CN112892566A - Method for regulating vanadium valence state in vanadium-phosphorus-oxygen catalyst and application thereof - Google Patents
Method for regulating vanadium valence state in vanadium-phosphorus-oxygen catalyst and application thereof Download PDFInfo
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- 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
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Abstract
The invention relates to a method for regulating and controlling the vanadium valence state in a vanadium-phosphorus-oxygen catalyst, which comprises the following steps: preparing a vanadium phosphorus oxide precursor; mixing the vanadium-phosphorus-oxygen precursor and balls in a ball-milling tank according to a mass ratio of 1: 0.5-2, vacuumizing the ball-milling tank, introducing gas, and performing ball milling by using a ball mill to obtain a ball-milled product, wherein the gas is oxygen or a mixed gas of oxygen and inert gas, and the inert gas is inert gas and/or nitrogen; and activating the ball-milled product to obtain the vanadium-phosphorus-oxygen catalyst. The method remarkably improves the activity and selectivity of the vanadium phosphorus oxide catalyst product compared with the existing catalyst by regulating the valence state of vanadium of the catalyst.
Description
Technical Field
The invention belongs to the field of chemical catalysis, and relates to a method for regulating and controlling a vanadium valence state in a vanadium-phosphorus-oxygen catalyst and application thereof.
Background
Maleic anhydride, also known as maleic anhydride for short, is white needle-shaped crystals at room temperature and emits an offensive odor, and maleic anhydride has unsaturated carbonyl bonds and ethylenic bonds in its molecular structure, so that various reactions such as alkylation, polymerization, redox, esterification, and the like can occur. Maleic anhydride is currently the third anhydride listed after acetic anhydride and phthalic anhydride in the world.
At present, the most effective catalyst for preparing maleic anhydride by oxidizing n-butane is a vanadium-phosphorus-oxygen catalyst, the preparation method of a precursor of the catalyst has great relationship with catalytic activity and selectivity, simultaneously the valence state of vanadium is crucial to redox cycle and the activity and the selectivity of the catalyst, and proper V5+And V4+The ratio of (a) to (b) can increase the selectivity of the catalyst.
Therefore, in order to improve the selectivity and activity of the vanadium phosphorus oxide catalyst, a large number of scholars at home and abroad deeply research on the regulation and control of the vanadium valence state. For example, patent CN109248699A changes V in vanadium phosphorus oxide catalyst system after adding active component bismuth5+And V4+To increase the activity of the catalyst. Patent CN103108694A discloses that conventional active vanadium phosphorus oxide catalyst with average vanadium valence of about 4.10-4.40 is contacted with organic solvent with dielectric constant of about 5-55, and the vanadium valence is reduced to below 4.10, so as to increase the activity of the catalyst. The above patent improves the selectivity of the vanadium phosphorus oxide catalyst to a certain extent by adding a cocatalyst, but the operation is complicated.
Disclosure of Invention
In view of the above problems in the prior art, the present invention aims to provide a method for regulating the vanadium valence state in a vanadium phosphorus oxide catalyst and an application thereof.
The invention provides a method for regulating and controlling the vanadium valence state in a vanadium-phosphorus-oxygen catalyst, which comprises the following steps:
preparing a vanadium phosphorus oxide precursor;
mixing the vanadium-phosphorus-oxygen precursor and balls in a ball-milling tank according to a mass ratio of 1: 0.5-2, vacuumizing the ball-milling tank, introducing gas, and performing ball milling by using a ball mill to obtain a ball-milled product, wherein the gas is oxygen or a mixed gas of oxygen and inert gas, and the inert gas is inert gas and/or nitrogen;
and activating the ball-milled product to obtain the vanadium-phosphorus-oxygen catalyst.
The invention also provides the application of the vanadium-phosphorus-oxygen catalyst obtained by the method for regulating the vanadium valence state in the vanadium-phosphorus-oxygen catalyst in the preparation of maleic anhydride by selective oxidation of n-butane.
The method for regulating the vanadium valence state in the vanadium-phosphorus-oxygen catalyst can regulate the vanadium valence state of the catalyst, so that the activity and the selectivity of the vanadium-phosphorus-oxygen catalyst are obviously improved compared with those of the existing catalyst. In addition, compared with the prior art, the method has the following advantages: (1) the method of the invention does not add any auxiliary agent, and has the advantages of saving energy, avoiding secondary pollution and the like compared with the method of adding the auxiliary agent. (2) The method regulates the valence state of vanadium by regulating the atmosphere in the ball milling tank, thereby effectively improving the selectivity and the activity of the vanadium-phosphorus-oxygen catalyst, and has the characteristics of simple method, low cost and controllable atmosphere type.
