CN107866241A - The catalyst of equal acid anhydride is made for durol oxidation - Google Patents
The catalyst of equal acid anhydride is made for durol oxidation Download PDFInfo
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- CN107866241A CN107866241A CN201610846448.4A CN201610846448A CN107866241A CN 107866241 A CN107866241 A CN 107866241A CN 201610846448 A CN201610846448 A CN 201610846448A CN 107866241 A CN107866241 A CN 107866241A
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- acid anhydride
- durol
- equal acid
- alkali metal
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/186—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J27/195—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with vanadium, niobium or tantalum
- B01J27/198—Vanadium
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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
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- 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
Abstract
The present invention relates to a kind of catalyst that equal acid anhydride is made for durol oxidation, mainly solve in the prior art that equal acid anhydride catalyst activity is low, accessory substance is more, the problem of so as to cause product 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, titanium elements, and the technical scheme of at least one of VA races element and alkali metal, preferably resolves the technical problem, greatly improve yield of the catalyst to equal acid anhydride.
Description
Technical field
The present invention relates to a kind of catalyst that equal acid anhydride is made for durol oxidation and preparation method thereof, and the conjunction of acid anhydride
Into 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 catalyst yield are low in the prior art, there is provided one
Kind is used for the catalyst that equal acid anhydride is made in durol oxidation, and the catalyst has 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 that equal acid anhydride is made in durol oxidation.
To solve one of above-mentioned technical problem, technical scheme disclosed in this invention is：One kind is used for durol and aoxidized
Make the catalyst of equal acid anhydride, it is characterised in that the catalyst uses inert carrier, and active component includes v element, titanium elements, with
And at least one of VA races element and alkali metal.It is preferred that the active component is simultaneously including v element, titanium elements, selected from VA
At least one element of race's element and selected from least one of alkali metal element.Now between VA races and the element of alkali metal
There is synergy in terms of improving equal acid anhydride yield.
In above-mentioned technical proposal, the VA elements are selected from least one of phosphorus, arsenic, antimony and bismuth.More preferably phosphorus and antimony.
In above-mentioned technical proposal, the alkali metal is selected from least one of lithium, sodium, potassium, rubidium and caesium.
In above-mentioned technical proposal, as most preferred technical scheme, the active component is simultaneously including v element, titanium member
Element, VA races element and alkali metal；Such as the active constituent includes vanadium, titanium, phosphorus and lithium, Huo Zhefan, titanium, phosphorus, antimony, potassium,
Or vanadium, titanium, phosphorus, antimony, potassium, rubidium.
In above-mentioned technical proposal, the ratio of v element and titanium elements is 1 in the catalyst:(1-10), more preferably 1:
(3-8)；V element and the ratio of VA elements and alkali metal summation are 1 in the catalyst：(0.01-1), more preferably 1：
(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 being used for durol oxidation and making equal acid anhydride catalyst, it includes several steps：
(1) vanadium source is added in oxalic acid solution, obtains mixed solution.By titanium source, VA races and alkali metal compound
Reaction system is added, 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, vanadium chloride
It is at least one.Step (1) described titanium source preferably is selected from titanium oxide, halogenated titanium, titanium salt, titanate, at least the one of organic titanic compound
Kind.The compound of step (1) the VA races element preferably be selected from ammonium dihydrogen phosphate, diammonium hydrogen phosphate, antimony pentoxide, nitric acid antimony,
At least one of antimony sulfate.The compound of step (1) described alkali metal preferably is selected from alkali metal oxide, alkali metal chlorination
At least one of thing, alkali nitrates, alkali metal sulfates and alkali metal acetate.
In above-mentioned technical proposal, the described preparation method for being used for durol oxidation and making equal acid anhydride catalyst, its feature exists
In, the presoma of catalyst is fitted into flush coater, at 220-260 DEG C heat after uniformly spray on carrier.
In above-mentioned technical proposal, the described preparation method for being used for durol oxidation and making equal acid anhydride catalyst, its feature exists
In the carrier of catalyst precursor will be coated with Muffle kiln roasting, and sintering temperature is 500-550 DEG C of temperature, roasting time
For 3-5h.
