CN107866256A - Catalyst for the equal acid anhydride of durol oxidative synthesis - Google Patents
Catalyst for the equal acid anhydride of durol oxidative synthesis Download PDFInfo
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- CN107866256A CN107866256A CN201610849389.6A CN201610849389A CN107866256A CN 107866256 A CN107866256 A CN 107866256A CN 201610849389 A CN201610849389 A CN 201610849389A CN 107866256 A CN107866256 A CN 107866256A
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- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/20—Carbon compounds
- B01J27/22—Carbides
- B01J27/224—Silicon carbide
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- 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
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Abstract
The present invention relates to a kind of catalyst that equal acid anhydride is synthesized for durol gaseous oxidation, mainly solves in the prior art the problem of reaction of durol oxidative synthesis can produce many accessory substances, cause equal acid anhydride yield low.The present invention uses oxide catalyst, and the catalyst uses α Al2O3, carborundum, ceramic ring or its mixture be carrier, active component includes v element, nonmetalloid and IVA races element and III B races element, at least one of technical scheme, preferably resolve the technical problem, side reaction when reducing equal acid anhydride synthesis occurs, and improves the yield of equal acid anhydride.
Description
Technical field
The present invention relates to a kind of catalyst for the equal acid anhydride of durol oxidative synthesis and preparation method thereof, and equal acid anhydride
Synthetic method.
Technical background
With developing rapidly for the industry such as oil refining, chemical fibre and polyester, large-scale ethylene plant, catalytic reforming unit, virtue
Hydrocarbon device, disproportionation, isomerization process etc. are by the substantial amounts of C10 aromatic hydrocarbons of by-product.Therefore, how effectively using C10 aromatic hydrocarbon resources into
For a big important topic of petrochemical industry.As the important intermediate of high added value fine chemical product, have 4 symmetrical carboxyls special
Many, which can be made, in the pyromellitic acid anhydride (PMDA, equal acid anhydride) of different structure has superior heat resistance, electrical insulating property and chemically-resistant medicine
The product of moral character.It is primarily useful for producing monomer, medicine intermediate, the epoxy resin of the heat stable resins such as polyimides, polyimidazole
Curing agent etc., the sophisticated technology such as aviation, aerospace, electronics industry field is can be widely applied to its manufactured product.Therefore, will refine
Change by-product C10 aromatic hydrocarbons in content it is higher durol extraction after be further processed into high added value equal acid anhydride have it is extremely important
Research Significance and significant economic benefit.
At present, vapour phase oxidation process is used mostly to prepare equal acid anhydride using durol as raw material, because the process is one multiple
Miscellaneous heterogeneous catalysis process, a variety of side reactions be present, cause the yield of equal acid anhydride very low.Vapour phase oxidation process prepares equal acid anhydride catalyst master
If using vanadium system as active component, it is aided with a small amount of metallic element, the theoretical yield that equal acid anhydride is calculated by chemical equation should
This reaches 163%, but the catalyst activity that traditional preparation method is worth is relatively low, and the actual recovery highest of equal acid anhydride is only capable of
Reach the 56% of theoretical yield.Therefore, it is to the selectivity of equal acid anhydride to improve catalyst by changing the preparation method of catalyst
It is very necessary.
CN101037439A discloses a kind of carrier model polyoxometallate catalyst, can react at a lower temperature.
CN01105883.8 reports one kind with V2O5And TiO2For major catalyst, Nb2O5、Cs2O and P2O5For the catalytic body of co-catalyst
System.US6084109 discloses a kind of V2O5-WO3Catalyst, manganese, antimony, bismuth, phosphorus, the oxide system of copper or its mixture.It is above-mentioned
Method is made in durol oxidation and had made great progress in the preparation of equal acid anhydride catalyst, but still it is relatively low equal acid anhydride yield to be present
Problem.
The content of the invention
One of technical problems to be solved by the invention are the problem of equal acid anhydride yield are low in the prior art, there is provided one kind is used for
The catalyst of the equal acid anhydride of durol oxidative synthesis, the catalyst have the characteristics of equal acid anhydride high income.
The two of the technical problems to be solved by the invention are to provide a kind of with solving one of technical problem corresponding catalysis
The preparation method of agent.
The three of the technical problems to be solved by the invention are to provide a kind of with solving that one of technical problem is corresponding to be used for
The method of the equal acid anhydride of durol oxidative synthesis.
