CN101037439A - Production technique of benzenetetracarboxylic dianhydride by catalyzing carrier-type polyoxometalates - Google Patents
Production technique of benzenetetracarboxylic dianhydride by catalyzing carrier-type polyoxometalates Download PDFInfo
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- CN101037439A CN101037439A CN 200710055552 CN200710055552A CN101037439A CN 101037439 A CN101037439 A CN 101037439A CN 200710055552 CN200710055552 CN 200710055552 CN 200710055552 A CN200710055552 A CN 200710055552A CN 101037439 A CN101037439 A CN 101037439A
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Abstract
The invention discloses a craft for producing pyromellitic dianhydride catalyzed by a carrier-type poly-oxometalate, including melting the pyromellitic dianhydride by the groove, feeding to the mixing machine for evapouration after pre-heating with a feed concentration of 15.0-19.5g/m3, mixing with the air, entering into the fixed bed reactor for a oxidation, oxidating with an airspeed of 4500-6500 h-1, cooling the produced air, then condensing in the collector, getting coarse pyromellitic dianhydride. At 300-340 DEG C, the catalyzer is mostly poly-oxometalate which is fixed on the catalyst bed after loading. The mass ratio of the catalyzer to pyromellitic dianhydride is 0.2-1%. The invention has the durene in the C10 heavy aromatics as raw material, produces the pyromellitic dianhydride by oxidation in air, makes the C10 heavy aromatics be with a higher added value, uses the current resource and industrial equipments as more as possible, exploits the catalysis and synthesis path of the pyromellitic dianhydride. The invention has a low pollution and production cost, a wide development prospect and is suitable for commercial process.
Description
Technical field
The present invention relates to the new production technique of pyromellitic acid anhydride, a kind of technology of carrier model polyoxometallate catalytic production pyromellitic acid anhydride especially is provided, belong to Chemicals preparing technique process field.
Background technology
The pyromellitic acid anhydride that the present invention relates to is called for short equal acid anhydride (Pyromellitic Dianhydride), is a kind of important Chemicals with high added value and raw material, and its topmost purposes is the raw material as synthesis of polyimides.
The production method of pyromellitic acid anhydride is more, because the raw material difference that adopts, the operational path of selection is different; Even adopt with a kind of raw material, its production technique also has multiple.For example: adopt the dimethylbenzene chloromethylation process to make PMDA, be will between contraposition account for 98% 2, isolate dichloride methyl dimethylbenzene after 4-dimethylbenzene and formaldehyde, the concentrated hydrochloric acid reaction, under 80～85 ℃, after dichloride methyl dimethylbenzene and nitric acid carried out the atmospheric pressure oxidation salify, under 92～101 ℃, carry out oxidation with potassium permanganate again, products therefrom through acidifying, crystallization, filter Pyromellitic Acid, be incubated, dewater, be cyclized into PMDA in 210 ℃ at last.Though this method raw material is easy to get, technology is longer relatively, and is seriously polluted, and the difficulty in the industrial production is bigger.
The unsym-trimethyl benzene alkylation process is at catalyst A lCl with unsym-trimethyl benzene and propylene
3Effect under carry out alkylated reaction, generate the 5-isopropyl pseudocumene, catalytic gas phase oxidation becomes PMDA then, this method is because raw material unsym-trimethyl benzene and propylene are easy to get, but this method is not advanced with equipment because of technology, and productive expense is higher, market does not have competitive power.
Summary of the invention
The present invention discloses a kind of technology of carrier model polyoxometallate catalytic production pyromellitic acid anhydride, and it is seriously polluted to have overcome existing equal acid anhydride production technique, and the difficulty in the industrial production is bigger, the more high shortcoming of production cost.
The present invention is raw material with the durol, and polyoxometallate is a catalyzer, utilizes air oxidation process to produce pyromellitic acid anhydride.