To solve the three of above-mentioned technical problem, technical scheme is as follows：The method that equal acid anhydride is made in durol oxidation,
Using durol, air as raw material, using fixed bed reactors, equal acid anhydride is synthesized in the presence of a catalyst.
Reaction process condition is as follows in above-mentioned technical proposal：The mass concentration of durol is 30-50g/m3, it reacts work
Skill condition：Air speed is 4000~6000hr-1, reaction temperature be 300~500 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, titanium
Element and selected from least one of VA races and alkali metal element, is advantageous to improve the activity and stability of catalyst, so as to carry
The high yield of equal acid anhydride.
Test result indicates that acid anhydride yield achieves preferable technique effect, especially up to 75.5% prepared by the present invention
Active component is simultaneously including v element, titanium elements, selected from least one of VA metallic elements and selected from alkali metal in catalyst
At least one of metallic element when, achieve more prominent technique effect, can be used in the synthesis of equal acid anhydride.Below by
The present invention is further elaborated for embodiment.
Embodiment
【Embodiment 1】
88g oxalic acid and 340ml distilled water are weighed in flask, stirring is warming up to 80 DEG C, after oxalic acid all dissolving, is made into
Oxalic acid solution.A vanadic anhydride is added in the oxalic acid solution prepared and continues to stir, obtains vanadyl oxalate ammonium salt solution.
By 5 parts of TiO2, 0.4 part of ammonium dihydrogen phosphate add 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 Alpha-alumina.Complex catalyst precursor will be coated with
The inert carrier of body is in Muffle furnace, 560 DEG C of roastings, and catalyst is obtained after natural cooling.Catalyst 480 DEG C of reaction temperature,
Air speed 5400h-1Under, checked and rated in fixed bed reactors, it is 71.4% to measure equal acid anhydride yield, and its appraisal result refers to table 1.
【Embodiment 2】
88g oxalic acid and 340ml distilled water are weighed in flask, stirring is warming up to 80 DEG C, after oxalic acid all dissolving, is made into
Oxalic acid solution.A vanadic anhydride is added in the oxalic acid solution prepared and continues to stir, obtains vanadyl oxalate ammonium salt solution.
By 5 parts of TiO2, 0.4 part of potassium nitrate add in solution, continue to obtain catalyst precursor after stirring.By catalyst precursor
After filtration drying, it is fitted into flush coater, uniformly sprays on inert carrier Alpha-alumina.Catalyst precursor will be coated with
Inert carrier is in Muffle furnace, 560 DEG C of roastings, and catalyst is obtained after natural cooling.Catalyst is in 480 DEG C of reaction temperature, air speed
5400h-1Under, checked and rated in fixed bed reactors, it is 71.2% to measure equal acid anhydride yield, and its appraisal result refers to table 1.
【Comparative example 1】
88g oxalic acid and 340ml distilled water are weighed in flask, stirring is warming up to 80 DEG C, after oxalic acid all dissolving, is made into
Oxalic acid solution.A vanadic anhydride is added in the oxalic acid solution prepared and continues to stir, obtains vanadyl oxalate ammonium salt solution.
By 5 parts of TiO2Add in solution, continue to obtain catalyst precursor after stirring.After catalyst precursor filtration drying,
It is fitted into flush coater, uniformly sprays on inert carrier Alpha-alumina.The inert carrier for being coated with catalyst precursor is existed
In Muffle furnace, 560 DEG C are calcined, and catalyst is obtained after natural cooling.Catalyst is in 480 DEG C of reaction temperature, air speed 5400h-1Under,
Checked and rated in fixed bed reactors, it is 67.2% 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, Ti and P activity
Component while catalyst performance ratio containing V, Ti and K active component is more excellent containing only the performance of V, Ti active constituent catalyst,
The yield of acid anhydride is higher.
【Embodiment 3】
88g oxalic acid and 340ml distilled water are weighed in flask, stirring is warming up to 80 DEG C, after oxalic acid all dissolving, is made into
Oxalic acid solution.A vanadic anhydride is added in the oxalic acid solution prepared and continues to stir, obtains vanadyl oxalate ammonium salt solution.