To solve one of above-mentioned technical problem, technical scheme disclosed in this invention is：One kind is used for durol and aoxidized
Synthesize the catalyst of equal acid anhydride, it is characterised in that the catalyst uses α-Al2O3, carborundum, ceramic ring or its mixture be carrier,
Active component includes v element, nonmetalloid, and at least one of IVA races element and III B races element.It is preferred that the activity
Component is simultaneously including v element, nonmetalloid, at least one element selected from IVA races element and in III B races element
At least one element.Now there is synergy between IVA races element and III B races element in terms of equal acid anhydride yield is improved.
In above-mentioned technical proposal, the nonmetalloid is selected from least one of B, Si, As, Te and Se.More preferably Si
And As.
In above-mentioned technical proposal, IVA races element is selected from Ge, Sn and Pb.
In above-mentioned technical proposal, the III B races element is selected from least one of Sc and Y.
In above-mentioned technical proposal, as most preferred technical scheme, the active component is simultaneously including v element, nonmetallic
Element, IVA races element and III B races element；Such as the active constituent includes V, Si, Ge and Sc, or V, As, Sn, Sc and Y,
Either V, Si, Sn, Pb, Sc and Y or V, Si, As, Sn, Pb, Sc and Y.
In above-mentioned technical proposal, the ratio of v element and nonmetalloid is 1 in the catalyst:(1-10), more preferably
For 1:(3-8)；The ratio of v element and IVA races element and III B races element summation is 1 in the catalyst：(0.01-1), it is more excellent
Elect 1 as：(0.02-0.5).
To solve the two of above-mentioned technical problem, technical solution of the present invention is as follows：The technical scheme of one of above-mentioned technical problem
Described in the preparation method for the equal acid anhydride catalyst of durol oxidative synthesis, it includes several steps：
(1) vanadium source is added in oxalic acid solution, obtains mixed solution；By nonmetalloid, IVA races element and III B races
Element compound adds reaction system, obtains presoma；
(2) presoma is sprayed on carrier, catalyst is obtained after roasting.
In above-mentioned technical proposal, step (1) the vanadium source preferably is selected from vanadium oxide, metavanadate, positive vanadate and vanadium chloride
At least one.The compound of step (1) described nonmetalloid preferably is selected from silica, silicate, silicic acid, chlorosilane, boric acid
At least one of salt, arsenic oxide arsenoxide, methyl arsenic, methanearsonic acid, arsenate.The compound of step (1) the IVA races element is preferred
Autoxidation germanium, germanium halide, organic germanide, tin oxide, artificial gold, tin halides, the inorganic salts of tin, lead oxide, vulcanized lead, sulfuric acid
At least one of lead, plumbi nitras, lead acetate.The compound of step (1) the III B races element preferably be selected from scandium oxide, scandium halide,
At least one of scandium sulfate, yittrium oxide, yttrofluorite.
In above-mentioned technical proposal, the described preparation method for being used to synthesize equal acid anhydride catalyst, it is characterised in that by catalyst
Presoma be fitted into flush coater, at 215-255 DEG C heat after uniformly spray on carrier.
In above-mentioned technical proposal, the described preparation method for being used for durol and preparing equal acid anhydride catalyst, it is characterised in that
The carrier of catalyst precursor will be coated with Muffle kiln roasting, sintering temperature is 495-575 DEG C of temperature, roasting time 2-
6h。
To solve the three of above-mentioned technical problem, technical scheme is as follows：The method that durol prepares equal acid anhydride, with
Durol, air are raw material, using fixed bed reactors, synthesize equal acid anhydride in the presence of a catalyst.
Reaction process condition is as follows in above-mentioned technical proposal：The mass concentration of durol is 33-53g/m3, it reacts work
Skill condition：Air speed is 4350~6450hr-1, reaction temperature be 285~515 DEG C, reaction pressure is normal pressure.
Compared with prior art, key of the invention is that the active component of catalyst includes a certain amount of v element, non-
Metallic element and selected from least one of IVA races element and III B races element element, be advantageous to improve the activity of catalyst and steady
It is qualitative, so as to improve the yield of equal acid anhydride.
