CN106582745B - Method for refining vanadium source in vanadium phosphorus oxide catalyst - Google Patents
Method for refining vanadium source in vanadium phosphorus oxide catalyst Download PDFInfo
- Publication number
- CN106582745B CN106582745B CN201510674651.3A CN201510674651A CN106582745B CN 106582745 B CN106582745 B CN 106582745B CN 201510674651 A CN201510674651 A CN 201510674651A CN 106582745 B CN106582745 B CN 106582745B
- Authority
- CN
- China
- Prior art keywords
- vanadium
- catalyst
- source compound
- phosphorus
- organic solvent
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Abstract
The invention relates to a method for refining a vanadium source in a vanadium phosphorus oxide catalyst. Mainly solves the problem that the performance of the generated catalyst is poor due to large vanadium source particles and small specific surface area in the prior art for preparing the vanadium phosphorus oxide catalyst. The invention adopts a main body comprising three elements of vanadium, phosphorus and oxygen, and is assisted by a trace amount of metal auxiliary agent; the catalyst comprises the following components in percentage by weight based on the total weight of the catalyst: 15-30% of vanadium, 15-30% of phosphorus and 15-35% of oxygen; the metal additive is 0.001-8% of catalyst, and the vanadium element is at least one of refined ammonium metavanadate, vanadium pentoxide or organic acid vanadium; the metal additive is selected from at least one of lithium, niobium, bismuth and molybdenum; the molar ratio of the phosphorus element to the vanadium element is 0.8-2.5, and the technical scheme of producing the vanadium source with the internal through pore channel structure by adopting a novel refining method can be applied to the field of preparing maleic anhydride by oxidizing n-butane.
Description
Technical Field
the invention relates to a method for refining a vanadium source in a vanadium phosphorus oxide catalyst.
Background
Maleic anhydride, called maleic anhydride for short, is a common important organic chemical raw material, and is the third largest anhydride product with the world consumption second to that of phthalic anhydride and acetic anhydride. Maleic anhydride is widely applied to the industries of petrochemical industry, food chemical industry, medicine, building materials and the like, and is mainly used for synthesizing a series of important organic chemicals and fine chemicals such as unsaturated polyester resin, lubricating oil additive, food additive, 1, 4-Butanediol (BDO), gamma-butyrolactone (GBL), Tetrahydrofuran (THF) and the like.
The early production of maleic anhydride was prepared by the selective oxidation of benzene, but the proportion of benzene process in maleic anhydride production is decreasing due to the hazard of benzene to human body and environment, and the influence of economic factors. The technology for preparing maleic anhydride by oxidizing n-butane gradually becomes a main route of maleic anhydride production due to the advantages of low raw material price, relatively light pollution, high carbon atom utilization rate, low maleic anhydride production cost and the like.
Currently, researchers have made extensive research and attempts on catalyst materials for the oxidation of n-butane to maleic anhydride, and vanadium-phosphorus-oxygen (VPO) catalysts are considered to be the most effective catalyst systems to date. There are a lot of publications and patent technologies on the preparation method of VPO catalyst, and it is summarized that VPO catalyst mainly focused on industrialization is usually prepared by using aqueous solvent or organic solvent method to prepare precursor, and the obtained precursor is calcined, activated and shaped to obtain final catalyst. The organic solvent method has certain advantages because the organic solvent method has larger specific surface area compared with the catalyst obtained by the aqueous phase method. The method mainly uses a single or mixed system of isobutyl alcohol and benzyl alcohol as a solvent. Therefore, the specific preparation process of the organic solvent method is to dissolve a vanadium source in an organic solvent, stir and reflux for reaction, add a phosphorus source, continue refluxing to obtain a precursor, and finally perform heat treatment and activation to obtain the catalyst.