5 parts of titanium tetrachlorides, 0.4 part of diammonium hydrogen phosphate are added in solution, continue to obtain catalyst precursor after stirring.Will catalysis
After agent presoma filtration drying, it is fitted into flush coater, uniformly sprays on inert carrier Alpha-alumina.Catalyst will be coated with
The inert carrier of presoma is in Muffle furnace, 560 DEG C of roastings, and catalyst is obtained after natural cooling.Catalyst is in reaction temperature 480
DEG C, air speed 5400h-1Under, checked and rated in fixed bed reactors, it is 71.3% to measure equal acid anhydride yield, and its appraisal result refers to table 1.
【Embodiment 4】
88g oxalic acid and 340ml distilled water are weighed in flask, stirring is warming up to 80 DEG C, after oxalic acid all dissolving, is made into
Oxalic acid solution.A ammonium metavanadate is added in the oxalic acid solution prepared and continues to stir, obtains vanadyl oxalate ammonium salt solution.Will
5 parts of titanium tetrachlorides, 0.4 part of nitric acid antimony 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 Alpha-alumina.Catalyst precursor will be coated with
Inert carrier in Muffle furnace, 560 DEG C of roastings, obtain catalyst after natural cooling.Catalyst is in 480 DEG C of reaction temperature, sky
Fast 5400h-1Under, checked and rated in fixed bed reactors, it is 71.5% to measure equal acid anhydride yield, and its appraisal result refers to table 1.
【Embodiment 5】
88g oxalic acid and 340ml distilled water are weighed in flask, stirring is warming up to 80 DEG C, after oxalic acid all dissolving, is made into
Oxalic acid solution.A ammonium metavanadate is added in the oxalic acid solution prepared and continues to stir, obtains vanadyl oxalate ammonium salt solution.Will
5 parts of titanium tetrachlorides, 0.4 part of sodium chloride 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 Alpha-alumina.Catalyst precursor will be coated with
Inert carrier in Muffle furnace, 560 DEG C of roastings, obtain catalyst after natural cooling.Catalyst is in 480 DEG C of reaction temperature, sky
Fast 5400h-1Under, checked and rated in fixed bed reactors, it is 71.7% to measure equal acid anhydride yield, and its appraisal result refers to table 1.
【Embodiment 6】
88g oxalic acid and 340ml distilled water are weighed in flask, stirring is warming up to 80 DEG C, after oxalic acid all dissolving, is made into
Oxalic acid solution.A vanadic anhydride is added in the oxalic acid solution prepared and continues to stir, obtains vanadyl oxalate ammonium salt solution.
5 parts of titanium tetrachlorides, 0.4 part of cesium sulfate 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 Alpha-alumina.Complex catalyst precursor will be coated with
The inert carrier of body is in Muffle furnace, 560 DEG C of roastings, and catalyst is obtained after natural cooling.Catalyst 480 DEG C of reaction temperature,
Air speed 5400h-1Under, checked and rated in fixed bed reactors, it is 71.6% to measure equal acid anhydride yield, and its appraisal result refers to table 1.
【Embodiment 7】
88g oxalic acid and 340ml distilled water are weighed in flask, stirring is warming up to 80 DEG C, after oxalic acid all dissolving, is made into
Oxalic acid solution.A vanadic anhydride is added in the oxalic acid solution prepared and continues to stir, obtains vanadyl oxalate ammonium salt solution.
5 parts of titanium dioxide, 0.2 part of diammonium hydrogen phosphate and 0.2 part of potassium nitrate are added in solution, continue to obtain catalyst after stirring
Presoma.After catalyst precursor filtration drying, it is fitted into flush coater, uniformly sprays on inert carrier Alpha-alumina.
The inert carrier of catalyst precursor will be coated with Muffle furnace, 560 DEG C of roastings, obtain catalyst after natural cooling.Catalysis
Agent is in 480 DEG C of reaction temperature, air speed 5400h-1Under, checked and rated in fixed bed reactors, it is 72.5% to measure equal acid anhydride yield, and it is examined
Comment the results detailed in Table 1.