Test result indicates that acid anhydride yield achieves preferable technique effect, especially up to 78.1% prepared by the present invention
In catalyst active component simultaneously including v element, nonmetalloid, selected from least one of IVA races element metallic element and
During selected from least one of III B races element metallic element, more prominent technique effect is achieved, can be used for the conjunction of equal acid anhydride
Cheng Zhong.Below by embodiment, the present invention is further elaborated.
Embodiment
【Embodiment 1】
98g oxalic acid and 400ml distilled water are weighed in flask, stirring is warming up to 85 DEG C, after oxalic acid all dissolving, is made into
Oxalic acid solution.1 part of vanadic anhydride is added in the oxalic acid solution prepared and continues to stir, obtains vanadyl oxalate ammonium salt solution.
4 parts of dichlorosilanes, 0.4 part of germanium oxide are added in solution, continue to obtain catalyst precursor after stirring.Before catalyst
After driving body filtration drying, it is fitted into flush coater, uniformly sprays on inert carrier carborundum.Catalyst precursor will be coated with
Inert carrier in Muffle furnace, 535 DEG C of roastings, obtain catalyst after natural cooling.Catalyst is in 525 DEG C of reaction temperature, sky
Fast 5250h-1Under, checked and rated in fixed bed reactors, it is 74.1% to measure equal acid anhydride yield, and its appraisal result refers to table 1.
【Embodiment 2】
98g oxalic acid and 400ml distilled water are weighed in flask, stirring is warming up to 85 DEG C, after oxalic acid all dissolving, is made into
Oxalic acid solution.1 part of vanadic anhydride is added in the oxalic acid solution prepared and continues to stir, obtains vanadyl oxalate ammonium salt solution.
4 parts of dichlorosilanes, 0.4 part of scandium oxide are added in solution, continue to obtain catalyst precursor after stirring.Before catalyst
After driving body filtration drying, it is fitted into flush coater, uniformly sprays on inert carrier carborundum.Catalyst precursor will be coated with
Inert carrier in Muffle furnace, 535 DEG C of roastings, obtain catalyst after natural cooling.Catalyst is in 525 DEG C of reaction temperature, sky
Fast 5250h-1Under, checked and rated in fixed bed reactors, it is 74.2% to measure equal acid anhydride yield, and its appraisal result refers to table 1.
【Comparative example 1】
98g oxalic acid and 400ml distilled water are weighed in flask, stirring is warming up to 85 DEG C, after oxalic acid all dissolving, is made into
Oxalic acid solution.1 part of vanadic anhydride is added in the oxalic acid solution prepared and continues to stir, obtains vanadyl oxalate ammonium salt solution.
4 parts of dichlorosilanes are added in solution, continue to obtain catalyst precursor after stirring.By catalyst precursor filtration drying
Afterwards, it is fitted into flush coater, uniformly sprays on inert carrier carborundum.The inert carrier for being coated with catalyst precursor is existed
In Muffle furnace, 535 DEG C are calcined, and catalyst is obtained after natural cooling.Catalyst is in 525 DEG C of reaction temperature, air speed 5250h-1Under,
Checked and rated in fixed bed reactors, it is 69.7% to measure equal acid anhydride yield, and its appraisal result refers to table 1.
The catalyst used by can be seen that the present invention compared with embodiment 1~2, using simultaneously containing V, Si and Ge work
Property component while catalyst performance ratio containing V, Si and Sc active component will be more containing only the performance of V, Si active constituent catalyst
Excellent, the yield of equal acid anhydride is higher.
【Embodiment 3】
98g oxalic acid and 400ml distilled water are weighed in flask, stirring is warming up to 85 DEG C, after oxalic acid all dissolving, is made into
Oxalic acid solution.1 part of vanadic anhydride is added in the oxalic acid solution prepared and continues to stir, obtains vanadyl oxalate ammonium salt solution.
4 parts of methanearsonic acids, 0.4 part of germanium chloride are added in solution, continue to obtain catalyst precursor after stirring.Before catalyst
After driving body filtration drying, it is fitted into flush coater, uniformly sprays on inert carrier carborundum.Catalyst precursor will be coated with
Inert carrier in Muffle furnace, 535 DEG C of roastings, obtain catalyst after natural cooling.Catalyst is in 525 DEG C of reaction temperature, sky
Fast 5250h-1Under, checked and rated in fixed bed reactors, it is 74.5% to measure equal acid anhydride yield, and its appraisal result refers to table 1.