Drawings
FIG. 1 is an XPS plot of V2p3/2 for the vanadium phosphorus oxide catalysts obtained in examples 1-5 and comparative example 1.
FIG. 2 is an XPS plot of O1s for the vanadium phosphorus oxide catalysts obtained in examples 1-5 and comparative example 1.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is described in further detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
The invention provides a method for regulating and controlling the vanadium valence state in a vanadium-phosphorus-oxygen catalyst, which comprises the following steps:
s01: preparing a vanadium phosphorus oxide precursor;
s02: mixing the vanadium-phosphorus-oxygen precursor and balls in a ball-milling tank according to a mass ratio of 1: 0.5-2, vacuumizing the ball-milling tank, introducing gas, and performing ball milling by using a ball mill to obtain a ball-milled product, wherein the gas is oxygen or a mixed gas of oxygen and inert gas, and the inert gas is inert gas and/or nitrogen;
s03: and activating the ball-milled product to obtain the vanadium-phosphorus-oxygen catalyst.
The invention also provides the application of the vanadium-phosphorus-oxygen catalyst obtained by the method for regulating the vanadium valence state in the vanadium-phosphorus-oxygen catalyst in the preparation of maleic anhydride by selective oxidation of n-butane.
Specifically, in step S01, the preparation method of the vanadium phosphorus oxide precursor is preferably: mixing a vanadium source, benzyl alcohol and isobutanol, heating to 135 ℃ for refluxing for 3 hours to obtain a mixture, cooling to 75 ℃, adding a phosphorus source, heating to 135 ℃ for refluxing for 16 hours, and filtering and drying a product to obtain the vanadium-phosphorus oxide precursor.
In step S02, preferably, the inert gas is nitrogen, the oxygen content is 30% to 60%, and the average valence of vanadium and V of the vanadium phosphorus oxide catalyst obtained in the atmosphere are5+And V4+The ratio of (A) is most favorable for improving the selectivity of the maleic anhydride. The ball milling tank is at least one of a stainless steel vacuum tank, a zirconia tank, an agate tank and a ceramic tank, and preferably, the ball milling tank is the zirconia tank; specifically, the ball is at least one of a stainless steel ball, a zirconia ball, an agate ball and a ceramic ball; preferably, the balls are zirconia balls; preferably, the vanadium phosphorus oxide precursor is mixed with the ball according to the mass ratio of 1: 1.
In step S03, a raw material gas (butane/air ═ 1.4/98.6) is introduced at a temperature of 430 ℃ to activate, and a vanadium phosphorus oxide catalyst is obtained.
The method of regulating the vanadium valence state in a vanadium phosphorus oxide catalyst is illustrated by the following specific examples. The compounds in the following examples can be prepared directly according to the existing methods, but of course, in other examples, they can be directly commercially available, and are not limited thereto.
Example 1:
preparation of vanadium phosphorus oxide precursor
Weighing 20g V2O5Mixing with benzyl alcohol and isobutanol, heating to 135 ℃ under the action of mechanical stirring, heating and refluxing for 3h, then cooling to 75 ℃, adding 16mL of phosphoric acid with the mass fraction of 85 wt%, heating to 135 ℃, heating and refluxing for 16h under continuous stirring, filtering the product, and drying to obtain the vanadium-phosphorus-oxygen precursor.
And filling oxygen into the air bag, vacuumizing the ball-milling tank filled with the vanadium-phosphorus-oxygen precursor, putting the gas in the air bag into the ball-milling tank, carrying out ball milling, tabletting the ball-milled powder, crushing and screening to obtain a ball-milled product with the particle size of 20-40 meshes.
Loading the ball-milled product into a fixed bed reactor for activation, wherein the activation condition is airspeed of 2000h-1Heating to 430 ℃ and activating for 12h to obtain the vanadium-phosphorus-oxygen catalyst, wherein the atmosphere contains butane/air which is 1.4/98.6. After the vanadium-phosphorus oxide catalyst is activated, the reaction temperature is reduced to 420 ℃ to carry out the reaction of preparing maleic anhydride by oxidizing n-butane. The reaction results are shown in Table 1.
Example 2:
preparation of vanadium phosphorus oxide precursor
Weighing 20g V2O5Mixing with benzyl alcohol and isobutanol, heating to 135 ℃ under the action of mechanical stirring, heating and refluxing for 3h, then cooling to 75 ℃, adding 16mL of phosphoric acid with the mass fraction of 85 wt%, heating to 135 ℃, heating and refluxing for 16h under continuous stirring, filtering the product, and drying to obtain the vanadium-phosphorus-oxygen precursor.