However, the research of the conventional preparation methods focuses on how to improve the reaction effect of the vanadium source and the phosphorus source, and the concentration of the phosphorus source is considered to obtain the VPO catalyst with higher purity and more obvious morphological characteristics. US4374043 describes the preparation of catalysts using a mixed phosphorus source which is a mixture of orthophosphoric acid, pyrophosphoric acid and a small amount of triphosphoric acid. US4365069 discloses a preparation process using 85% orthophosphoric acid as the phosphorus source. The methods mainly consider the influence of a phosphorus source on the catalyst, neglect the investigation of a vanadium source and do not consider the influence of the refining process of the vanadium source on the purity and the morphology of the VPO catalyst.
disclosure of Invention
One of the technical problems to be solved by the invention is to solve the problem that the catalyst morphology and performance are influenced by the vanadium source structure in the prior art, and disclose a vanadium phosphorus oxygen catalyst, and a novel vanadium source refining method thereof is used for producing a vanadium source with the particle size of 1-5 mu m, the specific surface area of 15-30m 2/g and rich pore channel structures, so that the catalyst structure morphology is improved, and the catalyst performance is improved.
The second technical problem to be solved by the present invention is to provide a method for preparing a catalyst corresponding to the first technical problem.
The third technical problem to be solved by the invention is to provide a method for improving the yield of maleic anhydride prepared by oxidizing n-butane, which corresponds to one of the technical problems to be solved
in order to solve one of the above technical problems, the technical solution disclosed by the present invention is: a vanadium phosphorus oxygen catalyst, the catalyst has a rose flower type structure; the main body of the catalyst comprises vanadium, phosphorus and oxygen elements, and is assisted by a trace amount of metal auxiliary agent; according to the total weight of the catalyst, the catalyst contains 15-30% of vanadium, 15-30% of phosphorus and 15-35% of oxygen; the metal additive is 0.001-8%.
In the technical scheme, the vanadium source compound is at least one of refined ammonium metavanadate, vanadium pentoxide or organic acid vanadium; the metal auxiliary agent is at least one of lithium, niobium, bismuth and molybdenum.
To solve the second technical problem, the invention adopts the following technical scheme: a preparation method of a vanadium phosphorus oxide catalyst mainly comprises the following steps: firstly, mixing a vanadium source compound in an organic solvent I, then adding a phosphorus source compound and a metal auxiliary agent, heating and refluxing for 1-20h under continuous stirring, filtering and drying the obtained product, and carrying out heat treatment at the temperature of 200-500 ℃ to obtain the catalyst.
In the technical scheme, the particle size of the vanadium source compound is 1-5 mu m. The P/V ratio of the phosphorus source compound to the vanadium source compound is 0.8-1.5; the organic solvent I is a primary alcohol solvent with reducing ability.
In the technical scheme, the preparation method of the Vanadium Phosphorus Oxide (VPO) catalyst for preparing maleic anhydride by oxidizing n-butane is characterized in that the vanadium source compound is required to be refined before being mixed with the organic solvent I, and the refining method mainly comprises the following steps:
(1) Carrying out ball milling on an industrial vanadium source compound in a ball mill;
(2) And stirring and washing the ball-milled vanadium source compound in an organic solvent II for 1-10h, carrying out suction filtration, and carrying out heat treatment on the filter cake for 1-20h to obtain the refined vanadium source.
In the scheme, in the step (1), after the vanadium source compound is subjected to ball milling, the particle size is 1-15 μm, and the specific surface area is 5-15m 2/g.
In the technical scheme, in the step (2), after the vanadium source compound is stirred, washed and thermally treated in the organic solvent II, the particle size is 1-4 mu m, and the specific surface area is 25-30m 2/g.
In the technical scheme, the preparation method of the vanadium phosphorus oxide catalyst is characterized in that an organic solvent II for washing the crude vanadium source is a mixed solution of polyhydric alcohol and aromatic alcohol, wherein the polyhydric alcohol is selected from at least one of glycerol, xylitol or sorbitol, the aromatic alcohol is selected from benzyl alcohol, and the molar ratio of hydroxyl to vanadium is 1-10: 1.
In the above technical scheme, the preferable technical scheme is that the molar ratio of the hydroxyl to the vanadium element is 2-8:1
In the above technical solution, the preferable technical solution is that the organic solvent ii is a mixture of glycerol, xylitol, sorbitol and benzyl alcohol, wherein the hydroxyl ratio of the four alcohols is 1: 1: 1: 1, and the molar ratio of the total hydroxyl groups to the vanadium element is (4-8): 1.
