CN107866241B - Catalyst for preparing pyromellitic anhydride by oxidizing durene - Google Patents

Catalyst for preparing pyromellitic anhydride by oxidizing durene Download PDF

Info

Publication number
CN107866241B
CN107866241B CN201610846448.4A CN201610846448A CN107866241B CN 107866241 B CN107866241 B CN 107866241B CN 201610846448 A CN201610846448 A CN 201610846448A CN 107866241 B CN107866241 B CN 107866241B
Authority
CN
China
Prior art keywords
catalyst
durene
oxalic acid
precursor
alkali metal
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
Application number
CN201610846448.4A
Other languages
Chinese (zh)
Other versions
CN107866241A (en
Inventor
徐俊峰
顾龙勤
金照生
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Sinopec Shanghai Research Institute of Petrochemical Technology
China Petrochemical Corp
Original Assignee
Sinopec Shanghai Research Institute of Petrochemical Technology
China Petrochemical Corp
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Sinopec Shanghai Research Institute of Petrochemical Technology, China Petrochemical Corp filed Critical Sinopec Shanghai Research Institute of Petrochemical Technology
Priority to CN201610846448.4A priority Critical patent/CN107866241B/en
Publication of CN107866241A publication Critical patent/CN107866241A/en
Application granted granted Critical
Publication of CN107866241B publication Critical patent/CN107866241B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/18—Arsenic, antimony or bismuth
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/20—Vanadium, niobium or tantalum
    • B01J23/22—Vanadium
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D493/00—Heterocyclic compounds containing oxygen atoms as the only ring hetero atoms in the condensed system
    • C07D493/02—Heterocyclic compounds containing oxygen atoms as the only ring hetero atoms in the condensed system in which the condensed system contains two hetero rings
    • C07D493/04—Ortho-condensed systems

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Heterocyclic Carbon Compounds Containing A Hetero Ring Having Oxygen Or Sulfur (AREA)
  • Catalysts (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)

Abstract

The invention relates to a catalyst for preparing pyromellitic anhydride by oxidizing durene, which mainly solves the problems of low activity of the catalyst and more byproducts in the prior art, thereby resulting in low product yield. The invention adopts oxide catalyst which adopts alpha-Al2O3The silicon carbide, the ceramic ring or the mixture thereof is used as a carrier, and the active component comprises vanadium element, titanium element and at least one of VA group element and alkali metal element, thereby better solving the technical problem and greatly improving the yield of the catalyst to the pyromellitic dianhydride.