【Embodiment 4】
98g oxalic acid and 400ml distilled water are weighed in flask, stirring is warming up to 85 DEG C, after oxalic acid all dissolving, is made into
Oxalic acid solution.1 part of ammonium metavanadate is added in the oxalic acid solution prepared and continues to stir, obtains vanadyl oxalate ammonium salt solution.By 4
Part methanearsonic acid, 0.4 part of germanium oxide are added in solution, continue to obtain catalyst precursor after stirring.By complex catalyst precursor
After body filtration drying, it is fitted into flush coater, uniformly sprays on inert carrier carborundum.Catalyst precursor will be coated with
Inert carrier is in Muffle furnace, 535 DEG C of roastings, and catalyst is obtained after natural cooling.Catalyst is in 525 DEG C of reaction temperature, air speed
5250h-1Under, checked and rated in fixed bed reactors, it is 74.4% to measure equal acid anhydride yield, and its appraisal result refers to table 1.
【Embodiment 5】
98g oxalic acid and 400ml distilled water are weighed in flask, stirring is warming up to 85 DEG C, after oxalic acid all dissolving, is made into
Oxalic acid solution.1 part of ammonium metavanadate is added in the oxalic acid solution prepared and continues to stir, obtains vanadyl oxalate ammonium salt solution.By 4
Part dichlorosilane, 0.4 part of yittrium oxide are added in solution, continue to obtain catalyst precursor after stirring.By complex catalyst precursor
After body filtration drying, it is fitted into flush coater, uniformly sprays on inert carrier carborundum.Catalyst precursor will be coated with
Inert carrier is in Muffle furnace, 535 DEG C of roastings, and catalyst is obtained after natural cooling.Catalyst is in 525 DEG C of reaction temperature, air speed
5250h-1Under, checked and rated in fixed bed reactors, it is 74.6% to measure equal acid anhydride yield, and its appraisal result refers to table 1.
【Embodiment 6】
98g oxalic acid and 400ml distilled water are weighed in flask, stirring is warming up to 85 DEG C, after oxalic acid all dissolving, is made into
Oxalic acid solution.1 part of vanadic anhydride is added in the oxalic acid solution prepared and continues to stir, obtains vanadyl oxalate ammonium salt solution.
4 parts of dichlorosilanes, 0.4 part of yittrium oxide are added in solution, continue to obtain catalyst precursor after stirring.Before catalyst
After driving body filtration drying, it is fitted into flush coater, uniformly sprays on inert carrier carborundum.Catalyst precursor will be coated with
Inert carrier in Muffle furnace, 535 DEG C of roastings, obtain catalyst after natural cooling.Catalyst is in 525 DEG C of reaction temperature, sky
Fast 5250h-1Under, checked and rated in fixed bed reactors, it is 74.7% to measure equal acid anhydride yield, and its appraisal result refers to table 1.
【Embodiment 7】
98g oxalic acid and 400ml distilled water are weighed in flask, stirring is warming up to 85 DEG C, after oxalic acid all dissolving, is made into
Oxalic acid solution.1 part of vanadic anhydride is added in the oxalic acid solution prepared and continues to stir, obtains vanadyl oxalate ammonium salt solution.
4 parts of dichlorosilanes, 0.2 part of germanium oxide and 0.2 part of scandium oxide are added in solution, continue to obtain complex catalyst precursor after stirring
Body.After catalyst precursor filtration drying, it is fitted into flush coater, uniformly sprays on inert carrier carborundum.Will spraying
There is the inert carrier of catalyst precursor in Muffle furnace, 535 DEG C are calcined, and catalyst is obtained after natural cooling.Catalyst is anti-
Answer 525 DEG C of temperature, air speed 5250h-1Under, checked and rated in fixed bed reactors, it is 75.3% to measure equal acid anhydride yield, its appraisal result
Refer to table 1.
The present embodiment is compared with embodiment 1~2 as can be seen that IVA races Ge elements and III B races Sc elements are improving equal acid anhydride receipts
Rate has preferably synergy.
【Embodiment 8】
98g oxalic acid and 400ml distilled water are weighed in flask, stirring is warming up to 85 DEG C, after oxalic acid all dissolving, is made into
Oxalic acid solution.1 part of vanadic anhydride is added in the oxalic acid solution prepared and continues to stir, obtains vanadyl oxalate ammonium salt solution.