In the technical scheme, the method is characterized in that the stirring speed of the vanadium source compound in the organic solvent II is 600r/min, and the heat treatment process of the filter cake is roasting at 500 ℃ at 100 ℃ in an air atmosphere.
In order to solve the third technical problem, the invention adopts the following technical scheme that a method for preparing maleic anhydride by n-butane oxidation adopts any one vanadium phosphorus oxygen catalyst of claims 1 to 9, and is characterized in that the vanadium phosphorus oxygen catalyst reacts with butane raw materials with the molar concentration of 1 to 1.5 percent mol in a fixed bed reactor to produce the maleic anhydride, wherein the reaction process conditions comprise that the space velocity is 1000 to 3000hr -1, the reaction temperature is 300 to 500 ℃, and the reaction pressure is normal pressure.
By adopting the technical scheme of the invention, after the industrial vanadium source compound is ball-milled, the industrial vanadium source compound is stirred and washed in an organic solvent and is subjected to heat treatment, the particle size of the prepared vanadium source compound is 1-5 mu m, a pore channel structure with communicated inner parts is formed among the particles, the specific surface area is 15-30m 2/g, the prepared catalyst has a rose flower type structure, the catalytic performance of the catalyst is greatly improved, and the yield of maleic anhydride prepared by oxidizing n-butane can reach 64%.
The invention is further illustrated by the following examples, which are not intended to limit the scope of the invention.
drawings
fig. 1 is an SEM photograph of the vanadium source refined according to the embodiment of the present invention.
FIG. 2 is an SEM photograph of a vanadium source that has not been treated by a refining process.
Detailed Description
[ example 1 ]
After ball milling, 1 part of industrial grade vanadium pentoxide is 1-15 mu m in particle size, the industrial grade vanadium pentoxide is stirred for 6h at 500r/min in a mixed solution of 3 parts of glycerol and 1 part of benzyl alcohol, and is roasted for 6h at 400 ℃ in a roasting furnace after suction filtration to obtain refined vanadium pentoxide with particles of 1-5 mu m, the specific surface area of 26m 2/g and rich pore canal structures, after 30g of refined vanadium pentoxide is mixed with 280ml of isobutanol, 32g of 100 wt% phosphoric acid and 0.8g of bismuth nitrate are added, the mixture is heated and refluxed for 16h under stirring, the obtained product is filtered and dried, and is subjected to heat treatment at 400 ℃ to obtain a catalyst, and the obtained catalyst is reacted with a butane raw material with the molar concentration of 1.5% mol under the reaction process conditions that the space velocity of 2000hr -1 and the normal pressure of 400 ℃ are evaluated in a fixed bed reactor, the conversion rate of butane is 85.1%, the yield of maleic anhydride is 62.4%, and the evaluation results are detailed in Table 1.
[ example 2 ]
Ball-milling 1 part of industrial grade vanadium pentoxide, stirring the industrial grade vanadium pentoxide with the particle size of 1-15 mu m at a speed of 500r/min in a mixed solution of 3 parts of xylitol and 1 part of benzyl alcohol for 6h, carrying out suction filtration, and roasting the industrial grade vanadium pentoxide in a roasting furnace at a temperature of 400 ℃ for 6h to obtain refined vanadium pentoxide with the particle size of 1-5 mu m, the specific surface area of 27m 2/g and rich pore channel structures, mixing 30g of refined vanadium pentoxide with 280ml of isobutanol, adding 32g of 100 wt% phosphoric acid and 0.8g of bismuth nitrate, heating and refluxing for 16h under stirring, filtering and drying the obtained product, carrying out heat treatment at a temperature of 400 ℃ to obtain a catalyst, and reacting the obtained catalyst with a butane raw material with the molar concentration of 1.5 mol% at a reaction process condition that the space velocity of 2000hr -1 and the normal pressure of 400 ℃ are evaluated in a fixed bed reactor, the butane conversion rate is 84.8%, the maleic anhydride yield is 62.5%, and the evaluation results are shown in Table 1.