Description

Catalyst for preparing pyromellitic anhydride by oxidizing durene
Technical Field
The invention relates to a catalyst for preparing pyromellitic anhydride by oxidizing durene, a preparation method thereof and a synthesis method of the pyromellitic anhydride.
Technical Field
With the rapid development of petroleum refining, chemical fiber, polyester and other industries, large-scale ethylene plants, catalytic reforming plants, aromatic hydrocarbon plants, disproportionation, isomerization processes and the like will produce a large amount of C10 aromatic hydrocarbons as by-products. Therefore, how to effectively utilize the C10 aromatic hydrocarbon resource has become an important issue in petrochemical industry. As an important intermediate of fine chemicals with high added value, pyromellitic dianhydride (PMDA, pyromellitic dianhydride) with a special structure of 4 symmetrical carboxyl groups can be prepared into a plurality of products with excellent heat resistance, electric insulation and chemical resistance. The product can be mainly used for producing monomers, medical intermediates, epoxy resin curing agents and the like of polyimide, polyimidazole and other heat-resistant resins, and products prepared from the product can be widely applied to advanced technical fields of aviation, aerospace, electronic industry and the like. Therefore, the pyromellitic dianhydride which is extracted from the pyromellitic dianhydride with high content of C10 aromatic hydrocarbon as a refining byproduct and is further processed into high added value has very important research significance and obvious economic benefit.
At present, a gas-phase oxidation method is mostly adopted for preparing the pyromellitic anhydride by taking durene as a raw material, and the process is a complex heterogeneous catalysis process and has various side reactions, so that the yield of the pyromellitic anhydride is very low. The catalyst for preparing the homoanhydride by the gas phase oxidation method mainly takes a vanadium system as an active component, a small amount of metal elements are used as auxiliary materials, the theoretical yield of the homoanhydride is calculated according to a chemical reaction equation and is up to 163%, but the catalyst obtained by the traditional preparation method is relatively low in activity, and the actual yield of the homoanhydride can only reach 56% of the theoretical yield at most. Therefore, it is necessary to improve the selectivity of the catalyst to the homoanhydride by changing the preparation method of the catalyst.
CN101037439A discloses a supported polyoxometallate catalyst, which can react at a lower temperature. CN01105883.8 reports a report on2O5And TiO2As main catalyst, Nb2O5、Cs2O and P2O5A catalytic system which is a cocatalyst. US6084109 discloses a V2O5-WO3Catalyst, oxide system of manganese, antimony, bismuth, phosphorus, copper or mixtures thereof. The method makes great progress in the preparation of the catalyst for preparing the pyromellitic anhydride by oxidizing durene, but still has the problem of low yield of the pyromellitic anhydride.
Disclosure of Invention
One of the technical problems to be solved by the invention is the problem of low yield of the pyromellitic anhydride catalyst in the prior art, and the catalyst for preparing the pyromellitic anhydride by oxidizing durene is provided and has the characteristic of high yield of the pyromellitic anhydride.
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 invention aims to solve the third technical problem and provide a method for preparing the pyromellitic anhydride by oxidizing durene, which corresponds to the solution of one of the technical problems.
In order to solve one of the above technical problems, the technical solution disclosed by the present invention is: the catalyst for preparing the pyromellitic anhydride by oxidizing durene is characterized in that an inert carrier is adopted, and active components comprise vanadium, titanium and at least one of VA group elements and alkali metal elements. Preferably, the active component includes vanadium, titanium, at least one element selected from group VA elements, and at least one element selected from alkali metals at the same time. At this time, the VA group and the alkali metal have synergistic effect on the aspect of improving the yield of the pyromellitic dianhydride.
In the above technical solution, the VA element is at least one selected from phosphorus, arsenic, antimony and bismuth. More preferred are phosphorus and antimony.
In the above technical solution, the alkali metal element is at least one selected from lithium, sodium, potassium, rubidium, and cesium.
In the above technical solutions, as the most preferable technical solution, the active component simultaneously includes a vanadium element, a titanium element, a VA group element, and an alkali metal element; for example, the active component includes vanadium, titanium, phosphorus and lithium, or vanadium, titanium, phosphorus, antimony, potassium, rubidium.
In the technical scheme, the ratio of vanadium element to titanium element in the catalyst is 1 (1-10), and more preferably 1 (3-8); the ratio of vanadium element to the sum of VA element and alkali metal element in the catalyst is 1: (0.01-1), more preferably 1: (0.02-0.5).
To solve the second technical problem, the technical solution of the present invention is as follows: the preparation method of the catalyst for preparing the pyromellitic anhydride by oxidizing the durene comprises the following steps:
(1) adding a vanadium source into the oxalic acid solution to obtain a mixed solution. Adding a titanium source, a VA group and an alkali metal element compound into a reaction system to obtain a precursor.
(2) Spraying the precursor on a carrier, and roasting to obtain the catalyst.
In the above technical solution, the vanadium source in step (1) is preferably at least one selected from vanadium oxide, metavanadate, orthovanadate and vanadium chloride. The titanium source in the step (1) is preferably at least one selected from titanium oxide, titanium halide, titanium salt, titanate and organic titanium compound. The compound of the VA group element in the step (1) is preferably at least one selected from ammonium dihydrogen phosphate, diammonium hydrogen phosphate, antimony pentoxide, antimony nitrate and antimony sulfate. The compound of the alkali metal element in the step (1) is preferably at least one selected from the group consisting of an alkali metal oxide, an alkali metal chloride, an alkali metal nitrate, an alkali metal sulfate and an alkali metal acetate.
In the technical scheme, the preparation method for preparing the catalyst for preparing the pyromellitic anhydride by oxidizing the durene is characterized in that a precursor of the catalyst is put into a spraying machine and is uniformly sprayed on a carrier after being heated at the temperature of 220-260 ℃.
In the technical scheme, the preparation method of the catalyst for preparing the pyromellitic anhydride by oxidizing the durene is characterized in that the carrier sprayed with the catalyst precursor is roasted in a muffle furnace, the roasting temperature is 500-550 ℃, and the roasting time is 3-5 h.
To solve the third technical problem, the technical scheme of the invention is as follows: the process for preparing sym-anhydride by oxidizing sym-tetramethylbenzene uses sym-tetramethylbenzene and air as raw materials and adopts a fixed bed reactor to synthesize sym-anhydride in the presence of catalyst.
The reaction process conditions in the technical scheme are as follows: the mass concentration of durene is 30-50g/m3The reaction process conditions are as follows: the airspeed is 4000-6000 hr-1The reaction temperature is 300-500 ℃, and the reaction pressure is normal pressure.
Compared with the prior art, the key point of the invention is that the active component of the catalyst comprises a certain amount of vanadium element, titanium element and at least one element selected from VA group and alkali metal, which is beneficial to improving the activity and stability of the catalyst, thereby improving the yield of the pyromellitic dianhydride.
The experimental result shows that the yield of the pyromellitic dianhydride prepared by the invention reaches 75.5%, and a better technical effect is achieved, particularly when the active component in the catalyst simultaneously comprises vanadium element, titanium element, at least one metal element selected from VA and at least one metal element selected from alkali metal, a more prominent technical effect is achieved, and the catalyst can be used for synthesis of pyromellitic dianhydride. The invention is further illustrated by the following examples.
Detailed Description
[ example 1 ]
88g of oxalic acid and 340ml of distilled water are weighed in a flask, stirred and heated to 80 ℃, and the oxalic acid solution is prepared after the oxalic acid is completely dissolved. Adding a part of vanadium pentoxide into the prepared oxalic acid solution, and continuously stirring to obtain the ammonium vanadyl oxalate solution. Adding 5 parts of TiO20.4 portion of ammonium dihydrogen phosphate is added into the solution and is stirred continuouslyAnd (4) homogenizing to obtain a catalyst precursor. And filtering and drying the catalyst precursor, filling the catalyst precursor into a spraying machine, and uniformly spraying the catalyst precursor on the inert carrier alpha-alumina. And roasting the inert carrier sprayed with the catalyst precursor in a muffle furnace at 560 ℃, and naturally cooling to obtain the catalyst. The catalyst is reacted at 480 ℃ and the space velocity of 5400h-1Next, the yield of the homogeneous anhydride was found to be 71.4% by evaluation in a fixed bed reactor, and the evaluation results are shown in Table 1.
[ example 2 ]
88g of oxalic acid and 340ml of distilled water are weighed in a flask, stirred and heated to 80 ℃, and the oxalic acid solution is prepared after the oxalic acid is completely dissolved. Adding a part of vanadium pentoxide into the prepared oxalic acid solution, and continuously stirring to obtain the ammonium vanadyl oxalate solution. Adding 5 parts of TiO2And 0.4 part of potassium nitrate is added into the solution, and the catalyst precursor is obtained after the mixture is continuously stirred uniformly. And filtering and drying the catalyst precursor, filling the catalyst precursor into a spraying machine, and uniformly spraying the catalyst precursor on the inert carrier alpha-alumina. And roasting the inert carrier sprayed with the catalyst precursor in a muffle furnace at 560 ℃, and naturally cooling to obtain the catalyst. The catalyst is reacted at 480 ℃ and the space velocity of 5400h-1Next, the yield of the homogeneous anhydride was found to be 71.2% by evaluation in a fixed bed reactor, and the evaluation results are shown in Table 1.
Comparative example 1
