CN107866252A - The catalyst of equal acid anhydride is synthesized for durol - Google Patents
The catalyst of equal acid anhydride is synthesized for durol Download PDFInfo
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- CN107866252A CN107866252A CN201610846336.9A CN201610846336A CN107866252A CN 107866252 A CN107866252 A CN 107866252A CN 201610846336 A CN201610846336 A CN 201610846336A CN 107866252 A CN107866252 A CN 107866252A
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- acid anhydride
- durol
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- equal
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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
- B01J27/20—Carbon compounds
- B01J27/22—Carbides
- B01J27/224—Silicon carbide
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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 synthesized for durol, mainly solves in the prior art the problem of equal anhydride reactant of durol 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 the technical scheme of at least one of v element, nonmetalloid and VA races element and III B races element, the technical problem is preferably resolved, 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 that equal acid anhydride is synthesized for durol and preparation method thereof, and the synthesis of acid anhydride
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.
US 4665200 discloses a kind of many body system catalyst, and active component includes V, Ti, P, Nb and Sb element, and such is urged
Agent has the longer life-span.CN 102008971 reports one kind using V-Ti as major catalyst, and alkali metal is co-catalyst
Catalyst system and catalyzing, good catalytic effect can also be obtained.JP 45-15252 disclose a kind of V-Ti-Na catalyst, are received in equal acid anhydride
There is certain progress in rate.The above method is made in durol oxidation and had made great progress in the preparation of equal acid anhydride catalyst, but still
The problem of equal acid anhydride yield is relatively low so be present.
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
Durol synthesizes the catalyst of equal acid anhydride, 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 durol synthesizes equal acid anhydride.
To solve one of above-mentioned technical problem, technical scheme disclosed in this invention is：One kind is used for durol and synthesized
The catalyst of equal acid anhydride, it is characterised in that the catalyst uses α-Al2O3, carborundum, ceramic ring or its mixture be carrier, activity
Component includes v element, nonmetalloid, and at least one of VA races element and III B races element.It is preferred that the active component
Simultaneously including v element, nonmetallic series elements, at least one element selected from VA races element and in III B races element at least
A kind of element.Now there is synergy between VA 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 and Te.More preferably B and Si.
In above-mentioned technical proposal, VA races element is selected from least one of P, Sb, Bi.
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, VA races element and III B races element；Such as the active constituent includes V, Si, P and Sc, either V, B, Bi, Sc and Y or
V, Si, P, Bi, Sc and Y, or V, B, Si, P, Bi, 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 VA 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 being used for durol and synthesizing equal acid anhydride catalyst, it includes several steps：
(1) vanadium source is added in oxalic acid solution, obtains mixed solution；By nonmetalloid, VA races element and III B races member
Plain 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 VA races element is preferred
From at least one of phosphoric acid, ammonium dihydrogen phosphate, diammonium hydrogen phosphate, bismuth nitrate, bismuth sulfate, halogenation bismuth, bismuth acetate.Step (1)
The compound of the III B races element preferably is selected from least one of scandium oxide, scandium halide, 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 190-260 DEG C heat after uniformly spray on carrier.
In above-mentioned technical proposal, the described preparation method for being used for durol and synthesizing equal acid anhydride catalyst, it is characterised in that
The carrier of catalyst precursor will be coated with Muffle kiln roasting, sintering temperature is 480-580 DEG C of temperature, roasting time 1-
10h。
To solve the three of above-mentioned technical problem, technical scheme is as follows：The method that durol synthesizes 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 25-60g/m3, it reacts work
Skill condition：Air speed is 4000~6500hr-1, reaction temperature be 200~600 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 VA 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 78.6% prepared by the present invention
In catalyst active component simultaneously including v element, nonmetalloid, selected from least one of VA 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】
85g oxalic acid and 320ml distilled water are weighed in flask, stirring is warming up to 88 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 8
Part boric acid, 0.4 part of bismuth nitrate are added in solution, continue to obtain catalyst precursor after stirring.By catalyst precursor mistake
Be filtered dry it is dry after, be fitted into flush coater, uniformly spray on inert carrier carborundum.The inertia of catalyst precursor will be coated with
Carrier is in Muffle furnace, 520 DEG C of roastings, and catalyst is obtained after natural cooling.Catalyst is in 480 DEG C of reaction temperature, air speed
5300h-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 2】
85g oxalic acid and 320ml distilled water are weighed in flask, stirring is warming up to 88 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 8
Part boric acid, 0.4 part of scandium sulfate are added in solution, continue to obtain catalyst precursor after stirring.By catalyst precursor mistake
Be filtered dry it is dry after, be fitted into flush coater, uniformly spray on inert carrier carborundum.The inertia of catalyst precursor will be coated with
Carrier is in Muffle furnace, 520 DEG C of roastings, and catalyst is obtained after natural cooling.Catalyst is in 480 DEG C of reaction temperature, air speed
5300h-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.