[ example 3 ]
Ball-milling 1 part of industrial grade vanadium pentoxide, stirring the industrial grade vanadium pentoxide with the particle size of 1-15 mu m at a speed of 500r/min in a mixed solution of 3 parts of sorbitol and 1 part of benzyl alcohol for 6h, carrying out suction filtration, and roasting the industrial grade vanadium pentoxide in a roasting furnace at a temperature of 400 ℃ for 6h to obtain refined vanadium pentoxide with the particle size of 1-5 mu m, the specific surface area of 26m 2/g and rich pore channel structures, mixing 30g of the refined vanadium pentoxide with 280ml of isobutanol, adding 32g of 100 wt% phosphoric acid and 0.8g of bismuth nitrate, heating and refluxing for 16h under stirring, filtering and drying the obtained product, carrying out heat treatment at a temperature of 400 ℃ to obtain a catalyst, and reacting the obtained catalyst with a butane raw material with a molar concentration of 1.5 mol% at a reaction process condition that the space velocity of 2000hr -1 and the normal pressure of 400 ℃ are evaluated in a fixed bed reactor, wherein the butane conversion rate is 84.6%, the maleic anhydride yield is 62.1%, and the evaluation results are shown in Table 1.
[ example 4 ]
After 1 part of industrial grade vanadium pentoxide is ball-milled, the particle size is 1-15 mu m, the mixture is stirred for 6h at 500r/min in a mixed solution of 1.5 parts of glycerin, 1.5 parts of xylitol and 1 part of benzyl alcohol, the mixture is filtered and then roasted for 6h at 400 ℃ in a roasting furnace to obtain refined vanadium pentoxide with the particle size of 1-4 mu m, the specific surface area of 28m 2/g and rich pore channel structure, after 30g of refined vanadium pentoxide is mixed with 280ml of isobutanol, 32g of 100 wt% phosphoric acid and 0.8g of bismuth nitrate are added, the mixture is heated and refluxed for 16h under stirring, the obtained product is filtered and dried, and is subjected to heat treatment at 400 ℃ to obtain a catalyst, the obtained catalyst is reacted with a butane raw material with the molar concentration of 1.5 mol, the reaction process conditions are that the butane conversion rate is 85.2% and the maleic anhydride yield is 63.5%, and the evaluation results are shown in table 1.
[ example 5 ]
After 1 part of industrial grade vanadium pentoxide is ball-milled, the particle size is 1-15 mu m, the mixture is stirred for 6h at 500r/min in a mixed solution of 1.5 parts of glycerin, 1.5 parts of sorbitol and 1 part of benzyl alcohol, the mixture is filtered and then roasted for 6h at 400 ℃ in a roasting furnace to obtain refined vanadium pentoxide with the particle size of 1-4 mu m, the specific surface area of 29m 2/g and rich pore channel structure, after 30g of refined vanadium pentoxide is mixed with 280ml of isobutanol, 32g of 100 wt% phosphoric acid and 0.8g of bismuth nitrate are added, the mixture is heated and refluxed for 16h under stirring, the obtained product is filtered and dried, and is subjected to heat treatment at 400 ℃ to obtain a catalyst, the obtained catalyst is reacted with a butane raw material with the molar concentration of 1.5 mol%, the reaction process conditions are that the space velocity of 2000hr -1 and the butane raw material at 400 ℃ is evaluated in a fixed bed reactor, the butane conversion rate is 85.1%, the maleic anhydride yield is 63.3%, and the evaluation results are shown in table 1.
[ example 6 ]
After 1 part of industrial grade vanadium pentoxide is ball-milled, the particle size is 1-15 mu m, the vanadium pentoxide is stirred for 6h at 500r/min in a mixed solution of 1.5 parts of xylitol, 1.5 parts of sorbitol and 1 part of benzyl alcohol, the vanadium pentoxide is refined to obtain 1-4 mu m particles, the specific surface area is 29m 2/g, the vanadium pentoxide is filtered and filtered, the vanadium pentoxide is roasted for 6h at 400 ℃ in a roasting furnace to obtain refined vanadium pentoxide, the refined vanadium pentoxide particles are mixed with 280ml of isobutanol, 32g of 100 wt% phosphoric acid and 0.8g of bismuth nitrate are added, the mixture is heated and refluxed for 16h under stirring, the obtained product is filtered and dried, and the catalyst is obtained after heat treatment at 400 ℃, the obtained catalyst is reacted with a butane raw material with the molar concentration of 1.5 mol%, the reaction process conditions are that the butane conversion rate is 85.4% and the maleic anhydride yield is 63.4%, and the evaluation results are shown in table 1.
