CN108404988A - A kind of catalyst and preparation method thereof of pyromellitic acid anhydride and Pyromellitic Acid - Google Patents
A kind of catalyst and preparation method thereof of pyromellitic acid anhydride and Pyromellitic Acid Download PDFInfo
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- CN108404988A CN108404988A CN201810370897.5A CN201810370897A CN108404988A CN 108404988 A CN108404988 A CN 108404988A CN 201810370897 A CN201810370897 A CN 201810370897A CN 108404988 A CN108404988 A CN 108404988A
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- catalyst
- pyromellitic acid
- titanium
- imitative
- durol
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- 239000003054 catalyst Substances 0.000 title claims abstract description 67
- CYIDZMCFTVVTJO-UHFFFAOYSA-N pyromellitic acid Chemical compound OC(=O)C1=CC(C(O)=O)=C(C(O)=O)C=C1C(O)=O CYIDZMCFTVVTJO-UHFFFAOYSA-N 0.000 title claims abstract description 44
- ANSXAPJVJOKRDJ-UHFFFAOYSA-N furo[3,4-f][2]benzofuran-1,3,5,7-tetrone Chemical compound C1=C2C(=O)OC(=O)C2=CC2=C1C(=O)OC2=O ANSXAPJVJOKRDJ-UHFFFAOYSA-N 0.000 title claims abstract description 31
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- 241000283966 Pholidota <mammal> Species 0.000 claims abstract description 61
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims abstract description 48
- GFNGCDBZVSLSFT-UHFFFAOYSA-N titanium vanadium Chemical compound [Ti].[V] GFNGCDBZVSLSFT-UHFFFAOYSA-N 0.000 claims abstract description 44
- 230000003647 oxidation Effects 0.000 claims abstract description 28
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 28
- SQNZJJAZBFDUTD-UHFFFAOYSA-N durene Chemical compound CC1=CC(C)=C(C)C=C1C SQNZJJAZBFDUTD-UHFFFAOYSA-N 0.000 claims abstract description 27
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 25
- 239000010936 titanium Substances 0.000 claims abstract description 25
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 25
- 229910052720 vanadium Inorganic materials 0.000 claims abstract description 25
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims abstract description 25
- 239000002243 precursor Substances 0.000 claims abstract description 23
- 239000004530 micro-emulsion Substances 0.000 claims abstract description 22
- 229920000642 polymer Polymers 0.000 claims abstract description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 19
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 claims abstract description 18
- 235000006408 oxalic acid Nutrition 0.000 claims abstract description 16
- 239000008367 deionised water Substances 0.000 claims abstract description 11
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 11
- 238000002156 mixing Methods 0.000 claims abstract description 9
- YONPGGFAJWQGJC-UHFFFAOYSA-K titanium(iii) chloride Chemical compound Cl[Ti](Cl)Cl YONPGGFAJWQGJC-UHFFFAOYSA-K 0.000 claims abstract description 9
- 238000009777 vacuum freeze-drying Methods 0.000 claims abstract description 8
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 34
- 239000000463 material Substances 0.000 claims description 26
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 20
- 239000000126 substance Substances 0.000 claims description 15
- 238000012545 processing Methods 0.000 claims description 13
- DCAYPVUWAIABOU-UHFFFAOYSA-N hexadecane Chemical compound CCCCCCCCCCCCCCCC DCAYPVUWAIABOU-UHFFFAOYSA-N 0.000 claims description 12
- 229940051841 polyoxyethylene ether Drugs 0.000 claims description 10
- 229920000056 polyoxyethylene ether Polymers 0.000 claims description 10
- LCKIEQZJEYYRIY-UHFFFAOYSA-N Titanium ion Chemical compound [Ti+4] LCKIEQZJEYYRIY-UHFFFAOYSA-N 0.000 claims description 9
- 238000005530 etching Methods 0.000 claims description 9
- 125000001421 myristyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 9
- 229920002401 polyacrylamide Polymers 0.000 claims description 8
- 150000000000 tetracarboxylic acids Chemical class 0.000 claims description 8
- 229910001456 vanadium ion Inorganic materials 0.000 claims description 8
- -1 Tetracarboxylic acid dianhydride Chemical class 0.000 claims description 2
- 238000007667 floating Methods 0.000 claims description 2
- 239000002736 nonionic surfactant Substances 0.000 claims description 2
- GCAIEATUVJFSMC-UHFFFAOYSA-N benzene-1,2,3,4-tetracarboxylic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C(C(O)=O)=C1C(O)=O GCAIEATUVJFSMC-UHFFFAOYSA-N 0.000 claims 2
- 150000001412 amines Chemical class 0.000 claims 1
- 230000003197 catalytic effect Effects 0.000 abstract description 15
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 11
- 239000010949 copper Substances 0.000 description 8
- 229910052802 copper Inorganic materials 0.000 description 8
- 239000002994 raw material Substances 0.000 description 7
- 239000002253 acid Substances 0.000 description 6
- 238000001816 cooling Methods 0.000 description 6
- 238000002425 crystallisation Methods 0.000 description 6
- 230000007062 hydrolysis Effects 0.000 description 6
- 238000006460 hydrolysis reaction Methods 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 244000025254 Cannabis sativa Species 0.000 description 4
- DCAYPVUWAIABOU-NJFSPNSNSA-N hexadecane Chemical group CCCCCCCCCCCCCCC[14CH3] DCAYPVUWAIABOU-NJFSPNSNSA-N 0.000 description 4
- 239000004094 surface-active agent Substances 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- 238000000498 ball milling Methods 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 235000001968 nicotinic acid Nutrition 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 241000254173 Coleoptera Species 0.000 description 1
- 241000790917 Dioxys <bee> Species 0.000 description 1
- 229910001051 Magnalium Inorganic materials 0.000 description 1
- 229910003978 SiClx Inorganic materials 0.000 description 1
- 238000003723 Smelting Methods 0.000 description 1
- 229910020994 Sn-Zn Inorganic materials 0.000 description 1
- 229910009069 Sn—Zn Inorganic materials 0.000 description 1
- 229910000635 Spelter Inorganic materials 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 230000003044 adaptive effect Effects 0.000 description 1