Filling oxygen and nitrogen into the air bag according to the flow ratio of 1:1 and the time ratio of 4:1, vacuumizing the ball-milling tank filled with the vanadium-phosphorus-oxygen precursor, putting the gas in the air bag into the ball-milling tank, performing ball milling, tabletting the ball-milled powder, crushing and screening to obtain a ball-milled product with 20-40 meshes.
Loading the ball-milled product into a fixed bed reactor for activation, wherein the activation condition is airspeed of 2000h-1The atmosphere contains butane/air which is 1.4/98.6, and the temperature is raised to 430 ℃ for activation for 12 h. After the vanadium phosphorus oxide catalyst is activated, the reaction temperature is reduced to 420 ℃ to carry out the reaction of preparing maleic anhydride by oxidizing n-butane. Reaction junctionThe results are shown in Table 1.
Example 3:
preparation of vanadium phosphorus oxide precursor
Weighing 20g V2O5Mixing with benzyl alcohol and isobutanol, heating to 135 ℃ under the action of mechanical stirring, heating and refluxing for 3h, then cooling to 75 ℃, adding 16mL of phosphoric acid with the mass fraction of 85 wt%, heating to 135 ℃, heating and refluxing for 16h under continuous stirring, filtering the product, and drying to obtain the vanadium-phosphorus-oxygen precursor.
Filling oxygen and nitrogen into the air bag according to the flow ratio of 1:1 and the time ratio of 3:2, vacuumizing the ball-milling tank filled with the vanadium-phosphorus-oxygen precursor, putting the gas in the air bag into the ball-milling tank, performing ball milling, tabletting the ball-milled powder, crushing and screening to obtain a ball-milled product with 20-40 meshes.
Loading the ball-milled product into a fixed bed reactor for activation, wherein the activation condition is airspeed of 2000h-1The atmosphere contains butane/air which is 1.4/98.6, and the temperature is raised to 430 ℃ for activation for 12 h. After the vanadium phosphorus oxide catalyst is activated, the reaction temperature is reduced to 420 ℃ to carry out the reaction of preparing maleic anhydride by oxidizing n-butane. The reaction results are shown in Table 1.
Example 4
Preparation of vanadium phosphorus oxide precursor
Weighing 20g V2O5Mixing with benzyl alcohol and isobutanol, heating to 135 ℃ under the action of mechanical stirring, heating and refluxing for 3h, then cooling to 75 ℃, adding 16mL of phosphoric acid with the mass fraction of 85 wt%, heating to 135 ℃, heating and refluxing for 16h under continuous stirring, filtering the product, and drying to obtain the vanadium-phosphorus-oxygen precursor.
Filling oxygen and nitrogen into the air bag according to the flow ratio of 1:1 and the time ratio of 2:3, vacuumizing the ball-milling tank filled with the vanadium-phosphorus-oxygen precursor, putting the gas in the air bag into the ball-milling tank, performing ball milling, tabletting the ball-milled powder, crushing and screening to obtain a ball-milled product with 20-40 meshes.
Loading the ball-milled product into a fixed bed reactor for activation, wherein the activation condition is airspeed of 2000h-1The atmosphere is butaneAnd (3) heating air to 1.4/98.6, and activating for 12h at 430 ℃. After the vanadium phosphorus oxide catalyst is activated, the reaction temperature is reduced to 420 ℃ to carry out the reaction of preparing maleic anhydride by oxidizing n-butane. The reaction results are shown in Table 1.
Example 5
Preparation of vanadium phosphorus oxide precursor
Weighing 20g V2O5Mixing with benzyl alcohol and isobutanol, heating to 135 ℃ under the action of mechanical stirring, heating and refluxing for 3h, then cooling to 75 ℃, adding 16mL of phosphoric acid with the mass fraction of 85 wt%, heating to 135 ℃, heating and refluxing for 16h under continuous stirring, filtering the product, and drying to obtain the vanadium-phosphorus-oxygen precursor.
Filling oxygen and nitrogen into the air bag according to the flow ratio of 1:1 and the time ratio of 1:4, vacuumizing the ball-milling tank filled with the vanadium-phosphorus-oxygen precursor, putting the gas in the air bag into the ball-milling tank, performing ball milling, tabletting the ball-milled powder, crushing and screening to obtain a ball-milled product with 20-40 meshes.
Loading the ball-milled product into a fixed bed reactor for activation, wherein the activation condition is airspeed of 2000h-1The atmosphere contains butane/air which is 1.4/98.6, and the temperature is raised to 430 ℃ for activation for 12 h. After the vanadium phosphorus oxygen is activated, the reaction temperature is reduced to 420 ℃ to carry out the reaction of preparing maleic anhydride by oxidizing n-butane. The reaction results are shown in Table 1.
Comparative example 1:
preparation of vanadium phosphorus oxide precursor
Weighing 20g V2O5Mixing with benzyl alcohol and isobutanol, heating to 135 ℃ under the action of mechanical stirring, heating and refluxing for 3h, then cooling to 75 ℃, adding 16mL of phosphoric acid with the mass fraction of 85 wt%, heating to 135 ℃, heating and refluxing for 16h under continuous stirring, filtering the product, and drying to obtain the vanadium-phosphorus-oxygen precursor.
And filling nitrogen into the air bag, vacuumizing the ball-milling tank filled with the vanadium-phosphorus-oxygen precursor, putting the gas in the air bag into the ball-milling tank, performing ball milling, tabletting the ball-milled powder, crushing and screening to obtain the 20-40-mesh vanadium-phosphorus-oxygen catalyst.
Catalyzing the above vanadium phosphorus oxygenThe agent is loaded into a fixed bed reactor for activation, and the activation condition is space velocity of 2000h-1The atmosphere contains butane/air which is 1.4/98.6, and the temperature is raised to 430 ℃ for activation for 12 h. After the vanadium phosphorus oxygen is activated, the reaction temperature is reduced to 420 ℃ to carry out the reaction of preparing maleic anhydride by oxidizing n-butane. The reaction results are shown in Table 1.
Comparative example 2:
preparation of vanadium phosphorus oxide precursor
Weighing 20g V2O5Mixing with benzyl alcohol and isobutanol, heating to 135 ℃ under the action of mechanical stirring, heating and refluxing for 3h, then cooling to 75 ℃, adding 16mL of phosphoric acid with the mass fraction of 85 wt%, heating to 135 ℃, heating and refluxing for 16h under continuous stirring, filtering the product, and drying to obtain the vanadium-phosphorus-oxygen precursor.
And directly filling the catalyst into a ball milling tank for ball milling, tabletting, crushing and screening the ball milled powder to obtain the vanadium-phosphorus-oxygen catalyst with the particle size of 20-40 meshes.
The vanadium phosphorus oxygen catalyst is loaded into a fixed bed reactor for activation, and the activation condition is space velocity of 2000h-1The atmosphere contains butane/air which is 1.4/98.6, and the temperature is raised to 430 ℃ for activation for 12 h. After the vanadium phosphorus oxygen is activated, the reaction temperature is reduced to 420 ℃ to carry out the reaction of preparing maleic anhydride by oxidizing n-butane. The reaction results are shown in Table 1.
Comparative example 3:
preparation of vanadium phosphorus oxide precursor
Weighing 20g V2O5Mixing with benzyl alcohol and isobutanol, heating to 135 ℃ under the action of mechanical stirring, heating and refluxing for 3h, then cooling to 75 ℃, adding 16mL of phosphoric acid with the mass fraction of 85 wt%, heating to 135 ℃, heating and refluxing for 16h under continuous stirring, filtering the product, and drying to obtain the vanadium-phosphorus-oxygen precursor.
And tabletting, crushing and screening the prepared catalyst precursor powder to obtain the 20-40-mesh vanadium-phosphorus-oxygen catalyst.
The vanadium phosphorus oxygen catalyst is loaded into a fixed bed reactor for activation, and the activation condition is space velocity of 2000h-1The atmosphere contains butane/air which is 1.4/98.6, and the temperature is raised to 430 ℃ for activation for 12 h. Vanadium phosphorus oxygen activationAfter the reaction is finished, the reaction temperature is reduced to 420 ℃ for the reaction of preparing maleic anhydride by oxidizing n-butane. The reaction results are shown in Table 1.
TABLE 1
The evaluation results in table 1 show that the ball milling atmosphere plays a key role in the catalyst, and the selectivity and yield of maleic anhydride are both significantly improved.