[ example 7 ]
After 1 part of industrial grade vanadium pentoxide is ball-milled, the particle size is 1-15 mu m, the vanadium pentoxide is stirred for 6h at 500r/min in a mixed solution of 1 part of glycerin, 1 part of xylitol, 1 part of sorbitol and 1 part of benzyl alcohol, the vanadium pentoxide is refined after suction filtration and is roasted for 6h at 400 ℃ in a roasting furnace to obtain refined vanadium pentoxide particles, the particle size is 2-4 mu m, the specific surface area is 30m 2/g, the vanadium pentoxide particles have rich pore channel structures, after 30g of refined vanadium pentoxide and 280ml of isobutanol are mixed, 32g of 100 wt% phosphoric acid and 0.8g of bismuth nitrate are added, the mixture is heated and refluxed for 16h under stirring, the obtained product is filtered and dried, and is subjected to heat treatment at 400 ℃ to obtain a catalyst, the obtained catalyst is reacted with a butane raw material with the molar concentration of 1.5 mol, the reaction process conditions are that the butane conversion rate is 85.4% and the maleic anhydride yield is 63.4%, and the evaluation results are shown in table 1.
Comparative example 1
After 1 part of industrial grade vanadium pentoxide is ball-milled, the particle size is 1-15 mu m, the specific surface area is 14m 2/g, 30g of refined vanadium pentoxide is mixed with 280ml of isobutanol, 32g of 100 wt% phosphoric acid and 0.8g of bismuth nitrate are added, the mixture is heated and refluxed for 16h under stirring, the obtained product is filtered and dried, and is thermally treated at 400 ℃ to obtain a catalyst, the obtained catalyst is reacted with a butane raw material with the molar concentration of 1.5% mol, the reaction process conditions are 2000hr -1 airspeed and 400 ℃ normal pressure are evaluated in a fixed bed reactor, the butane conversion rate is 83.1%, the yield of maleic anhydride is 59.7%, and the evaluation results are detailed in table 1.
Comparative example 2
30g of industrial grade vanadium pentoxide is mixed with 280ml of isobutanol, 32g of 100 wt% phosphoric acid and 0.8g of bismuth nitrate are added, the mixture is heated and refluxed for 16 hours under stirring, the obtained product is filtered and dried, and is subjected to heat treatment at 400 ℃ to obtain a catalyst, the catalyst is reacted with a butane raw material with the molar concentration of 1.5% mol, the reaction process conditions are evaluated in a fixed bed reactor at the space velocity of 2000hr -1 and the normal pressure of 400 ℃, the butane conversion rate is 83.6%, the maleic anhydride yield is 57.1%, and the evaluation results are detailed in table 1.
TABLE 1
Claims (10)
1. a vanadium phosphorus oxygen catalyst is characterized in that the catalyst has a rose flower type structure; the main body of the catalyst comprises vanadium, phosphorus and oxygen, and is assisted by a trace amount of metal additive; the catalyst comprises the following components in percentage by weight based on the total weight of the catalyst: 15-30% of vanadium, 15-30% of phosphorus and 15-35% of oxygen; 0.001-8% of metal auxiliary agent;
Wherein the vanadium source compound is at least one of refined ammonium metavanadate, vanadium pentoxide or organic acid vanadium; the metal additive is selected from at least one of lithium, niobium, bismuth and molybdenum;
Wherein the molar ratio of the phosphorus element to the vanadium element is 0.8-2.5;
The method for refining the vanadium source compound mainly comprises the following steps:
(1) carrying out ball milling on an industrial vanadium source compound in a ball mill;
(2) Stirring and washing the ball-milled vanadium source compound in an organic solvent II for 1-10h, carrying out suction filtration, and carrying out heat treatment on a filter cake for 1-20h to obtain a refined vanadium source compound;
The organic solvent II for washing the vanadium source compound is a mixed solution of polyhydric alcohol and aromatic alcohol, wherein the polyhydric alcohol is at least one of glycerol, xylitol or sorbitol, and the aromatic alcohol is benzyl alcohol; wherein the molar ratio of hydroxyl to vanadium in the organic solvent II is (1-10): 1.