The present embodiment is compared with embodiment 1~2 as can be seen that VA races P element and alkali metal K element are improving equal acid anhydride yield
With preferable synergy.
【Embodiment 8】
88g oxalic acid and 340ml distilled water are weighed in flask, stirring is warming up to 80 DEG C, after oxalic acid all dissolving, is made into
Oxalic acid solution.A vanadic anhydride is added in the oxalic acid solution prepared and continues to stir, obtains vanadyl oxalate ammonium salt solution.
5 parts of titanium dioxide, 0.1 part of diammonium hydrogen phosphate, 0.1 part of nitric acid antimony and 0.2 part of potassium nitrate are added in solution, continue to stir
After obtain catalyst precursor.After catalyst precursor filtration drying, it is fitted into flush coater, uniformly sprays in inert carrier
On Alpha-alumina.The inert carrier of catalyst precursor will be coated with Muffle furnace, 560 DEG C of roastings, obtained after natural cooling
Catalyst.Catalyst is in 480 DEG C of reaction temperature, air speed 5400h-1Under, checked and rated in fixed bed reactors, measuring equal acid anhydride yield is
73.7%, its appraisal result refers to table 1.
The present embodiment can be seen that VA races P and Sb elements and carried with the other active components of the present invention compared with Example 7
High acid anhydride yield has preferably synergy.
【Embodiment 9】
88g oxalic acid and 340ml distilled water are weighed in flask, stirring is warming up to 80 DEG C, after oxalic acid all dissolving, is made into
Oxalic acid solution.A vanadic anhydride is added in the oxalic acid solution prepared and continues to stir, obtains vanadyl oxalate ammonium salt solution.
5 parts of titanium dioxide, 0.2 part of nitric acid antimony, 0.1 part of rubidium nitrate and 0.1 part of potassium nitrate 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 in inert carrier α-oxygen
Change on aluminium.The inert carrier of catalyst precursor will be coated with Muffle furnace, 560 DEG C of roastings, be catalyzed after natural cooling
Agent.Catalyst is in 480 DEG C of reaction temperature, air speed 5400h-1Under, checked and rated in fixed bed reactors, measuring equal acid anhydride yield is
73.5%, its appraisal result refers to table 1.
The present embodiment can be seen that alkali metal Rb and K 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】
88g oxalic acid and 340ml distilled water are weighed in flask, stirring is warming up to 80 DEG C, after oxalic acid all dissolving, is made into
Oxalic acid solution.A vanadic anhydride is added in the oxalic acid solution prepared and continues to stir, obtains vanadyl oxalate ammonium salt solution.
5 parts of titanium dioxide, 0.1 part of diammonium hydrogen phosphate, 0.1 part of nitric acid antimony, 0.1 part of rubidium nitrate and 0.1 part of potassium nitrate are added in solution,
Continue to obtain catalyst precursor after stirring.After catalyst precursor filtration drying, it is fitted into flush coater, uniform spray
It is coated on inert carrier Alpha-alumina.The inert carrier of catalyst precursor will be coated with Muffle furnace, 560 DEG C of roastings, from
So catalyst is obtained after cooling.Catalyst is in 480 DEG C of reaction temperature, air speed 5400h-1Under, check and rate, survey in fixed bed reactors
It is 75.5% to obtain equal acid anhydride yield, and its appraisal result refers to table 1.
The present embodiment is compared with embodiment 8, embodiment 9 as can be seen that V, Ti, VA race P and Sb elements, alkali metal Rb and K
There is extraordinary synergy improving equal acid anhydride yield.
Table 1
Claims (10)
1. a kind of catalyst that equal acid anhydride is made for durol oxidation, it is characterised in that the catalyst uses inert carrier, living
Property component include v element, titanium elements, and at least one of VA races element and alkali metal.
2. catalyst as claimed in claim 1, it is characterised in that the VA elements are selected from least one of phosphorus, arsenic, antimony and bismuth.