Reaction formula is as follows:
Concrete production technique is as follows: durol through changing 190～195 ℃ of fusings of hopper, is delivered to 200～210 ℃ of vaporizations of mixing tank, input concentration 15.0-19.5g/m after the preheating
3, with air mixed, mixed gas enters the fixed-bed reactor oxidation, and under 300～340 ℃, catalyzer is to be fixed on the catalytic bed after multiple-metal oxygen-containing hydrochlorate (POM) supports, the mass ratio 2-10 ‰ of catalyzer and durol, air speed is 4500-6500h
-1Carry out oxidizing reaction, reacted gas solidifies in trap after cooling off, and obtains thick pyromellitic acid anhydride; All the acid anhydride yield is greater than 90%, and all the acid anhydride selectivity is greater than 85%, waste gas emptying after the absorption tower absorbs moisture etc.
Described multiple-metal oxygen-containing hydrochlorate (POM) has following general formula
M
3H
nAMo
12-XV
XO
40/SiO
2
Wherein, M=H, C
21H
37NH; A=As; Pn=1～3; X=1～3.
The catalyzer multiple-metal oxygen-containing hydrochlorate (POM) that the present invention relates to also claims heteropolyacid (salt) (Polyoxometalates).Just begin the seventies it is systematically studied, the multiple-metal oxygen-containing hydrochlorate especially can be used as the redox or the dual-function catalyst of excellent performance in homogeneous phase and nonhomogeneous system.Heteropolyacid is a strong acid, and the simple oxygen acid identical with the respective element that constitutes them compared acid strong.In the oxygen containing polar solvents such as the same soluble in water, pure, ether with sulfuric acid of image height chloric acid and ketone, heteropolyacid is catalyzer efficiently to a lot of reactions, particularly for redox reaction.
Adopt sol-gel technique, the multiple-metal oxygen-containing hydrochlorate that has high catalytic activity by a large amount of experimental selection is unique catalyzer, method for hydrolysis by tetraethoxy-silicane (TEOS), the multiple-metal oxygen-containing hydrochlorate is stated from the silica matrix, obtain the reaction that supported catalyst is used for the equal acid anhydride of Pyromellitic Acid oxidation method for preparing with this novel carrying method, help the recovery and the regeneration of catalyzer.
Durol per pass conversion＞90% of production technique of the present invention; Equal acid anhydride selectivity＞90%; All the acid anhydride yield is more than 80% of durol; Reaction pressure is a normal pressure.
Positively effect of the present invention is: along with the continuous development of petrochemical industry, by-product C
10The total amount of hydrocarbon resource is also very considerable, at by-product C
10In, have a large amount of durols, and its isolation technique is simpler, thereby raw materials cost declines to a great extent.Polyoxometallate is the good catalysis of a class, polyoxometallate catalyst is when avoiding equipment corrosion and reducing the pollution pollution problem in process of production, can remain on active high advantage under the relative low temperature again, special polyoxometallate supports technology can make catalyzer can more help reclaiming and regeneration.But production method continuous production of the present invention pollutes for a short time, and production cost is low, has opened up the new synthetic route of catalytic production pyromellitic acid anhydride, is suitable for suitability for industrialized production, has wide development and application prospect.
Description of drawings
Fig. 1 is a process flow sheet of the present invention.
Embodiment
Embodiment 1
Durol through changing 190 ℃ of fusings of hopper, is delivered to 200 ℃ of vaporizations of mixing tank, input concentration 17.0-17.5g/m after the preheating
3, with air mixed, mixed gas enters the fixed-bed reactor oxidation, and under 320 ℃, catalyzer is that multiple-metal oxygen-containing hydrochlorate (POM) supports and is fixed on the catalytic bed multiple-metal oxygen-containing hydrochlorate: (C
21H
37NH)
3H
3AsMo
9V
3O
40/ SiO
2With the mass ratio 5 ‰ of durol, air speed is 6500h
-1Carry out oxidizing reaction.Reacted gas solidifies in trap after cooling off, and obtains thick pyromellitic acid anhydride.
Embodiment 2
Durol through changing 193 ℃ of fusings of hopper, is delivered to 205 ℃ of vaporizations of mixing tank, input concentration 15.5g/m after the preheating
3, with air mixed, mixed gas enters the fixed-bed reactor oxidation, and under 340 ℃, catalyzer is that multiple-metal oxygen-containing hydrochlorate (POM) supports and is fixed on the catalytic bed multiple-metal oxygen-containing hydrochlorate (C
21H
37NH)
3H
2AsMo
10V
2O
40/ SiO
2With the mass ratio 8 ‰ of durol, air speed is 4500h
-1Carry out oxidizing reaction.Reacted gas solidifies in trap after cooling off, and obtains thick pyromellitic acid anhydride.