2. A method for preparing the vanadium phosphorus oxide catalyst as claimed in claim 1, which is characterized by comprising the following main steps: firstly, mixing a vanadium source compound in an organic solvent I, then adding a phosphorus source compound and a metal auxiliary agent, heating and refluxing for 1-20h under continuous stirring, filtering and drying the obtained product, and carrying out heat treatment at the temperature of 200-500 ℃ to obtain the catalyst.
3. The method for preparing a vanadium phosphorus oxide catalyst according to claim 2, wherein the vanadium source compound used has a particle size of 1 to 5 μm.
4. The method of claim 2, wherein the molar ratio of P/V in the desired phosphorus source compound to vanadium source compound is 0.8 to 1.5; the organic solvent I is a primary alcohol solvent with reducing ability.
5. The method for preparing a vanadium phosphorus oxide catalyst as claimed in claim 2, wherein the vanadium source compound is purified before being mixed with the organic solvent I, and the purification method mainly comprises the steps of:
(1) Carrying out ball milling on an industrial vanadium source compound in a ball mill;
(2) And stirring and washing the ball-milled vanadium source compound in an organic solvent II for 1-10h, carrying out suction filtration, and carrying out heat treatment on the filter cake for 1-20h to obtain the refined vanadium source compound.
6. the method for preparing a vanadium phosphorus oxide catalyst according to claim 5, wherein the particles of the purified vanadium source compound have a through-hole structure therein, and the specific surface area is 15 to 30m 2/g.
7. the method of claim 5, wherein the organic solvent II for washing the vanadium source compound is a mixed solution of a polyhydric alcohol selected from at least one of glycerol, xylitol or sorbitol and an aromatic alcohol selected from benzyl alcohol; wherein the molar ratio of hydroxyl to vanadium in the organic solvent II is (1-10): 1.
8. The method for preparing a vanadium-phosphorus-oxygen catalyst according to claim 7, wherein the molar ratio of the hydroxyl group to the vanadium element in the organic solvent II is (2-8): 1.
9. The method for preparing a vanadium phosphorus oxide catalyst as claimed in claim 5, wherein the stirring speed of the vanadium source compound in the organic solvent II is 100-600r/min, and the heat treatment process of the filter cake is roasting at 500 ℃ and 100-in the air atmosphere.
10. A method for preparing maleic anhydride by n-butane oxidation adopts the catalyst of claim 1 or the catalyst prepared by any one of the methods of claims 2 to 9, and is characterized in that the catalyst reacts with butane raw material with the molar concentration of 1 to 1.5 percent in a fixed bed reactor to produce the maleic anhydride, wherein the reaction process conditions comprise that the space velocity is 1000 to 3000hr -1, the reaction temperature is 300 to 500 ℃, and the reaction pressure is normal pressure.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510674651.3A CN106582745B (en) | 2015-10-19 | 2015-10-19 | Method for refining vanadium source in vanadium phosphorus oxide catalyst |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510674651.3A CN106582745B (en) | 2015-10-19 | 2015-10-19 | Method for refining vanadium source in vanadium phosphorus oxide catalyst |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106582745A CN106582745A (en) | 2017-04-26 |
| CN106582745B true CN106582745B (en) | 2019-12-10 |
Family
ID=58553867
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510674651.3A Active CN106582745B (en) | 2015-10-19 | 2015-10-19 | Method for refining vanadium source in vanadium phosphorus oxide catalyst |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106582745B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109550515B (en) * | 2017-09-30 | 2020-10-13 | 中国科学院过程工程研究所 | Preparation method and application of vanadium-phosphorus-oxygen catalyst |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3759847B2 (en) * | 1999-02-16 | 2006-03-29 | 株式会社日本触媒 | Method for activating vanadium-phosphorus catalyst |