4 parts of dichlorosilanes, 0.1 part of germanium oxide, 0.1 part of stannic chloride and 0.2 part of scandium oxide are added in solution, continue to obtain after stirring
To catalyst precursor.After catalyst precursor filtration drying, it is fitted into flush coater, uniformly sprays and be carbonized in inert carrier
On silicon.The inert carrier of catalyst precursor will be coated with Muffle furnace, 535 DEG C of roastings, obtain catalyst after natural cooling.
Catalyst is in 525 DEG C of reaction temperature, air speed 5250h-1Under, checked and rated in fixed bed reactors, it is 75.9% to measure equal acid anhydride yield,
Its appraisal result refers to table 1.
The present embodiment can be seen that IVA races Ge elements and Sn elements and the other activearms of the present invention compared with Example 7
Divide and improving equal acid anhydride yield with preferably synergy.
【Embodiment 9】
98g oxalic acid and 400ml distilled water are weighed in flask, stirring is warming up to 85 DEG C, after oxalic acid all dissolving, is made into
Oxalic acid solution.1 part of vanadic anhydride is added in the oxalic acid solution prepared and continues to stir, obtains vanadyl oxalate ammonium salt solution.
4 parts of dichlorosilanes, 0.2 part of germanium oxide, 0.1 part of scandium chloride and 0.1 part of yittrium oxide are added in solution, continue to obtain after stirring
To catalyst precursor.After catalyst precursor filtration drying, it is fitted into flush coater, uniformly sprays and be carbonized in inert carrier
On silicon.The inert carrier of catalyst precursor will be coated with Muffle furnace, 535 DEG C of roastings, obtain catalyst after natural cooling.
Catalyst is in 525 DEG C of reaction temperature, air speed 5250h-1Under, checked and rated in fixed bed reactors, it is 76.6% to measure equal acid anhydride yield,
Its appraisal result refers to table 1.
The present embodiment can be seen that III B races Sc and Y element and exists with the other active components of the present invention compared with Example 7
Improving equal acid anhydride yield has preferably synergy.
【Embodiment 10】
98g oxalic acid and 400ml distilled water are weighed in flask, stirring is warming up to 85 DEG C, after oxalic acid all dissolving, is made into
Oxalic acid solution.1 part of vanadic anhydride is added in the oxalic acid solution prepared and continues to stir, obtains vanadyl oxalate ammonium salt solution.
4 parts of dichlorosilanes, 0.1 part of germanium oxide, 0.1 part of stannic chloride, 0.1 part of scandium chloride and 0.1 part of yittrium oxide are added in solution, continued
Catalyst precursor is obtained after stirring.After catalyst precursor filtration drying, it is fitted into flush coater, uniformly sprays
On inert carrier carborundum.The inert carrier of catalyst precursor will be coated with Muffle furnace, 535 DEG C of roastings, natural cooling
After obtain catalyst.Catalyst is in 525 DEG C of reaction temperature, air speed 5250h-1Under, checked and rated in fixed bed reactors, measure equal acid anhydride
Yield is 77.4%, and its appraisal result refers to table 1.
The present embodiment is compared with embodiment 8, embodiment 9 as can be seen that V, nonmetallic Si elements, IVA races Ge and Sn elements
There is extraordinary synergy in the equal acid anhydride yield of raising with III B races Sc and Y element.
【Embodiment 11】
98g oxalic acid and 400ml distilled water are weighed in flask, stirring is warming up to 85 DEG C, after oxalic acid all dissolving, is made into
Oxalic acid solution.1 part of vanadic anhydride is added in the oxalic acid solution prepared and continues to stir, obtains vanadyl oxalate ammonium salt solution.
2 parts of dichlorosilanes, 2 parts of methanearsonic acids, 0.1 part of germanium oxide, 0.1 part of stannic chloride, 0.1 part of scandium chloride and 0.1 part of yittrium oxide are added
Enter in solution, continue to obtain catalyst precursor after stirring.After catalyst precursor filtration drying, load flush coater
In, uniformly spray on inert carrier carborundum.The inert carrier of catalyst precursor will be coated with Muffle furnace, 535
DEG C roasting, obtains catalyst after natural cooling.Catalyst is in 525 DEG C of reaction temperature, air speed 5250h-1Under, in fixed bed reactors
Middle examination, it is 78.1% to measure equal acid anhydride yield, and its appraisal result refers to table 1.