Embodiment 3
Durol through changing 195 ℃ of fusings of hopper, is delivered to 210 ℃ of vaporizations of mixing tank, input concentration 19.5g/m after the preheating
3, with air mixed, mixed gas enters the fixed-bed reactor oxidation, and under 320 ℃, catalyzer is that multiple-metal oxygen-containing hydrochlorate (POM) supports and is fixed on the catalytic bed multiple-metal oxygen-containing hydrochlorate (C
21H
17NH)
3HAsMo
11VO
40/ SiO
2With the mass ratio 6 ‰ of durol, air speed is 6500h
-1Carry out oxidizing reaction.Reacted gas solidifies in trap after cooling off, and obtains thick pyromellitic acid anhydride.
Embodiment 4
Durol through changing 195 ℃ of fusings of hopper, is delivered to 210 ℃ of vaporizations of mixing tank, input concentration 17.5g/m after the preheating
3, with air mixed, mixed gas enters the fixed-bed reactor oxidation, and under 320 ℃, catalyzer is that multiple-metal oxygen-containing hydrochlorate (POM) supports and is fixed on the catalytic bed multiple-metal oxygen-containing hydrochlorate (C
21H
37NH)
3H
3PMo
9V
3O
40/ SiO
2With the mass ratio 5 ‰ of durol, air speed is 6500h
-1Carry out oxidizing reaction.Reacted gas solidifies in trap after cooling off, and obtains thick pyromellitic acid anhydride.
Embodiment 5
Durol through changing 195 ℃ of fusings of hopper, is delivered to 210 ℃ of vaporizations of mixing tank, input concentration 17.5g/m after the preheating
3, with air mixed, mixed gas enters the fixed-bed reactor oxidation, and under 320 ℃, catalyzer is that multiple-metal oxygen-containing hydrochlorate (POM) supports and is fixed on the catalytic bed multiple-metal oxygen-containing hydrochlorate (C
21H
37NH)
3H
2PMo
10V
2O
40/ SiO
2With the mass ratio 2 ‰ of durol, air speed is 5500h
-1Carry out oxidizing reaction.Reacted gas solidifies in trap after cooling off, and obtains thick pyromellitic acid anhydride.
Embodiment 6
Durol through changing 195 ℃ of fusings of hopper, is delivered to 210 ℃ of vaporizations of mixing tank, input concentration 17.5g/m after the preheating
3, with air mixed, mixed gas enters the fixed-bed reactor oxidation, and under 320 ℃, catalyzer is that multiple-metal oxygen-containing hydrochlorate (POM) supports and is fixed on the catalytic bed multiple-metal oxygen-containing hydrochlorate (C
21H
37NH)
3HPMo
11VO
40/ SiO
2With the mass ratio 5 ‰ of durol, air speed is 6500h
-1Carry out oxidizing reaction.Reacted gas solidifies in trap after cooling off, and obtains thick pyromellitic acid anhydride.
Embodiment 7
Durol through changing 190 ℃ of fusings of hopper, is delivered to 200 ℃ of vaporizations of mixing tank, input concentration 17.0-17.5g/m after the preheating
3, with air mixed, mixed gas enters the fixed-bed reactor oxidation, and under 330 ℃, catalyzer is that multiple-metal oxygen-containing hydrochlorate (POM) supports and is fixed on the catalytic bed multiple-metal oxygen-containing hydrochlorate: H
6AsMo
9V
3O
40/ SiO
2With the mass ratio 8 ‰ of durol, air speed is 6500h
-1Carry out oxidizing reaction.Reacted gas solidifies in trap after cooling off, and obtains thick pyromellitic acid anhydride.
Embodiment 8
Durol through changing 193 ℃ of fusings of hopper, is delivered to 205 ℃ of vaporizations of mixing tank, input concentration 17.5g/m after the preheating
3, with air mixed, mixed gas enters the fixed-bed reactor oxidation, and under 335 ℃, catalyzer is that multiple-metal oxygen-containing hydrochlorate (POM) supports and is fixed on the catalytic bed multiple-metal oxygen-containing hydrochlorate H
5AsMo
10V
2O
40/ SiO
2With the mass ratio 3 ‰ of durol, air speed is 6500h
-1Carry out oxidizing reaction.Reacted gas solidifies in trap after cooling off, and obtains thick pyromellitic acid anhydride.
Embodiment 9
Durol through changing 195 ℃ of fusings of hopper, is delivered to 210 ℃ of vaporizations of mixing tank, input concentration 17.5g/m after the preheating
3, with air mixed, mixed gas enters the fixed-bed reactor oxidation, and under 330 ℃, catalyzer is that multiple-metal oxygen-containing hydrochlorate (POM) supports and is fixed on the catalytic bed multiple-metal oxygen-containing hydrochlorate H
4AsMo
11VO
40/ SiO
2With the mass ratio 5 ‰ of durol, air speed is 6500h
-1Carry out oxidizing reaction.Reacted gas solidifies in trap after cooling off, and obtains thick pyromellitic acid anhydride.
Embodiment 10
Durol through changing 195 ℃ of fusings of hopper, is delivered to 210 ℃ of vaporizations of mixing tank, input concentration 17.5g/m after the preheating
3, with air mixed, mixed gas enters the fixed-bed reactor oxidation, and under 330 ℃, catalyzer is that multiple-metal oxygen-containing hydrochlorate (POM) supports and is fixed on the catalytic bed multiple-metal oxygen-containing hydrochlorate H
3PMo
9V
3O
40/ SiO
2With the mass ratio 4 ‰ of durol, air speed is 6500h
-1Carry out oxidizing reaction.Reacted gas solidifies in trap after cooling off, and obtains thick pyromellitic acid anhydride.
Embodiment 11
Durol through changing 195 ℃ of fusings of hopper, is delivered to 210 ℃ of vaporizations of mixing tank, input concentration 17.5g/m after the preheating
3, with air mixed, mixed gas enters the fixed-bed reactor oxidation, and under 340 ℃, catalyzer is that multiple-metal oxygen-containing hydrochlorate (POM) supports and is fixed on the catalytic bed multiple-metal oxygen-containing hydrochlorate H
5PMo
10V
2O
40/ SiO
2With the mass ratio 5 ‰ of durol, air speed is that 6500h-1 carries out oxidizing reaction.Reacted gas solidifies in trap after cooling off, and obtains thick pyromellitic acid anhydride.
Embodiment 12
Durol through changing 195 ℃ of fusings of hopper, is delivered to 210 ℃ of vaporizations of mixing tank, input concentration 17.5g/m after the preheating
3, with air mixed, mixed gas enters the fixed-bed reactor oxidation, and under 330 ℃, catalyzer is that multiple-metal oxygen-containing hydrochlorate (POM) supports and is fixed on the catalytic bed multiple-metal oxygen-containing hydrochlorate H
4PMo
11VO
40/ SiO
2With the mass ratio 5 ‰ of durol, air speed is 6500h
-1Carry out oxidizing reaction.Reacted gas solidifies in trap after cooling off, and obtains thick pyromellitic acid anhydride.
Embodiment 13
Durol through changing 190 ℃ of fusings of hopper, is delivered to 200 ℃ of vaporizations of mixing tank, input concentration 17.0-17.5g/m after the preheating
3, with air mixed, mixed gas enters the fixed-bed reactor oxidation, and under 320 ℃, catalyzer is that multiple-metal oxygen-containing hydrochlorate (POM) supports and is fixed on the catalytic bed multiple-metal oxygen-containing hydrochlorate: (C
21H
37NH)
3H
3AsMo
9V
3O
40/ SiO
2With the mass ratio 10 ‰ of durol, air speed is 5500h
-1Carry out oxidizing reaction.Reacted gas solidifies in trap after cooling off, and obtains thick pyromellitic acid anhydride.
Embodiment 14
Durol through changing 193 ℃ of fusings of hopper, is delivered to 205 ℃ of vaporizations of mixing tank, input concentration 17.5g/m after the preheating
3, with air mixed, mixed gas enters the fixed-bed reactor oxidation, and under 300 ℃, catalyzer is that multiple-metal oxygen-containing hydrochlorate (POM) supports and is fixed on the catalytic bed multiple-metal oxygen-containing hydrochlorate (C
21H
37NH)
3H
2AsMo
10V
2O
40/ SiO
2With the mass ratio 5 ‰ of durol, air speed is 5500h
-1Carry out oxidizing reaction.Reacted gas solidifies in trap after cooling off, and obtains thick pyromellitic acid anhydride.
Embodiment 15
Durol through changing 195 ℃ of fusings of hopper, is delivered to 210 ℃ of vaporizations of mixing tank, input concentration 17.5g/m after the preheating
3, with air mixed, mixed gas enters the fixed-bed reactor oxidation, and under 320 ℃, catalyzer is that multiple-metal oxygen-containing hydrochlorate (POM) supports and is fixed on the catalytic bed multiple-metal oxygen-containing hydrochlorate (C
21H
37NH)
3HAsMo
11VO
40/ SiO
2With the mass ratio 5 ‰ of durol, air speed is 5500h
-1Carry out oxidizing reaction.Reacted gas solidifies in trap after cooling off, and obtains thick pyromellitic acid anhydride.
Embodiment 16
Durol through changing 195 ℃ of fusings of hopper, is delivered to 210 ℃ of vaporizations of mixing tank, input concentration 17.5g/m after the preheating
3, with air mixed, mixed gas enters the fixed-bed reactor oxidation, and under 320 ℃, catalyzer is that multiple-metal oxygen-containing hydrochlorate (POM) supports and is fixed on the catalytic bed multiple-metal oxygen-containing hydrochlorate (C
21H
37NH)
3H
3PMo
9V
3O
40/ SiO
2With the mass ratio 8 ‰ of durol, air speed is 5500h
-1Carry out oxidizing reaction.Reacted gas solidifies in trap after cooling off, and obtains thick pyromellitic acid anhydride.
Embodiment 17
Durol through changing 195 ℃ of fusings of hopper, is delivered to 210 ℃ of vaporizations of mixing tank, input concentration 17.5g/m after the preheating
3, with air mixed, mixed gas enters the fixed-bed reactor oxidation, and under 300 ℃, catalyzer is that multiple-metal oxygen-containing hydrochlorate (POM) supports and is fixed on the catalytic bed multiple-metal oxygen-containing hydrochlorate (C
21H
37NH)
3H
2PMo
10V
2O
40/ SiO
2With the mass ratio 5 ‰ of durol, air speed is 5500h
-1Carry out oxidizing reaction.Reacted gas solidifies in trap after cooling off, and obtains thick pyromellitic acid anhydride.
Embodiment 18
Durol through changing 195 ℃ of fusings of hopper, is delivered to 210 ℃ of vaporizations of mixing tank, input concentration 17.5g/m after the preheating
3, with air mixed, mixed gas enters the fixed-bed reactor oxidation, and under 320 ℃, catalyzer is that multiple-metal oxygen-containing hydrochlorate (POM) supports and is fixed on the catalytic bed multiple-metal oxygen-containing hydrochlorate (C
21H
37NH)
3HPMo
11VO
40/ SiO
2With the mass ratio 8 ‰ of durol, air speed is 5500h
-1Carry out oxidizing reaction.Reacted gas solidifies in trap after cooling off, and obtains thick pyromellitic acid anhydride.
Embodiment 19
Durol through changing 190 ℃ of fusings of hopper, is delivered to 200 ℃ of vaporizations of mixing tank, input concentration 17.0-17.5g/m after the preheating
3, with air mixed, mixed gas enters the fixed-bed reactor oxidation, and under 330 ℃, catalyzer is that multiple-metal oxygen-containing hydrochlorate (POM) supports and is fixed on the catalytic bed multiple-metal oxygen-containing hydrochlorate: H
6AsMo
9V
3O
40/ SiO
2With the mass ratio 5 ‰ of durol, air speed is 5000h
-1Carry out oxidizing reaction.Reacted gas solidifies in trap after cooling off, and obtains thick pyromellitic acid anhydride.
Embodiment 20
Durol through changing 193 ℃ of fusings of hopper, is delivered to 205 ℃ of vaporizations of mixing tank, input concentration 17.5g/m after the preheating
3, with air mixed, mixed gas enters the fixed-bed reactor oxidation, and under 335 ℃, catalyzer is that multiple-metal oxygen-containing hydrochlorate (POM) supports and is fixed on the catalytic bed multiple-metal oxygen-containing hydrochlorate H
5AsMo
10V
2O
40/ SiO
2With the mass ratio 5 ‰ of durol, air speed is 5500h
-1Carry out oxidizing reaction.Reacted gas solidifies in trap after cooling off, and obtains thick pyromellitic acid anhydride.
Embodiment 21
Durol through changing 195 ℃ of fusings of hopper, is delivered to 210 ℃ of vaporizations of mixing tank, input concentration 17.5g/m after the preheating
3, with air mixed, mixed gas enters the fixed-bed reactor oxidation, and under 330 ℃, catalyzer is that multiple-metal oxygen-containing hydrochlorate (POM) supports and is fixed on the catalytic bed multiple-metal oxygen-containing hydrochlorate H
4AsMo
11VO
40/ SiO
2With the mass ratio 5 ‰ of durol, air speed is 5500h
-1Carry out oxidizing reaction.Reacted gas solidifies in trap after cooling off, and obtains thick pyromellitic acid anhydride.
Embodiment 22
Durol through changing 195 ℃ of fusings of hopper, is delivered to 210 ℃ of vaporizations of mixing tank, input concentration 17.5g/m after the preheating
3, with air mixed, mixed gas enters the fixed-bed reactor oxidation, and under 330 ℃, catalyzer is that multiple-metal oxygen-containing hydrochlorate (POM) supports and is fixed on the catalytic bed multiple-metal oxygen-containing hydrochlorate H
3PMo
9V
3O
40/ SiO
2With the mass ratio 5 ‰ of durol, air speed is that 6500h-1 carries out oxidizing reaction.Reacted gas solidifies in trap after cooling off, and obtains thick pyromellitic acid anhydride.
Embodiment 23
Durol through changing 195 ℃ of fusings of hopper, is delivered to 210 ℃ of vaporizations of mixing tank, input concentration 17.5g/m after the preheating
3, with air mixed, mixed gas enters the fixed-bed reactor oxidation, and under 330 ℃, catalyzer is that multiple-metal oxygen-containing hydrochlorate (POM) supports and is fixed on the catalytic bed multiple-metal oxygen-containing hydrochlorate H
5PMo
10V
2O
40/ SiO
2With the mass ratio 5 ‰ of durol, air speed is 5500h
-1Carry out oxidizing reaction.Reacted gas solidifies in trap after cooling off, and obtains thick pyromellitic acid anhydride.
Embodiment 24
Durol through changing 195 ℃ of fusings of hopper, is delivered to 210 ℃ of vaporizations of mixing tank, input concentration 17.5g/m after the preheating
3, with air mixed, mixed gas enters the fixed-bed reactor oxidation, and under 330 ℃, catalyzer is that multiple-metal oxygen-containing hydrochlorate (POM) supports and is fixed on the catalytic bed multiple-metal oxygen-containing hydrochlorate H
4PMo
11VO
40/ SiO
2With the mass ratio 5 ‰ of durol, air speed is 4500h
-1Carry out oxidizing reaction.Reacted gas solidifies in trap after cooling off, and obtains thick pyromellitic acid anhydride.
Claims (2)
1, a kind of technology of carrier model polyoxometallate catalytic production pyromellitic acid anhydride may further comprise the steps: durol through changing 190～195 ℃ of fusings of hopper, is delivered to 200～210 ℃ of vaporizations of mixing tank, input concentration 15.0-19.5g/m after the preheating
3, with air mixed, mixed gas enters the fixed-bed reactor oxidation, and under 300～340 ℃, catalyzer is fixed on the catalytic bed after supporting for the multiple-metal oxygen-containing hydrochlorate, the mass ratio 2-10 ‰ of catalyzer and durol, air speed is 4500-6500h
-1Carry out oxidizing reaction, reacted gas solidifies in trap after cooling off, and obtains thick pyromellitic acid anhydride; All the acid anhydride yield is greater than 90%, and all the acid anhydride selectivity is greater than 85%, waste gas emptying after the absorption tower absorbs moisture.
2, production technique according to claim 1 is characterized in that: described multiple-metal oxygen-containing hydrochlorate has following general formula
M
3H
nAMo
12-XV
XO
40/SiO
2
Wherein, M=H, C
21H
37NH; A=As; Pn=1～3; X=1～3.
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| CN101266021B (en) * | 2008-04-29 | 2012-01-11 | 常熟市联邦化工有限公司 | Liquid durene conveying and metering mechanism |
| CN102773119A (en) * | 2012-07-10 | 2012-11-14 | 东北师范大学 | Tantalum-tungsten mixed polyoxometallate photocatalyst for generating hydrogen activity and preparation method thereof |
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| CN107629066A (en) * | 2017-10-27 | 2018-01-26 | 济南隆凯能源科技有限公司 | The production system and production method for the pyromellitic acid anhydride that a kind of process tail gas recycles |
| CN107866257A (en) * | 2016-09-23 | 2018-04-03 | 中国石油化工股份有限公司 | The catalyst of equal acid anhydride is prepared for durol |
| CN108329327A (en) * | 2018-04-17 | 2018-07-27 | 连云港鹏辰特种新材料有限公司 | A kind of method of purification of the thick pyromellitic acid anhydride based on crystallization distillation |
| CN110746435A (en) * | 2019-10-31 | 2020-02-04 | 曹正国 | Method for producing pyromellitic dianhydride by low-temperature liquid-phase continuous oxidation of durene |
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|---|---|---|---|---|
| CN101266021B (en) * | 2008-04-29 | 2012-01-11 | 常熟市联邦化工有限公司 | Liquid durene conveying and metering mechanism |
| CN102773119A (en) * | 2012-07-10 | 2012-11-14 | 东北师范大学 | Tantalum-tungsten mixed polyoxometallate photocatalyst for generating hydrogen activity and preparation method thereof |
| CN104230835A (en) * | 2014-09-01 | 2014-12-24 | 福建师范大学 | Method for synthesizing N-styryl oxazolidine-2-ketone derivative |
| CN107866257A (en) * | 2016-09-23 | 2018-04-03 | 中国石油化工股份有限公司 | The catalyst of equal acid anhydride is prepared for durol |
| CN107866257B (en) * | 2016-09-23 | 2020-01-03 | 中国石油化工股份有限公司 | Catalyst for preparing pyromellitic anhydride from durene |
| CN107629066A (en) * | 2017-10-27 | 2018-01-26 | 济南隆凯能源科技有限公司 | The production system and production method for the pyromellitic acid anhydride that a kind of process tail gas recycles |
| CN108329327A (en) * | 2018-04-17 | 2018-07-27 | 连云港鹏辰特种新材料有限公司 | A kind of method of purification of the thick pyromellitic acid anhydride based on crystallization distillation |
| CN110746435A (en) * | 2019-10-31 | 2020-02-04 | 曹正国 | Method for producing pyromellitic dianhydride by low-temperature liquid-phase continuous oxidation of durene |
| CN110746435B (en) * | 2019-10-31 | 2022-04-29 | 曹正国 | Method for producing pyromellitic dianhydride by low-temperature liquid-phase continuous oxidation of durene |
| CN111675593A (en) * | 2020-06-24 | 2020-09-18 | 中海油天津化工研究设计院有限公司 | C9Method for synthesizing sym-tetraalkylbenzene from mixed aromatic hydrocarbon |
| CN111675593B (en) * | 2020-06-24 | 2023-04-18 | 中海油天津化工研究设计院有限公司 | C 9 Method for synthesizing sym-tetraalkylbenzene from mixed aromatic hydrocarbon |
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