| CN1849170A (en) * | 2003-09-15 | 2006-10-18 | 隆萨公开有限公司 | Niobium-doped vanadium/phosphorus mixed oxide catalyst |
| CN103769181A (en) * | 2012-10-24 | 2014-05-07 | 中国石油化工股份有限公司 | Vanadium-phosphorus-oxygen catalyst, and preparation method thereof |
-
2015
- 2015-10-19 CN CN201510674651.3A patent/CN106582745B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3759847B2 (en) * | 1999-02-16 | 2006-03-29 | 株式会社日本触媒 | Method for activating vanadium-phosphorus catalyst |
| CN1849170A (en) * | 2003-09-15 | 2006-10-18 | 隆萨公开有限公司 | Niobium-doped vanadium/phosphorus mixed oxide catalyst |
| CN103769181A (en) * | 2012-10-24 | 2014-05-07 | 中国石油化工股份有限公司 | Vanadium-phosphorus-oxygen catalyst, and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| 不同P与V比的Mo/VPO催化剂物相组成及其催化性能;曾炜等;《工业催化》;20140815;第22卷(第8期);第596页左栏第3段、第1.1、1.3节，第597页第2.3节、 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN106582745A (en) | 2017-04-26 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105413725B (en) | Vanadium phosphorus catalyst and preparation method thereof | |
| JPS6176470A (en) | Manufacture of maleic anhydride | |
| CN106582745B (en) | Method for refining vanadium source in vanadium phosphorus oxide catalyst | |
| CN107866244B (en) | Vanadium phosphorus catalyst and preparation method thereof | |
| US20120022291A1 (en) | Catalyst for production of acrolein and acrylic acid by means of dehydration reaction of glycerin, and process for producing same | |
| CN106582744B (en) | Preparation method of catalyst for improving yield of maleic anhydride prepared by n-butane oxidation | |
| KR101033660B1 (en) | Calcium phosphate-silica catalysts for dehydration reaction of lactates, preparation thereof, and Process for the preparation of acrylic compounds from lactates | |
| CN107983381B (en) | Preparation method of vanadyl phosphate catalyst and application of vanadyl phosphate catalyst in catalytic oxidation reaction | |
| CN113877612B (en) | Multifunctional catalyst compounded by FeMo component and VPO component, and preparation method and application thereof | |
| CN101723925A (en) | Preparation method of 7-hydroxy-4-methylcoumarin | |
| JPH02235827A (en) | Preparation of alkanol | |
| CN106582748A (en) | Preparation method for improving activity of catalyst used for producing maleic anhydride | |
| CN103044234A (en) | Method and catalyst for preparing adipic acid | |
| CN107866242B (en) | Preparation method of catalyst for producing maleic anhydride | |
| CN105536831A (en) | Method for preparing maleic anhydride VPO catalyst through n-butane oxidation method | |
| CN1312102C (en) | Preparation method of antimony triacetate | |
| CN106582746A (en) | Catalyst for preparation of maleic anhydride by n-butane oxidation | |
| CN106582751A (en) | Catalyst for synthesis of maleic anhydride and preparation method thereof | |
| CN114643051B (en) | Catalyst for synthesizing pyromellitic anhydride by oxidizing pyromellitic benzene and preparation method and application thereof | |
| CN106582747B (en) | For producing the preparation method of the catalyst of cis-butenedioic anhydride | |
| CN114797921B (en) | Maleic anhydride catalyst and preparation method and application thereof | |
| CN116020502A (en) | Catalyst for hydrocarbon selective oxidation reaction and preparation method and application thereof | |
| CN111097465B (en) | Preparation method of vanadium phosphorus oxide catalyst | |
| CN115536495B (en) | Method for preparing 1, 4-pentanediol | |
| CN114425447B (en) | Heteropoly acid modified catalyst, preparation method and application thereof and butene oxidative dehydrogenation method |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |