CN112495410A - Vanadium phosphorus oxygen catalyst, preparation method and application - Google Patents
Vanadium phosphorus oxygen catalyst, preparation method and application Download PDFInfo
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- CN112495410A CN112495410A CN202110067388.7A CN202110067388A CN112495410A CN 112495410 A CN112495410 A CN 112495410A CN 202110067388 A CN202110067388 A CN 202110067388A CN 112495410 A CN112495410 A CN 112495410A
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- 238000002360 preparation method Methods 0.000 title claims abstract description 23
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- 238000006243 chemical reaction Methods 0.000 claims abstract description 66
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 claims abstract description 50
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims abstract description 44
- 239000012298 atmosphere Substances 0.000 claims abstract description 37
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 34
- 238000001035 drying Methods 0.000 claims abstract description 33
- 238000010438 heat treatment Methods 0.000 claims abstract description 24
- LJYCJDQBTIMDPJ-UHFFFAOYSA-N [P]=O.[V] Chemical compound [P]=O.[V] LJYCJDQBTIMDPJ-UHFFFAOYSA-N 0.000 claims abstract description 23
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 claims abstract description 23
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims abstract description 22
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 14
- 238000000034 method Methods 0.000 claims abstract description 13
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 8
- 239000012018 catalyst precursor Substances 0.000 claims abstract description 6
- 238000001914 filtration Methods 0.000 claims abstract description 6
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims abstract description 6
- 230000003647 oxidation Effects 0.000 claims abstract description 6
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 6
- 239000011259 mixed solution Substances 0.000 claims abstract description 3
- WVDDGKGOMKODPV-ZQBYOMGUSA-N phenyl(114C)methanol Chemical compound O[14CH2]C1=CC=CC=C1 WVDDGKGOMKODPV-ZQBYOMGUSA-N 0.000 claims abstract description 3
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 claims description 33
- 239000007789 gas Substances 0.000 claims description 21
- 235000019445 benzyl alcohol Nutrition 0.000 claims description 11
- 229910052720 vanadium Inorganic materials 0.000 claims description 10
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims description 10
- 238000010992 reflux Methods 0.000 claims description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 4
- 230000001681 protective effect Effects 0.000 claims description 4
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 claims description 2
- 235000018660 ammonium molybdate Nutrition 0.000 claims description 2
- 239000011609 ammonium molybdate Substances 0.000 claims description 2
- 229940010552 ammonium molybdate Drugs 0.000 claims description 2
- 229910052750 molybdenum Inorganic materials 0.000 claims description 2
- 239000011733 molybdenum Substances 0.000 claims description 2
- 229910052759 nickel Inorganic materials 0.000 claims description 2
- 235000015393 sodium molybdate Nutrition 0.000 claims description 2
- 239000011684 sodium molybdate Substances 0.000 claims description 2
- TVXXNOYZHKPKGW-UHFFFAOYSA-N sodium molybdate (anhydrous) Chemical compound [Na+].[Na+].[O-][Mo]([O-])(=O)=O TVXXNOYZHKPKGW-UHFFFAOYSA-N 0.000 claims description 2
- 239000000243 solution Substances 0.000 abstract description 12
- 230000000694 effects Effects 0.000 abstract description 5
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- 238000009776 industrial production Methods 0.000 abstract description 2
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- 239000001273 butane Substances 0.000 description 18
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- 238000006555 catalytic reaction Methods 0.000 description 2
- XPPKVPWEQAFLFU-UHFFFAOYSA-N diphosphoric acid Chemical compound OP(O)(=O)OP(O)(O)=O XPPKVPWEQAFLFU-UHFFFAOYSA-N 0.000 description 2
- 238000003837 high-temperature calcination Methods 0.000 description 2
- 239000013557 residual solvent Substances 0.000 description 2
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/186—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J27/195—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with vanadium, niobium or tantalum
- B01J27/198—Vanadium
-
- 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
- C07D307/56—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 hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D307/60—Two oxygen atoms, e.g. succinic anhydride
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- Catalysts (AREA)
Abstract
The invention provides a vanadium phosphorus oxide catalyst, a preparation method and application thereof, wherein the preparation method comprises the following steps: will V2O5Dissolving the auxiliary agent and the auxiliary agent in a mixed solution of isobutanol and benzyl alcohol, adding phosphoric acid at 45-85 ℃, heating the reaction solution to 100-150 ℃, reacting for 10-16 h, and filtering; and drying the catalyst precursor for 5-12 h at 100-260 ℃ in a certain atmosphere or a mixed atmosphere of nitrogen, air and vacuum to obtain the vanadium-phosphorus-oxygen catalyst. The invention also provides application of the vanadium phosphorus oxide catalyst in preparation of maleic anhydride by catalyzing oxidation of n-butane. The method realizes the performance improvement of the catalyst through the regulation and control of the drying atmosphere, has good effect and has important application value. Through the regulation and control of program drying, the solvent can be more fully removed, and the vanadium phosphorus oxide catalyst is ensured to have good crystal phase structure and surface property. The method is more economical, has high feasibility and simple preparation process, and is suitable for industrial production.
Description
Technical Field
The invention relates to the field of chemical catalysis, in particular to a vanadium phosphorus oxide catalyst, a preparation method and application thereof.
Background
The selective oxidation of n-butane to Maleic Anhydride (MA) is the most successful commercial process for commercial application of alkane conversion. With vanadium-based pyrophosphoric acid (VO)2P2O7The vanadium phosphorus oxide catalyst (VPO) which is the main active phase, in which the active phase (VO) is the most effective catalyst for the reaction, is considered to be the most effective catalyst for the reaction2P2O7VOHPO mainly achieved by heat treatment of semi-hydrate precursors4·0.5H2O topology transformation to obtain vanadium phosphorus oxygen catalyst active phase (VO)2P2O7. The heat treatment process can affect the removal of the solvent remained on the surface of the catalyst, the transformation of the active phase of the precursor and the morphology of the catalyst, so the research of the heat treatment environment becomes a key step for regulating and controlling the performance of the catalyst.
Most studies have generally employed high temperature calcination for heat treatment of the precursor, which causes damage to dehydration of the precursor, removal of residual solvent, and oxidation of the precursor, resulting in oxidation of the active phase and collapse of the catalyst structure, thereby reducing the activity and stability of the catalyst. Most of drying processes for pilot scale of the catalyst have the defects of complex operation, poor controllability, energy waste and the like. The drying procedure and atmosphere in the current heat treatment are not reasonably researched, so that the drying effect and cost control cannot be reasonably controlled when the pilot-scale catalyst is subjected to amplification drying.
Disclosure of Invention
The invention provides a vanadium phosphorus oxide catalyst, a preparation method and application thereof, and solves the problems of complicated drying procedure, poor controllability, energy waste and the like of the existing catalyst.
The technical scheme for realizing the invention is as follows:
a preparation method of a vanadium phosphorus oxide catalyst comprises the following steps:
(1) will V2O5Dissolving the auxiliary agent and the mixed solution of isobutanol and benzyl alcohol, adding phosphoric acid, heating for reflux reaction, and filtering to obtain a catalyst precursor;
(2) and drying the catalyst precursor in a protective gas atmosphere to obtain the vanadium-phosphorus-oxygen catalyst.
The volume ratio of the isobutanol to the benzyl alcohol in the step (1) is (6-10): 1, V2O5The dosage is 400-600 g, and the dosage of isobutanol is 3000-5000 ml.
The auxiliary agent is any one of sodium molybdate, molybdenum acetyl, ammonium molybdate and nickel orthomolybdate, and the molar ratio of Mo to V in the auxiliary agent is 1: 100.
the temperature of the added phosphoric acid is 45-85 ℃, the temperature is raised to 100-150 ℃ after the phosphoric acid is added, the reflux reaction is carried out for 10-16 hours, the concentration of the added phosphoric acid is 85-110 wt%, and the dosage of the phosphoric acid is 550-600 g.
The temperature of the phosphoric acid is 60-70 ℃, the temperature is increased to 120-140 ℃ after the phosphoric acid is added, the reflux reaction is carried out for 11-13 hours, and water separation treatment is carried out in the reaction process.
The protective gas in the step (2) is nitrogen, air or vacuum atmosphere.
And (3) drying for 5-12 hours at the drying treatment temperature of 100-260 ℃ in the step (2).