The present embodiment can be seen that V, nonmetallic Si and As elements, IVA races Ge and Sn elements and III compared with Example 10
B races Sc and Y element have extraordinary synergy in the equal acid anhydride yield of raising.
Table 1
Claims (10)
1. a kind of catalyst for the equal acid anhydride of durol oxidative synthesis, it is characterised in that the catalyst uses α-Al2O3, carbon
SiClx, ceramic ring or its mixture are carrier, and active component includes v element, nonmetalloid, and IVA races element and III B races
At least one of element.
2. catalyst as claimed in claim 1, it is characterised in that the nonmetalloid in B, Si, As and Te at least one
Kind.
3. catalyst as claimed in claim 1, it is characterised in that IVA races element is selected from Ge, Sn and Pb.
4. catalyst as claimed in claim 1, it is characterised in that the III B races element is selected from least one of Sc and Y.
5. catalyst as claimed in claim 1, it is characterised in that the ratio of v element and nonmetalloid is 1 in catalyst：(1-
10)。
6. catalyst as claimed in claim 1, it is characterised in that v element and IVA races element and III B races element are total in catalyst
The ratio of sum is 1：(0.01-1).
A kind of 7. preparation method for being used for durol and preparing equal acid anhydride catalyst described in claim 1, it is characterised in that including
Several steps：
(1) vanadium source is added in oxalic acid solution, obtains mixed solution；By nonmetalloid, IVA races element and III B races element
Compound adds reaction system, obtains presoma；
(2) presoma is sprayed on carrier, catalyst is obtained after roasting.
8. the preparation method for being used for durol and preparing equal acid anhydride catalyst as described in right 6, it is characterised in that by catalyst
Presoma is fitted into flush coater, is uniformly sprayed after being heated at 215-255 DEG C on carrier.
9. the preparation method of equal acid anhydride catalyst is prepared for durol as claimed in claim 6, it is characterised in that will spray
There is the carrier of catalyst precursor in Muffle kiln roasting, sintering temperature is 495-575 DEG C of temperature, roasting time 2-6h.
10. a kind of method for preparing equal acid anhydride for durol, using durol, air as raw material, using fixed bed reactors,
The mass concentration of durol is 33-53g/m3, its reaction process condition：Air speed is 4350~6450hr-1, reaction temperature be
285~515 DEG C, reaction pressure is normal pressure, and equal acid anhydride is synthesized in the presence of any one catalyst described in Claims 1 to 5.
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| CN201610849389.6A CN107866256B (en) | 2016-09-23 | 2016-09-23 | Catalyst for synthesizing pyromellitic dianhydride by oxidizing pyromellitic dianhydride |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN115228462A (en) * | 2021-04-23 | 2022-10-25 | 中国石油化工股份有限公司 | Supported catalyst for synthesizing pyromellitic dianhydride by gas phase oxidation, preparation method thereof and method for synthesizing pyromellitic dianhydride by oxidation of pyromellitic dianhydride |
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| CN1294942A (en) * | 1999-11-03 | 2001-05-16 | 中国石油化工集团公司 | Catalyst for acrylonitrile fluid bed |
| CN102626648A (en) * | 2012-03-20 | 2012-08-08 | 常熟市联邦化工有限公司 | Preparation of pyromellitic dianhydride (PMDA) multi-component oxide catalyst through catalytic gas phase oxidation method |
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| CN1294942A (en) * | 1999-11-03 | 2001-05-16 | 中国石油化工集团公司 | Catalyst for acrylonitrile fluid bed |
| CN102626648A (en) * | 2012-03-20 | 2012-08-08 | 常熟市联邦化工有限公司 | Preparation of pyromellitic dianhydride (PMDA) multi-component oxide catalyst through catalytic gas phase oxidation method |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN115228462A (en) * | 2021-04-23 | 2022-10-25 | 中国石油化工股份有限公司 | Supported catalyst for synthesizing pyromellitic dianhydride by gas phase oxidation, preparation method thereof and method for synthesizing pyromellitic dianhydride by oxidation of pyromellitic dianhydride |
| CN115228462B (en) * | 2021-04-23 | 2023-11-24 | 中国石油化工股份有限公司 | Supported catalyst for synthesizing maleic anhydride by gas phase oxidation, preparation method thereof and method for synthesizing maleic anhydride by durene oxidation |
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