【Comparative example 1】
85g oxalic acid and 320ml distilled water are weighed in flask, stirring is warming up to 88 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 8
Part boric acid is added in solution, continues to obtain catalyst precursor after stirring.After catalyst precursor filtration drying, load
In flush coater, uniformly spray on inert carrier carborundum.The inert carrier of catalyst precursor will be coated with Muffle furnace
In, 520 DEG C are calcined, and catalyst is obtained after natural cooling.Catalyst is in 480 DEG C of reaction temperature, air speed 5300h-1Under, in fixed bed
Checked and rated in reactor, it is 74.7% 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, B and Bi activity
Component while catalyst performance ratio containing V, B and Bi active component is more excellent containing only V, B activity component catalyst performance,
The yield of acid anhydride is higher.
【Embodiment 3】
85g oxalic acid and 320ml distilled water are weighed in flask, stirring is warming up to 88 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.
8 parts of trichlorosilanes, 0.4 part of ammonium dihydrogen 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 carborundum.Before catalyst being coated with
The inert carrier of body is driven in Muffle furnace, 520 DEG C are calcined, and catalyst is obtained after natural cooling.Catalyst is in reaction temperature 480
DEG C, air speed 5300h-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】
85g oxalic acid and 320ml distilled water are weighed in flask, stirring is warming up to 88 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.
8 parts of boric acid, 0.4 part of diammonium hydrogen phosphate 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, 520 DEG C of roastings, obtain catalyst after natural cooling.Catalyst is in 480 DEG C of reaction temperature, sky
Fast 5300h-1Under, checked and rated in fixed bed reactors, it is 74.8% to measure equal acid anhydride yield, and its appraisal result refers to table 1.
【Embodiment 5】
85g oxalic acid and 320ml distilled water are weighed in flask, stirring is warming up to 88 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 8
Part trichlorosilane, 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, 520 DEG C of roastings, and catalyst is obtained after natural cooling.Catalyst is in 480 DEG C of reaction temperature, air speed
5300h-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】
85g oxalic acid and 320ml distilled water are weighed in flask, stirring is warming up to 88 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.
8 parts of boric acid, 0.4 part of scandium sulfate are added 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 carborundum.The lazy of catalyst precursor will be coated with
Property carrier in Muffle furnace, 520 DEG C of roastings, obtain catalyst after natural cooling.Catalyst is in 480 DEG C of reaction temperature, air speed
5300h-1Under, checked and rated in fixed bed reactors, it is 74.9% to measure equal acid anhydride yield, and its appraisal result refers to table 1.
【Embodiment 7】
85g oxalic acid and 320ml distilled water are weighed in flask, stirring is warming up to 88 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 8
Part boric acid, 0.2 part of bismuth nitrate and 0.2 part of scandium sulfate are added in solution, continue to obtain catalyst precursor after stirring.It will urge
After agent presoma filtration drying, it is fitted into flush coater, uniformly sprays on inert carrier carborundum.Catalyst will be coated with
The inert carrier of presoma is in Muffle furnace, 520 DEG C of roastings, and catalyst is obtained after natural cooling.Catalyst is in reaction temperature 480
DEG C, air speed 5300h-1Under, checked and rated in fixed bed reactors, it is 75.8% to measure equal acid anhydride yield, and its appraisal result refers to table 1.
The present embodiment is compared with embodiment 1~2 as can be seen that VA races Bi elements and III B races Sc elements are improving equal acid anhydride receipts
Rate has preferably synergy.
【Embodiment 8】
85g oxalic acid and 320ml distilled water are weighed in flask, stirring is warming up to 88 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 8
Part boric acid, 0.1 part of bismuth nitrate, 0.1 part of dihydrogen sulfate ammonium and 0.2 part of scandium sulfate are added in solution, continue to obtain after stirring
Catalyst precursor.After catalyst precursor filtration drying, it is fitted into flush coater, uniformly sprays in inert carrier carborundum
On.The inert carrier of catalyst precursor will be coated with Muffle furnace, 520 DEG C of roastings, obtain catalyst after natural cooling.Urge
Agent is in 480 DEG C of reaction temperature, air speed 5300h-1Under, checked and rated in fixed bed reactors, it is 76.1% to measure equal acid anhydride yield, its
Appraisal result refers to table 1.