3. catalyst as claimed in claim 1, it is characterised in that the alkali metal in lithium, sodium, potassium, rubidium and caesium extremely
Few one kind.
4. catalyst as claimed in claim 1, it is characterised in that the ratio of v element and Ti elements is 1 in catalyst：(1-10).
5. catalyst as claimed in claim 1, it is characterised in that v element and VA elements and alkali metal summation in catalyst
Ratio be 1：(0.01-1).
A kind of 6. preparation method for being used for durol oxidation and making equal acid anhydride catalyst described in claim 1, it is characterised in that bag
Include several steps：
(1) vanadium source is added in oxalic acid solution, obtains mixed solution；Titanium source, VA races and alkali metal compound are added
Reaction system, obtain presoma；
(2) presoma is sprayed on carrier, catalyst is obtained after roasting.
7. the preparation method of equal acid anhydride catalyst is made for durol oxidation as claimed in claim 6, it is characterised in that will urge
The presoma of agent is fitted into flush coater, is uniformly sprayed after being heated at 220-260 DEG C on carrier.
8. the preparation method of equal acid anhydride catalyst is made for durol oxidation as claimed in claim 6, it is characterised in that will spray
The carrier of catalyst precursor is scribbled in Muffle kiln roasting, sintering temperature is 500-550 DEG C of temperature, roasting time 3-5h.
A kind of 9. method for making equal acid anhydride for durol oxidation, using durol, air as raw material, using fixed bed reaction
Device, equal acid anhydride is synthesized in the presence of any one catalyst described in Claims 1 to 5.
10. according to the method for claim 9, it is characterised in that the mass concentration of durol is 30-50g/m3, it reacts
Process conditions：Air speed is 4000~6000hr-1, reaction temperature be 300~500 DEG C, reaction pressure is normal pressure.
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Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
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| 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 |
| CN110560111A (en) * | 2018-06-05 | 2019-12-13 | 中国石油化工股份有限公司 | Catalyst for synthesizing meta-anhydride from pseudocumene |
| CN110560115A (en) * | 2018-06-05 | 2019-12-13 | 中国石油化工股份有限公司 | Catalyst for synthesizing trimellitic anhydride |
| CN110560116A (en) * | 2018-06-05 | 2019-12-13 | 中国石油化工股份有限公司 | Catalyst for oxidation of pseudocumene to prepare meta-anhydride |
| CN110560110A (en) * | 2018-06-05 | 2019-12-13 | 中国石油化工股份有限公司 | Catalyst for synthesizing meta-anhydride by oxidizing meta-trimethylbenzene |
| CN110560112A (en) * | 2018-06-05 | 2019-12-13 | 中国石油化工股份有限公司 | Catalyst for preparing trimellitic anhydride |
| CN110560109A (en) * | 2018-06-05 | 2019-12-13 | 中国石油化工股份有限公司 | Catalyst for producing trimellitic anhydride |
| CN110560113A (en) * | 2018-06-05 | 2019-12-13 | 中国石油化工股份有限公司 | Catalyst for pseudocumene catalytic oxidation |
| CN110560114A (en) * | 2018-06-05 | 2019-12-13 | 中国石油化工股份有限公司 | Catalyst for improving yield of trimellitic anhydride |
| CN111097466A (en) * | 2018-10-25 | 2020-05-05 | 中国石油化工股份有限公司 | Preparation method of catalyst for preparation of pyromellitic anhydride |
| CN112536025A (en) * | 2019-09-20 | 2021-03-23 | 中国石油化工股份有限公司 | Catalyst for preparing pyromellitic anhydride by oxidizing durene and preparation method and application thereof |
| CN113877569A (en) * | 2020-07-03 | 2022-01-04 | 中国石油化工股份有限公司 | Catalyst for producing pyromellitic dianhydride and preparation method thereof |
| CN114425325A (en) * | 2020-09-28 | 2022-05-03 | 中国石油化工股份有限公司 | Catalyst for preparing pyromellitic anhydride by oxidizing durene and preparation method and application thereof |
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