The drying treatment is stage program atmosphere drying and is divided into four stages, specifically as follows: the temperature of the first stage is 110-130 ℃ and is kept for 5-7 h, the temperature of the second stage is 140-160 ℃ and is kept for 2-6 h, the temperature of the third stage is 210-230 ℃ and is kept for 1-3 h, and the temperature of the fourth stage is 245-260 ℃ and is kept for 1-3 h.
The average valence of vanadium in the catalyst is 3.82-3.95.
Preferably, the catalyst prepared by the invention is applied to the preparation of maleic anhydride by selective oxidation of n-butane.
The invention has the beneficial effects that:
(1) according to the preparation method, the solid raw materials can be well dispersed and the solid-liquid mixed phase can be rapidly stabilized by adjusting the feeding proportion, the feeding sequence, the drying program and the drying atmosphere during the preparation of the catalyst, so that the problem of poor heat transfer and mass transfer is solved; through the regulation and control of program drying, the solvent can be more fully removed, and the vanadium phosphorus oxide catalyst is ensured to have good crystal phase structure and surface property. The method is more economical, has high feasibility and simple preparation process, and is suitable for industrial production.
(2) The method removes the solvent remained on the surface of the precursor by optimizing the atmosphere of the low-temperature section in the drying stage; the subsequent phase controls the temperature and adjusts the composition of the atmosphere to effect the topological transformation of the precursor. Compared with the high-temperature calcination of the heat treatment of most of the existing catalysts, the method can realize the effective removal of the solvent, realize the controllable transformation of the precursor, has strong display controllability, simple operation and high economical efficiency, and can realize the pilot-scale drying treatment of the catalyst precursor.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only some embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to the drawings without creative efforts.
FIG. 1 is a graph showing the performance test of the catalyst of the present invention.
FIG. 2 is a scanning electron micrograph of a vanadium phosphorus oxide catalyst obtained in example 2 of the present invention.
Detailed Description
The technical solutions of the present invention will be described clearly and completely with reference to the following embodiments of the present invention, and it should be understood that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be obtained by a person skilled in the art without inventive effort based on the embodiments of the present invention, are within the scope of the present invention.
Example 1
A preparation method of a vanadium phosphorus oxide catalyst comprises the following steps:
3000ml of isobutanol and 550ml of benzyl alcohol are added into a 10L glass reaction kettle and stirred, and 500g V is added2O51470ml of isobutanol is added after mixing evenly. The reaction solution was heated to 65 ℃ and 577.5g of 100wt% phosphoric acid (65 ℃) were added, and the mixture was heated to 130 ℃ and refluxed for 12 hours. Pumping out the reactant, vacuum drying the reactant at 120 deg.C for 6h in nitrogen atmosphere as compensation gas, heating to 150 deg.C under the atmosphere condition, continuing drying for 1h, then closing vacuum, balancing pressure in the furnace to normal pressure (completed within 1 h) with nitrogen, and storing in 350ml-1Keeping the temperature at 150 ℃ for 2h at min air flow rate, heating to 220 ℃ for 2h, and then heating to 255 ℃ for 2h to obtain gray-black catalyst powder.
Forming catalyst powder in a tablet press with 15MPa, physically crushing, sieving to obtain 20-40 mesh catalyst particles, weighing 3ml catalyst particles, and filling in a fixed bed reactor with an inner diameter of 14mm under a reaction atmosphere of butane gas mixture (V)Butane：VNitrogen gas：VOxygen gas=1.4：19.5：79.1），2000h-1And (3) carrying out performance evaluation reaction for 24 hours at a reaction space velocity, wherein the reaction space velocity is that after the activation for 12 hours at 430 ℃, the temperature is reduced to 420 ℃.
Example 2
A preparation method of a vanadium phosphorus oxide catalyst comprises the following steps:
3000ml of isobutanol and 550ml of benzyl alcohol are added into a 10L glass reaction kettle and stirred, and 500g V is added2O51470ml of isobutanol is added after mixing evenly. The reaction solution was heated to 65 ℃ and 577.5g of 100wt% phosphoric acid (65 ℃) were added, and the mixture was heated to 130 ℃ and refluxed for 12 hours. Pumping out the reactant, vacuum drying the reactant at 120 deg.C for 6h in nitrogen atmosphere as compensation gas, heating to 150 deg.C under the atmosphere condition, continuing drying for 1h, closing vacuum, balancing pressure in the furnace to normal pressure with nitrogen gas (completed within 1 h), and storing in 300ml-1min nitrogen and 50ml-1min air (V)Nitrogen gas：VAir (a)= 6: 1) keeping the temperature at 150 ℃ for 2h at the flow rate, heating to 220 ℃ for 2h, and then heating to 255 ℃ for 2h to obtain the gray-black catalyst powder.
Forming catalyst powder in a tablet press with 15MPa, physically crushing, sieving to obtain 20-40 mesh catalyst particles, weighing 3ml catalyst particles, and filling in a fixed bed reactor with an inner diameter of 14mm under a reaction atmosphere of butane gas mixture (V)Butane：VNitrogen gas：VOxygen gas=1.4：19.5：79.1），2000h-1And (3) carrying out performance evaluation reaction for 24 hours at a reaction space velocity, wherein the reaction space velocity is that after the activation for 12 hours at 430 ℃, the temperature is reduced to 420 ℃.
As can be seen from the SEM image of the vanadium phosphorus oxide catalyst in FIG. 2, the catalyst is in a hierarchical and multi-level 'tremella' shape, the surface of the catalyst is a wrinkled nano-sheet layer, and the whole catalyst is in an assembled and interconnected porous network structure. The hierarchical and multi-layer structure can increase the specific surface area of the catalyst, is beneficial to the exposure of active sites, and the characteristics of the porous network structure can enhance mass transfer and heat transfer and promote reaction.
Example 3
A preparation method of a vanadium phosphorus oxide catalyst comprises the following steps:
3000ml of isobutanol and 550ml of benzyl alcohol are added into a 10L glass reaction kettle and stirred, and 500g V is added2O51470ml of isobutanol is added after mixing evenly. The reaction solution was heated to 65 ℃ and 577.5g of 100wt% phosphoric acid (65 ℃) were added, and the mixture was heated to 130 ℃ and refluxed for 12 hours. Pumping out the reactant, vacuum drying the reactant at 120 deg.C for 6h in nitrogen atmosphere as compensation gas, heating to 150 deg.C under the atmosphere condition, continuing drying for 1h, closing vacuum, balancing pressure in furnace to normal pressure with nitrogen gas (completed within 1 h), and adding 323ml of the solution-1min nitrogen and 27ml-1min air (V)Nitrogen gas：VAir (a)= 12: 1) keeping the temperature at 150 ℃ for 2h at the flow rate, heating to 220 ℃ for 2h, and then heating to 255 ℃ for 2h to obtain the gray-black catalyst powder.
Molding the catalyst powder in a tablet press with 15MPa, physically crushing, and sieving to obtain 20-40 mesh catalyst particlesWeighing 3ml of catalyst particles, and filling the catalyst particles into a fixed bed reactor with an inner diameter of 14mm in a reaction atmosphere of butane gas mixture (V)Butane：VNitrogen gas：VOxygen gas=1.4：19.5：79.1），2000h-1And (3) carrying out performance evaluation reaction for 24 hours at a reaction space velocity, wherein the reaction space velocity is that after the activation for 12 hours at 430 ℃, the temperature is reduced to 420 ℃.
Example 4
A preparation method of a vanadium phosphorus oxide catalyst comprises the following steps:
3000ml of isobutanol and 550ml of benzyl alcohol are added into a 10L glass reaction kettle and stirred, and 500g V is added2O51470ml of isobutanol is added after mixing evenly. The reaction solution was heated to 65 ℃ and 577.5g of 100wt% phosphoric acid (65 ℃) were added, and the mixture was heated to 130 ℃ and refluxed for 12 hours. Pumping out the reactant, vacuum drying the reactant at 120 deg.C for 6h in nitrogen atmosphere as compensation gas, heating to 150 deg.C under the atmosphere condition, continuing drying for 1h, closing vacuum, balancing pressure in the furnace to normal pressure with nitrogen gas (completed within 1 h), and storing in 332ml-1min nitrogen and 18ml-1min air (V)Nitrogen gas：VAir (a)= 18: 1) keeping the temperature at 150 ℃ for 2h at the flow rate, heating to 220 ℃ for 2h, and then heating to 255 ℃ for 2h to obtain the gray-black catalyst powder.
Forming catalyst powder in a tablet press with 15MPa, physically crushing, sieving to obtain 20-40 mesh catalyst particles, weighing 3ml catalyst particles, and filling in a fixed bed reactor with an inner diameter of 14mm under a reaction atmosphere of butane gas mixture (V)Butane：VNitrogen gas：VOxygen gas=1.4：19.5：79.1），2000h-1And (3) carrying out performance evaluation reaction for 24 hours at a reaction space velocity, wherein the reaction space velocity is that after the activation for 12 hours at 430 ℃, the temperature is reduced to 420 ℃.
Example 5
A preparation method of a vanadium phosphorus oxide catalyst comprises the following steps:
3000ml of isobutanol and 550ml of benzyl alcohol are added into a 10L glass reaction kettle and stirred, and 500g V is added2O51470ml of isobutanol is added after mixing evenly. The reaction solution was heated to 65 ℃ and 577.5g of 100wt% phosphoric acid (65 ℃) were added, and the mixture was heated to 130 ℃ and refluxed for 12 hours.Pumping out the reactant, vacuum drying the reactant at 120 deg.C for 6h in nitrogen atmosphere as compensation gas, heating to 150 deg.C under the atmosphere condition, continuing drying for 1h, then closing vacuum, balancing pressure in the furnace to normal pressure (completed within 1 h) with nitrogen, and storing in 350ml-1Keeping the temperature at 150 ℃ for 2h under the flow of min nitrogen, heating to 220 ℃ for 2h, and then heating to 255 ℃ for 2h to obtain gray black catalyst powder.
Forming catalyst powder in a tablet press with 15MPa, physically crushing, sieving to obtain 20-40 mesh catalyst particles, weighing 3ml catalyst particles, and filling in a fixed bed reactor with an inner diameter of 14mm under a reaction atmosphere of butane gas mixture (V)Butane：VNitrogen gas：VOxygen gas=1.4：19.5：79.1），2000h-1And (3) carrying out performance evaluation reaction for 24 hours at a reaction space velocity, wherein the reaction space velocity is that after the activation for 12 hours at 430 ℃, the temperature is reduced to 420 ℃.
Example 6
A preparation method of a vanadium phosphorus oxide catalyst comprises the following steps:
adding 3000ml of isobutanol and 550ml of benzyl alcohol into a 10L glass reaction kettle, stirring, and adding 500gV2O51470ml of isobutanol is added after mixing evenly. The reaction solution was heated to 65 ℃ and 577.5g of 100wt% phosphoric acid (65 ℃) were added and the mixture was heated to 130 ℃ and refluxed for 12 hours. Pumping and filtering the reactant, drying the reactant in vacuum at 120 ℃ for 6h in the atmosphere of nitrogen as compensation gas, raising the temperature to 150 ℃ under the atmosphere condition, continuing to dry for 4h, raising the temperature to 220 ℃ for 2h, and raising the temperature to 255 ℃ for 2h to obtain gray-black catalyst powder.
Forming catalyst powder in a tablet press with 15MPa, physically crushing, sieving to obtain 20-40 mesh catalyst particles, weighing 3ml catalyst particles, and filling in a fixed bed reactor with an inner diameter of 14mm under a reaction atmosphere of butane gas mixture (V)Butane：VNitrogen gas：VOxygen gas=1.4：19.5：79.1），2000h-1And (3) carrying out performance evaluation reaction for 24 hours at a reaction space velocity, wherein the reaction space velocity is that after the activation for 12 hours at 430 ℃, the temperature is reduced to 420 ℃.
Example 7
A preparation method of a vanadium phosphorus oxide catalyst comprises the following steps:
1800ml of isobutanol and 745ml of benzyl alcohol are added into a 10L glass reaction kettle and stirred, and 400g V is added2O51200ml of isobutanol is added after uniform mixing. The reaction solution was heated to 45 ℃ and 577.5g of 85wt% phosphoric acid (65 ℃) were added, and the mixture was heated to 100 ℃ and refluxed for 10 hours. Pumping and filtering the reactant, drying the reactant in vacuum for 5h at 110 ℃ in the atmosphere of nitrogen as compensation gas, raising the temperature to 140 ℃ under the atmosphere condition, continuing to dry for 2h, then raising the temperature to 210 ℃ for 1h, and raising the temperature to 245 ℃ for 1h to obtain gray-black catalyst powder.