88g of oxalic acid and 340ml of distilled water are weighed in a flask, stirred and heated to 80 ℃, and the oxalic acid solution is prepared after the oxalic acid is completely dissolved. Adding a part of vanadium pentoxide into the prepared oxalic acid solution, and continuously stirring to obtain the ammonium vanadyl oxalate solution. Adding 5 parts of TiO2Adding the solution into the solution, and continuously stirring the solution uniformly to obtain a catalyst precursor. And filtering and drying the catalyst precursor, filling the catalyst precursor into a spraying machine, and uniformly spraying the catalyst precursor on the inert carrier alpha-alumina. And roasting the inert carrier sprayed with the catalyst precursor in a muffle furnace at 560 ℃, and naturally cooling to obtain the catalyst. The catalyst is reacted at 480 ℃ and the space velocity of 5400h-1Next, the yield of the homogeneous anhydride was found to be 67.2% by evaluation in a fixed bed reactor, and the evaluation results are shown in Table 1.
Compared with the examples 1-2, the catalyst adopted by the invention has better performance than that of a catalyst only containing V, Ti active components and has higher yield of the pyromellitic dianhydride, and the catalyst contains V, Ti and P active components and V, Ti and K active components.
[ example 3 ]
88g of oxalic acid and 340ml of distilled water are weighed in a flask, stirred and heated to 80 ℃, and the oxalic acid solution is prepared after the oxalic acid is completely dissolved. Adding a part of vanadium pentoxide into the prepared oxalic acid solution, and continuously stirring to obtain the ammonium vanadyl oxalate solution. And adding 5 parts of titanium tetrachloride and 0.4 part of diammonium hydrogen phosphate into the solution, and continuously and uniformly stirring to obtain a catalyst precursor. And filtering and drying the catalyst precursor, filling the catalyst precursor into a spraying machine, and uniformly spraying the catalyst precursor on the inert carrier alpha-alumina. And roasting the inert carrier sprayed with the catalyst precursor in a muffle furnace at 560 ℃, and naturally cooling to obtain the catalyst. The catalyst is reacted at 480 ℃ and the space velocity of 5400h-1Next, the yield of the homogeneous anhydride was found to be 71.3% by evaluation in a fixed bed reactor, and the evaluation results are shown in Table 1.
[ example 4 ]
88g of oxalic acid and 340ml of distilled water are weighed in a flask, stirred and heated to 80 ℃, and the oxalic acid solution is prepared after the oxalic acid is completely dissolved. And adding a part of ammonium metavanadate into the prepared oxalic acid solution, and continuously stirring to obtain the ammonium vanadyl oxalate solution. And adding 5 parts of titanium tetrachloride and 0.4 part of antimony nitrate into the solution, and continuously and uniformly stirring to obtain a catalyst precursor. And filtering and drying the catalyst precursor, filling the catalyst precursor into a spraying machine, and uniformly spraying the catalyst precursor on the inert carrier alpha-alumina. And roasting the inert carrier sprayed with the catalyst precursor in a muffle furnace at 560 ℃, and naturally cooling to obtain the catalyst. The catalyst is reacted at 480 ℃ and the space velocity of 5400h-1Next, the yield of the homogeneous anhydride was found to be 71.5% by evaluation in a fixed bed reactor, and the evaluation results are shown in Table 1.
[ example 5 ]
88g of oxalic acid and 340ml of distilled water are weighed in a flask, stirred and heated to 80 ℃, and the oxalic acid solution is prepared after the oxalic acid is completely dissolved. Adding a part of ammonium metavanadate into the prepared oxalic acid solution for relayStirring is continued to obtain the ammonium vanadyl oxalate solution. And adding 5 parts of titanium tetrachloride and 0.4 part of sodium chloride into the solution, and continuously and uniformly stirring to obtain a catalyst precursor. And filtering and drying the catalyst precursor, filling the catalyst precursor into a spraying machine, and uniformly spraying the catalyst precursor on the inert carrier alpha-alumina. And roasting the inert carrier sprayed with the catalyst precursor in a muffle furnace at 560 ℃, and naturally cooling to obtain the catalyst. The catalyst is reacted at 480 ℃ and the space velocity of 5400h-1Next, the yield of the homogeneous anhydride was found to be 71.7% by evaluation in a fixed bed reactor, and the evaluation results are shown in Table 1.
[ example 6 ]
88g of oxalic acid and 340ml of distilled water are weighed in a flask, stirred and heated to 80 ℃, and the oxalic acid solution is prepared after the oxalic acid is completely dissolved. Adding a part of vanadium pentoxide into the prepared oxalic acid solution, and continuously stirring to obtain the ammonium vanadyl oxalate solution. And adding 5 parts of titanium tetrachloride and 0.4 part of cesium sulfate into the solution, and continuously and uniformly stirring to obtain a catalyst precursor. And filtering and drying the catalyst precursor, filling the catalyst precursor into a spraying machine, and uniformly spraying the catalyst precursor on the inert carrier alpha-alumina. And roasting the inert carrier sprayed with the catalyst precursor in a muffle furnace at 560 ℃, and naturally cooling to obtain the catalyst. The catalyst is reacted at 480 ℃ and the space velocity of 5400h-1Next, the yield of the homogeneous anhydride was found to be 71.6% by evaluation in a fixed bed reactor, and the evaluation results are shown in Table 1.
[ example 7 ]
88g of oxalic acid and 340ml of distilled water are weighed in a flask, stirred and heated to 80 ℃, and the oxalic acid solution is prepared after the oxalic acid is completely dissolved. Adding a part of vanadium pentoxide into the prepared oxalic acid solution, and continuously stirring to obtain the ammonium vanadyl oxalate solution. And adding 5 parts of titanium dioxide, 0.2 part of diammonium phosphate and 0.2 part of potassium nitrate into the solution, and continuously stirring uniformly to obtain the catalyst precursor. And filtering and drying the catalyst precursor, filling the catalyst precursor into a spraying machine, and uniformly spraying the catalyst precursor on the inert carrier alpha-alumina. And roasting the inert carrier sprayed with the catalyst precursor in a muffle furnace at 560 ℃, and naturally cooling to obtain the catalyst. The catalyst is reacted at 480 ℃ and the space velocity of 5400h-1In a fixed bed reactorThe yield of the homogeneous anhydride is 72.5 percent by middle evaluation, and the evaluation results are detailed in table 1.
Compared with the examples 1-2, the VA group P element and the alkali metal K element have better synergistic effect on improving the yield of the pyromellitic dianhydride.
[ example 8 ]
88g of oxalic acid and 340ml of distilled water are weighed in a flask, stirred and heated to 80 ℃, and the oxalic acid solution is prepared after the oxalic acid is completely dissolved. Adding a part of vanadium pentoxide into the prepared oxalic acid solution, and continuously stirring to obtain the ammonium vanadyl oxalate solution. 5 parts of titanium dioxide, 0.1 part of diammonium hydrogen phosphate, 0.1 part of antimony nitrate and 0.2 part of potassium nitrate are added into the solution, and the catalyst precursor is obtained after the mixture is continuously and uniformly stirred. And filtering and drying the catalyst precursor, filling the catalyst precursor into a spraying machine, and uniformly spraying the catalyst precursor on the inert carrier alpha-alumina. And roasting the inert carrier sprayed with the catalyst precursor in a muffle furnace at 560 ℃, and naturally cooling to obtain the catalyst. The catalyst is reacted at 480 ℃ and the space velocity of 5400h-1Next, the yield of the homogeneous anhydride was found to be 73.7% by evaluation in a fixed bed reactor, and the evaluation results are shown in Table 1.
Compared with example 7, this example shows that the elements of VA group P and Sb have better synergistic effect with other active components of the invention in increasing the yield of the pyromellitic dianhydride.
[ example 9 ]
88g of oxalic acid and 340ml of distilled water are weighed in a flask, stirred and heated to 80 ℃, and the oxalic acid solution is prepared after the oxalic acid is completely dissolved. Adding a part of vanadium pentoxide into the prepared oxalic acid solution, and continuously stirring to obtain the ammonium vanadyl oxalate solution. And adding 5 parts of titanium dioxide, 0.2 part of antimony nitrate, 0.1 part of rubidium nitrate and 0.1 part of potassium nitrate into the solution, and continuously and uniformly stirring to obtain a catalyst precursor. And filtering and drying the catalyst precursor, filling the catalyst precursor into a spraying machine, and uniformly spraying the catalyst precursor on the inert carrier alpha-alumina. And roasting the inert carrier sprayed with the catalyst precursor in a muffle furnace at 560 ℃, and naturally cooling to obtain the catalyst. The catalyst is reacted at 480 ℃ and the space velocity of 5400h-1Then, the yield of the homogeneous anhydride is measured to be 73.5 percent by evaluation in a fixed bed reactor,the evaluation results are shown in Table 1.
Compared with example 7, this example shows that alkali metal Rb and K and other active components of the present invention have a better synergistic effect in increasing the yield of the pyromellitic dianhydride.
[ example 10 ]
88g of oxalic acid and 340ml of distilled water are weighed in a flask, stirred and heated to 80 ℃, and the oxalic acid solution is prepared after the oxalic acid is completely dissolved. Adding a part of vanadium pentoxide into the prepared oxalic acid solution, and continuously stirring to obtain the ammonium vanadyl oxalate solution. Adding 5 parts of titanium dioxide, 0.1 part of diammonium hydrogen phosphate, 0.1 part of antimony nitrate, 0.1 part of rubidium nitrate and 0.1 part of potassium nitrate into the solution, and continuously stirring uniformly to obtain a catalyst precursor. And filtering and drying the catalyst precursor, filling the catalyst precursor into a spraying machine, and uniformly spraying the catalyst precursor on the inert carrier alpha-alumina. And roasting the inert carrier sprayed with the catalyst precursor in a muffle furnace at 560 ℃, and naturally cooling to obtain the catalyst. The catalyst is reacted at 480 ℃ and the space velocity of 5400h-1Next, the yield of the homogeneous anhydride was found to be 75.5% by evaluation in a fixed bed reactor, and the evaluation results are shown in Table 1.
Compared with examples 8 and 9, the method for preparing the organic acid by using the organic acid has the advantages that V, Ti, VA group P and Sb elements and alkali metals Rb and K have very good synergistic effect on improving the yield of the pyromellitic dianhydride.
TABLE 1
Figure BDA0001119272730000071

Claims (6)

1. The catalyst for preparing the pyromellitic anhydride by oxidizing durene is characterized in that the catalyst adopts an inert carrier, and active components comprise vanadium elements, titanium elements, VA group elements and alkali metal elements; the VA element is phosphorus and antimony; the alkali metal elements are potassium and rubidium, and the ratio of the vanadium element to the Ti element in the catalyst is 1: (1-10), the ratio of vanadium element to the sum of VA element and alkali metal element is 1: (0.01-1).
2. A process for preparing the catalyst for the oxidation of durene to pyromellitic anhydride according to claim 1, which comprises the steps of:
(1) adding a vanadium source into an oxalic acid solution to obtain a mixed solution; adding a titanium source, a VA group and an alkali metal element compound into a reaction system to obtain a precursor;
(2) spraying the precursor on a carrier, and roasting to obtain the catalyst.
3. The method as claimed in claim 2, wherein the precursor of the catalyst is loaded into a spraying machine, heated at 220-260 ℃ and then uniformly sprayed on the carrier.
4. The method as claimed in claim 2, wherein the carrier coated with the catalyst precursor is calcined in a muffle furnace at 500-550 ℃ for 3-5 h.
5. A method for preparing pyromellitic anhydride by oxidizing durene, which takes durene and air as raw materials and adopts a fixed bed reactor to synthesize the pyromellitic anhydride in the presence of any one of the catalysts of claim 1.
6. The method according to claim 5, wherein the mass concentration of durene is 30-50g/m3The reaction process conditions are as follows: the airspeed is 4000-6000 hr-1The reaction temperature is 300-500 ℃, and the reaction pressure is normal pressure.
CN201610846448.4A 2016-09-23 2016-09-23 Catalyst for preparing pyromellitic anhydride by oxidizing durene Active CN107866241B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201610846448.4A CN107866241B (en) 2016-09-23 2016-09-23 Catalyst for preparing pyromellitic anhydride by oxidizing durene

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201610846448.4A CN107866241B (en) 2016-09-23 2016-09-23 Catalyst for preparing pyromellitic anhydride by oxidizing durene

Publications (2)

Publication Number Publication Date
CN107866241A CN107866241A (en) 2018-04-03
CN107866241B true CN107866241B (en) 2020-01-03

Family

ID=61751595

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201610846448.4A Active CN107866241B (en) 2016-09-23 2016-09-23 Catalyst for preparing pyromellitic anhydride by oxidizing durene

Country Status (1)

Country Link
CN (1) CN107866241B (en)

Families Citing this family (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110560112B (en) * 2018-06-05 2021-11-30 中国石油化工股份有限公司 Catalyst for preparing trimellitic anhydride
CN110560116B (en) * 2018-06-05 2021-11-30 中国石油化工股份有限公司 Catalyst for oxidation of pseudocumene to prepare meta-anhydride
CN110560110B (en) * 2018-06-05 2021-11-30 中国石油化工股份有限公司 Catalyst for synthesizing meta-anhydride by oxidizing meta-trimethylbenzene
CN110560111B (en) * 2018-06-05 2021-11-30 中国石油化工股份有限公司 Catalyst for synthesizing meta-anhydride from pseudocumene
CN110560115B (en) * 2018-06-05 2021-11-30 中国石油化工股份有限公司 Catalyst for synthesizing trimellitic anhydride
CN110560113B (en) * 2018-06-05 2021-11-30 中国石油化工股份有限公司 Catalyst for pseudocumene catalytic oxidation
CN110560109B (en) * 2018-06-05 2021-11-30 中国石油化工股份有限公司 Catalyst for producing trimellitic anhydride
CN110560114B (en) * 2018-06-05 2021-11-30 中国石油化工股份有限公司 Catalyst for improving yield of trimellitic anhydride
CN111097466B (en) * 2018-10-25 2023-03-03 中国石油化工股份有限公司 Preparation method of catalyst for preparation of pyromellitic anhydride
CN109336900A (en) * 2018-11-19 2019-02-15 鹏辰新材料科技股份有限公司 Pyromellitic acid anhydride preparation method based on modified vanadium titanium oxide composite catalyzing
CN112536025B (en) * 2019-09-20 2023-04-07 中国石油化工股份有限公司 Catalyst for preparing pyromellitic anhydride by oxidization of durene and preparation method and application thereof
CN113877569B (en) * 2020-07-03 2023-08-29 中国石油化工股份有限公司 Catalyst for producing pyromellitic dianhydride and preparation method thereof
CN114425325B (en) * 2020-09-28 2024-05-28 中国石油化工股份有限公司 Catalyst for preparing pyromellitic anhydride by oxidizing pyromellitic benzene and preparation method and application thereof
CN116059994A (en) 2021-11-01 2023-05-05 中国石油化工股份有限公司 Catalyst for preparing maleic anhydride by gas-phase oxidation of durene, preparation method thereof and method for preparing maleic anhydride by gas-phase oxidation of durene

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1321543A (en) * 2001-04-06 2001-11-14 陈永和 Catalyst for preparing pyromellitic acid dianhydride by gas phase oxidation of durene and its preparation method
CN102008971A (en) * 2010-10-19 2011-04-13 黑龙江省科学院石油化学研究院 Pyromellitic dianhydride catalyst and preparation method thereof
CN105582928A (en) * 2014-10-24 2016-05-18 中国石油化工股份有限公司 3-acetoxypropanal catalyst

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1321543A (en) * 2001-04-06 2001-11-14 陈永和 Catalyst for preparing pyromellitic acid dianhydride by gas phase oxidation of durene and its preparation method
CN102008971A (en) * 2010-10-19 2011-04-13 黑龙江省科学院石油化学研究院 Pyromellitic dianhydride catalyst and preparation method thereof
CN105582928A (en) * 2014-10-24 2016-05-18 中国石油化工股份有限公司 3-acetoxypropanal catalyst

Also Published As

Publication number Publication date
CN107866241A (en) 2018-04-03

Similar Documents

Publication Publication Date Title
CN107866241B (en) Catalyst for preparing pyromellitic anhydride by oxidizing durene
CN107866215B (en) Catalyst for synthesizing pyromellitic anhydride from durene
CN107866257B (en) Catalyst for preparing pyromellitic anhydride from durene
CN107866254B (en) Catalyst for preparing pyromellitic anhydride by gas-phase oxidation of durene
CN107866259B (en) catalyst for durene gas-phase oxidation reaction
CN111097466B (en) Preparation method of catalyst for preparation of pyromellitic anhydride
CN112536025B (en) Catalyst for preparing pyromellitic anhydride by oxidization of durene and preparation method and application thereof
CN107866251B (en) Catalyst for preparation of pyromellitic anhydride
CN107866252B (en) Catalyst for synthesizing pyromellitic anhydride from durene
CN113877569B (en) Catalyst for producing pyromellitic dianhydride and preparation method thereof
CN107866258B (en) Catalyst for durene oxidation reaction
CN107866228B (en) Catalyst for synthesizing homoanhydride
CN107866256B (en) Catalyst for synthesizing pyromellitic dianhydride by oxidizing pyromellitic dianhydride
CN108043435B (en) Catalyst for preparing pyromellitic dianhydride by gas-phase oxidation of durene and preparation and application thereof
CN107866255B (en) Catalyst for preparing pyromellitic anhydride
CN115518683B (en) Supported catalyst, preparation method and application thereof, and method for synthesizing pyromellitic dianhydride by gas-phase oxidation of durene
CN107866229B (en) Catalyst for durene oxidation
CN107866253B (en) catalyst for synthesis reaction of pyromellitic anhydride
JP6321799B2 (en) Method for producing butadiene
CN114433155B (en) Catalyst for synthesizing pyromellitic anhydride by oxidizing pyromellitic benzene and preparation method and application thereof
CN109647470B (en) Catalyst for preparing partial anhydride
CN114643052A (en) Catalyst for synthesizing pyromellitic dianhydride and preparation method and application thereof
CN114643051B (en) Catalyst for synthesizing pyromellitic anhydride by oxidizing pyromellitic benzene and preparation method and application thereof
CN110560116B (en) Catalyst for oxidation of pseudocumene to prepare meta-anhydride
CN109647467B (en) Catalyst for oxidation of pseudocumene

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