
2. the V-Ag-Si-O catalyst of claim 1, wherein: the precursor of vanadium comprises at least one of ammonium metavanadate, vanadyl oxalate, vanadyl sulfate or vanadium pentoxide.
3. the V-Ag-Si-O catalyst of claim 2, wherein: the precursor of vanadium comprises at least one of ammonium metavanadate, vanadyl oxalate or vanadium pentoxide.
4. The V-Ag-Si-O catalyst of any one of claims 1 to 3, wherein: the precursor of silver comprises at least one of silver nitrate or silver acetate; the precursor of silicon is ethyl silicate.
5. the V-Ag-Si-O catalyst of any one of claims 1 to 3, wherein: the C3-C6 alcohol is at least one of n-propanol, isopropanol, n-butanol, isobutanol, n-pentanol, isoamyl alcohol, n-hexanol or cyclohexanol.
6. use of the V-Ag-Si-O catalyst according to claim 1, characterized in that: used for preparing aldehyde, carboxylic acid or carboxylic anhydride by catalytic oxidation.
7. the use of claim 6, wherein: the catalytic oxidation reaction is carried out on a fixed bed reactor, the reaction raw material is preheated and gasified at the temperature of 100-650 ℃, and then enters the reactor with air, the reaction temperature is 300-650 ℃, and the liquid space velocity is 1-10h-1The gas space velocity is 0.1-50000h-1。
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| CN109718768A (en) * | 2017-10-31 | 2019-05-07 | 中国石油化工股份有限公司 | A kind of vanadium silver molybdenum oxide catalyst, preparation method and applications |
| CN109718754A (en) * | 2017-10-31 | 2019-05-07 | 中国石油化工股份有限公司 | A kind of vanadium silver nickel metal oxide catalyst, preparation method and applications |
| CN109718769A (en) * | 2017-10-31 | 2019-05-07 | 中国石油化工股份有限公司 | A kind of vanadium silver silicon metal oxide catalyst, preparation method and applications |
| CN110961104A (en) * | 2018-09-28 | 2020-04-07 | 中国石油化工股份有限公司 | Vanadium-silver-tungsten metal oxide catalyst, preparation method and application thereof |
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