Forming catalyst powder in a tablet press with 15MPa, physically crushing, sieving to obtain 20-40 mesh catalyst particles, weighing 3ml catalyst particles, and filling in a fixed bed reactor with an inner diameter of 14mm under a reaction atmosphere of butane gas mixture (V)Butane：VNitrogen gas：VOxygen gas=1.4：19.5：79.1），2000h-1And (3) carrying out performance evaluation reaction for 24 hours at a reaction space velocity, wherein the reaction space velocity is that after the activation for 12 hours at 430 ℃, the temperature is reduced to 420 ℃.
Example 8
A preparation method of a vanadium phosphorus oxide catalyst comprises the following steps:
3000ml of isobutanol and 300ml of benzyl alcohol are added into a 10L glass reaction kettle and stirred, and 600g V is added2O5After mixing uniformly, 2000ml of isobutanol was added. The reaction solution was heated to 85 ℃ and 577.5g of 110wt% phosphoric acid (65 ℃) were added, and the mixture was heated to 150 ℃ and refluxed for 16 hours. Pumping and filtering the reactant, drying the reactant in vacuum at 130 ℃ for 7h in an atmosphere with nitrogen as compensation gas, raising the temperature to 160 ℃ under the atmosphere condition, continuing to dry for 6h, raising the temperature to 230 ℃ for 3h, and raising the temperature to 260 ℃ for 3h to obtain gray-black catalyst powder.
Forming catalyst powder in a tablet press with 15MPa, physically crushing, sieving to obtain 20-40 mesh catalyst particles, weighing 3ml catalyst particles, and filling in a fixed bed reactor with an inner diameter of 14mm under a reaction atmosphere of butane gas mixture (V)Butane：VNitrogen gas：VOxygen gas=1.4：19.5：79.1），2000h-1The reaction space velocity is reduced to 420 ℃ after activation for 12h at 430 ℃ for performance evaluation reaction24h。
Comparative example 1
3000ml of isobutanol and 550ml of benzyl alcohol are added into a 10L glass reaction kettle and stirred, and 500g V is added2O51470ml of isobutanol is added after mixing evenly. The reaction solution was heated to 65 ℃ and 577.5g of 100wt% phosphoric acid (65 ℃) were added, and the mixture was heated to 130 ℃ and refluxed for 12 hours. The reaction mass is filtered and dried in air: drying at 50 ℃ for 2h, drying at 95 ℃ for 3h, drying at 110 ℃ for 5h, and drying at 120 ℃ for 4h to obtain the catalyst powder.
Forming catalyst powder in a tablet press with 15MPa, physically crushing, sieving to obtain 20-40 mesh catalyst particles, weighing 3ml catalyst particles, and filling in a fixed bed reactor with an inner diameter of 14mm under a reaction atmosphere of butane gas mixture (V)Butane：VNitrogen gas：VOxygen gas=1.4：19.5：79.1），2000h-1And (3) carrying out performance evaluation reaction for 24 hours at a reaction space velocity, wherein the reaction space velocity is that after the activation for 12 hours at 430 ℃, the temperature is reduced to 420 ℃.
The catalyst is used for selectively oxidizing n-butane to prepare maleic anhydride, and the performance is as follows:
the valence state analysis is carried out on the catalyst prepared by the invention, and the vanadium average valence state information of the vanadium phosphorus oxide catalyst is shown in a table 2:
from the vanadium average valence test of the vanadium phosphorus oxide catalyst, it can be observed that the average valence of vanadium reaches the highest value under the dry atmosphere in vacuum (3.99), the average valence of vanadium is the lowest value under the nitrogen atmosphere (3.8260), and the average valence of vanadium is 3.9514 under the air atmosphere, and the above results show that the vanadium phosphorus oxide precursor can be easily converted into V under the dry atmosphere in vacuum4+Oxides, i.e. having an oxygen-free content in a nitrogen atmosphere, allowing partial conversion of the vanadium phosphorus oxygen precursor into V3+Vanadium phosphorus oxygen catalysis of oxides, but with too low a valence stateThe agent is unfavorable for the utilization of active components, and the average valence state of vanadium is close to V under the air atmosphere4+，V3+/V4+Balance is achieved; in a mixed atmosphere of air and nitrogen, nitrogen: air = 12: when 1, the average valence of vanadium is highest, and V is realized3+/V4+Reasonable distribution and balance, and the result pair not only ensures the removal of residual solvent by precursor drying, but also improves the activity of the vanadium phosphorus oxide catalyst.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.