TABLE 2
FIGS. 1 and 2 are XPS plots of V2p3/2 and O1s for the catalysts after conditioning the ball milling atmosphere in example 1, example 2, example 3, example 4, example 5 and comparative example 1, respectively. From the results, it can be seen that the vanadium valence state in the catalyst is different in different ball milling atmospheres, and from the XPS processing results of different ball milling atmosphere catalysts in Table 2, it can be seen that the vanadium valence state in the prepared catalyst is firstly increased and then decreased along with the increase of the oxygen content, and the experimental results in Table 1 show that the performance of the prepared catalyst in the oxidation reaction of n-butane is also increased and then decreased along with the increase of the oxygen content, and the peak value appears in O2(vol%)The performance of the vanadium phosphorus oxide catalyst is optimal at 40%, i.e. at a volume fraction of oxygen of 40%. The optimal catalyst is found by experiments to be 40% O2VPO, compared with 0% O2The selectivity of n-butane to VPO is improved by 10.66 percent, the molar yield of maleic anhydride is improved by 8.82 percent, and the suitable V is shown5+/V4+Is beneficial to the reaction of preparing maleic anhydride by oxidizing n-butane, thereby improving the activity of the catalyst.
The applicant states that the present invention is illustrated in detail by the above examples, but the present invention is not limited to the above detailed methods, i.e. it is not meant that the present invention must rely on the above detailed methods for its implementation. It should be understood by those skilled in the art that any modification of the present invention, equivalent substitutions of the raw materials of the product of the present invention, addition of auxiliary components, selection of specific modes, etc., are within the scope and disclosure of the present invention.
Claims (10)
1. A method of modulating the vanadium valence state in a vanadium phosphorus oxide catalyst, the method comprising the steps of:
preparing a vanadium phosphorus oxide precursor;
mixing the vanadium-phosphorus-oxygen precursor and balls in a ball-milling tank according to a mass ratio of 1: 0.5-2, vacuumizing the ball-milling tank, introducing gas, and performing ball milling by using a ball mill to obtain a ball-milled product, wherein the gas is oxygen or a mixed gas of oxygen and inert gas, and the inert gas is inert gas and/or nitrogen;
and activating the ball-milled product to obtain the vanadium-phosphorus-oxygen catalyst.
2. The method according to claim 1, wherein the vanadium phosphorus oxide precursor is prepared by the following steps: mixing a vanadium source, benzyl alcohol and isobutanol, heating to 135 ℃ for refluxing for 3 hours to obtain a mixture, cooling to 75 ℃, adding a phosphorus source, heating to 135 ℃ for refluxing for 16 hours, and filtering and drying a product to obtain the vanadium-phosphorus oxide precursor.
3. The method of claim 1, wherein the inert gas is nitrogen.
4. The method of claim 1, wherein the oxygen content is 30% to 60%.
5. The method of claim 1, wherein the ball mill jar is at least one of a stainless steel vacuum jar, a zirconia jar, an agate jar, a ceramic jar.
6. The method of claim 5, wherein the ball mill pot is a zirconia pot.
7. The method of claim 1, wherein the balls are at least one of stainless steel balls, zirconia balls, agate balls, and ceramic balls.
8. The method of claim 7, wherein the balls are zirconia balls.
9. The method of claim 1, wherein the temperature of activation is 430 ℃.
10. The application of the vanadium phosphorus oxide catalyst obtained by the method for regulating and controlling the vanadium valence state in the vanadium phosphorus oxide catalyst according to claims 1-9 in preparation of maleic anhydride by selective oxidation of n-butane.
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Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN1311058A (en) * | 2000-12-29 | 2001-09-05 | 南京大学 | Small granular size vanadium-phosphorus-oxygen catalyst and its preparation and use |
CN111701608A (en) * | 2020-07-09 | 2020-09-25 | 中国科学院过程工程研究所 | Method for preparing vanadium-phosphorus-oxygen catalyst with assistance of hydrotalcite |
CN111701624A (en) * | 2020-07-09 | 2020-09-25 | 中国科学院过程工程研究所 | Regeneration method and application of deactivated vanadium phosphorus oxide catalyst |
CN111701609A (en) * | 2020-07-09 | 2020-09-25 | 中国科学院过程工程研究所 | Method for assisting vanadium-phosphorus-oxygen catalyst by using rare earth-based hydrotalcite |
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Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN1311058A (en) * | 2000-12-29 | 2001-09-05 | 南京大学 | Small granular size vanadium-phosphorus-oxygen catalyst and its preparation and use |
CN111701608A (en) * | 2020-07-09 | 2020-09-25 | 中国科学院过程工程研究所 | Method for preparing vanadium-phosphorus-oxygen catalyst with assistance of hydrotalcite |
CN111701624A (en) * | 2020-07-09 | 2020-09-25 | 中国科学院过程工程研究所 | Regeneration method and application of deactivated vanadium phosphorus oxide catalyst |
CN111701609A (en) * | 2020-07-09 | 2020-09-25 | 中国科学院过程工程研究所 | Method for assisting vanadium-phosphorus-oxygen catalyst by using rare earth-based hydrotalcite |
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