The present embodiment can be seen that VA races Bi elements and P element and the other active components of the present invention compared with Example 7
There is preferably synergy improving equal acid anhydride yield.
【Embodiment 9】
85g oxalic acid and 320ml distilled water are weighed in flask, stirring is warming up to 88 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 8
Part boric acid, 0.2 part of bismuth nitrate, 0.1 part of scandium sulfate and 0.1 part of yttrium chloride are added in solution, continue to be catalyzed after stirring
Agent presoma.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, 520 DEG C of roastings, obtain catalyst after natural cooling.Catalysis
Agent is in 480 DEG C of reaction temperature, air speed 5300h-1Under, checked and rated in fixed bed reactors, it is 76.9% to measure equal acid anhydride yield, and it is examined
Comment the results detailed in 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】
85g oxalic acid and 320ml distilled water are weighed in flask, stirring is warming up to 88 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 8
Part boric acid, 0.1 part of bismuth nitrate, 0.1 part of dihydrogen sulfate ammonium, 0.1 part of scandium sulfate and 0.1 part of yttrium chloride are added in solution, continue to stir
Catalyst precursor is obtained after mixing uniformly.After catalyst precursor filtration drying, it is fitted into flush coater, uniformly sprays lazy
On property carrier carborundum.The inert carrier of catalyst precursor will be coated with Muffle furnace, 520 DEG C of roastings, after natural cooling
Obtain catalyst.Catalyst is in 480 DEG C of reaction temperature, air speed 5300h-1Under, checked and rated in fixed bed reactors, measure equal acid anhydride and receive
Rate is 77.8%, 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 B element, VA races Bi and P element and III
B races Sc and Y element have extraordinary synergy in the equal acid anhydride yield of raising.
【Embodiment 11】
85g oxalic acid and 320ml distilled water are weighed in flask, stirring is warming up to 88 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 8
Part boric acid, 0.1 part of bismuth nitrate, 0.1 part of dihydrogen sulfate ammonium, 0.1 part of scandium sulfate and 0.1 part of yttrium chloride are added in solution, continue to stir
Catalyst precursor is obtained after mixing uniformly.After catalyst precursor filtration drying, it is fitted into flush coater, uniformly sprays lazy
On property carrier carborundum.The inert carrier of catalyst precursor will be coated with Muffle furnace, 520 DEG C of roastings, after natural cooling
Obtain catalyst.Catalyst is in 480 DEG C of reaction temperature, air speed 5300h-1Under, checked and rated in fixed bed reactors, measure equal acid anhydride and receive
Rate is 78.6%, and its appraisal result refers to table 1.
The present embodiment can be seen that V, nonmetallic B, Si element, VA races Bi and P element and III B races compared with Example 10
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 VA races element and III B races member
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 VA races element is selected from least one of P, Sb, Bi.
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 VA races element and III B races element summation in catalyst
Ratio be 1：(0.01-1).
A kind of 7. preparation method for being used for durol and synthesizing 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, VA 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 synthesizing 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 190-260 DEG C on carrier.
9. the preparation method of equal acid anhydride catalyst is synthesized 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 480-580 DEG C of temperature, roasting time 1-10h.
10. a kind of method that equal acid anhydride is synthesized for durol, using durol, air as raw material, using fixed bed reactors,
The mass concentration of durol is 25-60g/m3, its reaction process condition：Air speed is 4000~6500hr-1, reaction temperature be
200~600 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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| CN201610846336.9A CN107866252B (en) | 2016-09-23 | 2016-09-23 | Catalyst for synthesizing pyromellitic anhydride from durene |
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| CN201610846336.9A CN107866252B (en) | 2016-09-23 | 2016-09-23 | Catalyst for synthesizing pyromellitic anhydride from durene |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| 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 |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1232033A (en) * | 1998-03-17 | 1999-10-20 | 株式会社日本触媒 | Production process for pyromellitic dianhydride |
-
2016
- 2016-09-23 CN CN201610846336.9A patent/CN107866252B/en active Active
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1232033A (en) * | 1998-03-17 | 1999-10-20 | 株式会社日本触媒 | Production process for pyromellitic dianhydride |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| 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 |
| 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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