Claims (10)
1. The preparation method of the vanadium phosphorus oxide catalyst is characterized by comprising the following steps:
(1) will V2O5Dissolving the auxiliary agent and the mixed solution of isobutanol and benzyl alcohol, adding phosphoric acid, heating for reflux reaction, and filtering to obtain a catalyst precursor;
(2) and drying the catalyst precursor in a protective gas atmosphere to obtain the vanadium-phosphorus-oxygen catalyst.
2. The method of claim 1, wherein: the volume ratio of the isobutanol to the benzyl alcohol in the step (1) is (6-10): 1, V2O5The dosage is 400-600 g, and the dosage of isobutanol is 3000-5000 ml.
3. The method of claim 1, wherein: the auxiliary agent is any one of sodium molybdate, molybdenum acetyl, ammonium molybdate and nickel orthomolybdate, and the molar ratio of Mo to V in the auxiliary agent is 1: 100.
4. the method of claim 1, wherein: the temperature of the phosphoric acid is 45-85 ℃ during adding, the temperature is raised to 100-150 ℃ after adding, the reflux reaction is carried out for 10-16 h, and the concentration of the phosphoric acid after adding is 85-110 wt%.
5. The method of claim 4, wherein: the temperature of the phosphoric acid is 60-70 ℃, the temperature is increased to 120-140 ℃ after the phosphoric acid is added, and the reflux reaction is carried out for 11-13 h.
6. The method of claim 1, wherein: the protective gas in the step (2) is nitrogen, air or vacuum atmosphere.
7. The method according to any one of claims 1 to 6, wherein the drying treatment temperature in the step (2) is 100 to 260 ℃ and the drying time is 5 to 12 hours.
8. The method according to claim 7, wherein the drying treatment is a step-programmed atmosphere drying, which is divided into four steps, specifically as follows: the temperature of the first stage is 110-130 ℃ and is kept for 5-7 h, the temperature of the second stage is 140-160 ℃ and is kept for 2-6 h, the temperature of the third stage is 210-230 ℃ and is kept for 1-3 h, and the temperature of the fourth stage is 245-260 ℃ and is kept for 1-3 h.
9. The catalyst prepared by the preparation method of claim 8, wherein: the average valence of vanadium in the catalyst is 3.82-3.95.
10. Use of the catalyst of claim 9 in the selective oxidation of n-butane to maleic anhydride.
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| CN1067189A (en) * | 1992-07-21 | 1992-12-23 | 中国石油化工总公司 | The preparation method who is used for the vanadium-phosphorus-Zr mixed oxide catalyst of production MALEIC ANHYDRIDE |
| CN1241147A (en) * | 1997-06-04 | 2000-01-12 | 萨索尔技术(控股)有限公司 | Process for producing vanadium phosphorus oxide catalyst |
| CN104549392A (en) * | 2013-10-22 | 2015-04-29 | 中国石油化工股份有限公司 | Preparation method for vanadium-phosphorus oxide catalyst |
| US20170014812A1 (en) * | 2015-07-16 | 2017-01-19 | Ineos Europe Ag | CATALYST FOR n-BUTANE OXIDATION TO MALEIC ANHYDRIDE |
| CN111514828A (en) * | 2020-04-17 | 2020-08-11 | 中国科学院上海硅酸盐研究所 | Barium stannate composite silica aerogel powder and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1067189A (en) * | 1992-07-21 | 1992-12-23 | 中国石油化工总公司 | The preparation method who is used for the vanadium-phosphorus-Zr mixed oxide catalyst of production MALEIC ANHYDRIDE |
| CN1241147A (en) * | 1997-06-04 | 2000-01-12 | 萨索尔技术(控股)有限公司 | Process for producing vanadium phosphorus oxide catalyst |
| CN104549392A (en) * | 2013-10-22 | 2015-04-29 | 中国石油化工股份有限公司 | Preparation method for vanadium-phosphorus oxide catalyst |
| US20170014812A1 (en) * | 2015-07-16 | 2017-01-19 | Ineos Europe Ag | CATALYST FOR n-BUTANE OXIDATION TO MALEIC ANHYDRIDE |
| CN111514828A (en) * | 2020-04-17 | 2020-08-11 | 中国科学院上海硅酸盐研究所 | Barium stannate composite silica aerogel powder and preparation method thereof |
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