- 239000000443 aerosol Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 239000003610 charcoal Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- LIKFHECYJZWXFJ-UHFFFAOYSA-N dimethyldichlorosilane Chemical compound C[Si](C)(Cl)Cl LIKFHECYJZWXFJ-UHFFFAOYSA-N 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 230000006870 function Effects 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 239000003863 metallic catalyst Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000010257 thawing Methods 0.000 description 1
- 239000011573 trace mineral Substances 0.000 description 1
- 235000013619 trace mineral Nutrition 0.000 description 1
- 238000009692 water atomization Methods 0.000 description 1
Classifications
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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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/22—Organic complexes
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/34—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation
- B01J37/341—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation
- B01J37/344—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation of electromagnetic wave energy
- B01J37/346—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation of electromagnetic wave energy of microwave energy
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/16—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation
- C07C51/21—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen
- C07C51/255—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of compounds containing six-membered aromatic rings without ring-splitting
- C07C51/265—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of compounds containing six-membered aromatic rings without ring-splitting having alkyl side chains which are oxidised to carboxyl groups
-
- 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
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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
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/70—Oxidation reactions, e.g. epoxidation, (di)hydroxylation, dehydrogenation and analogues
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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
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
- B01J2523/50—Constitutive chemical elements of heterogeneous catalysts of Group V (VA or VB) of the Periodic Table
- B01J2523/55—Vanadium
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- Chemical & Material Sciences (AREA)
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- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Physics & Mathematics (AREA)
- Materials Engineering (AREA)
- Electromagnetism (AREA)
- Inorganic Chemistry (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Optics & Photonics (AREA)
- Health & Medical Sciences (AREA)
- Plasma & Fusion (AREA)
- Toxicology (AREA)
- Catalysts (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Heterocyclic Carbon Compounds Containing A Hetero Ring Having Oxygen Or Sulfur (AREA)
Abstract
The present invention provides a kind of catalyst and preparation method thereof of pyromellitic acid anhydride and Pyromellitic Acid, and preparation process is：Oxalic acid is add to deionized water dissolving, ammonium metavanadate mixing is added, titanium trichloride solution is added, high-speed stirred forms the precursor solution of the titanium containing vanadium；Polymer solution will be added in the precursor solution of the titanium containing vanadium, the microemulsion of stable suspersion is formed after high-speed stirred, microemulsion is poured into the reeded fan-shaped flake mold of tool of imitative pangolin scales, after low temperature quick freeze, vacuum freeze drying, it takes out, then is handled through surface micro etch, the porous vanadium titanium catalyst of imitative pangolin scales structure is prepared.The sector structure with microcosmic and macroscopical groove of porous vanadium titanium catalyst prepared by the present invention with imitative pangolin scales, pyromellitic acid anhydride and Pyromellitic Acid are prepared for durol gas phase oxidation, large specific surface area, catalytic activity is big, excellent catalytic effect.
Description
Technical field
The invention belongs to chemical solvent catalyst material technical fields, and in particular to a kind of pyromellitic acid anhydride and equal benzene
Catalyst of tetracarboxylic acid and preparation method thereof.
Background technology
Many biologies have exquisite incomparable microstructure in nature, if diatom is a kind of unicellular organism, have dioxy
The rich and varied porous shell structure of SiClx composition, in the scale structure of butterfly, thickness is only 1mm, is much smaller than artificial broadband light
The necessary thickness for learning reflector is typically larger than 50mm, and the scale structure of beetle has for selection characteristic, and people are in research material
During material and its structure design, the adaptive structure and performance of nature biotechnology system give people and much enlighten.
The scale of pangolin has special high-strength and wear-resisting performance, can play important protective action, and have
There are certain resilience and the de- soil of visbreaking, therefore be commonly used for preparing wear-resisting anti-sticking macromolecule bionics function materials, but with science skill
The rapid development of art, research find that the scale surface of pangolin has microcosmic stratiform scale structure, stacking, squama are formed between scale
Also contain the various trace elements such as magnalium silico-calcium iron in piece, have more deep understanding in special material and medicinal applications, still
Research by the special construction of pangolin scales in the preparation of catalyst is actually rare.
A kind of preparation method of composite copper powder catalyst disclosed in Chinese patent CN 102941102B, by copper scale through ball milling
Sheet of copper is formed after being sieved with air current classifying, electrolysis copper billet, which is put into thawing in smelting furnace, forms copper liquid, is covered with charcoal layer anti-
After oxidation processes, the block tin and spelter of high-purity is successively added in heating, Cu-Sn-Zn mixed liquor is formed, through water atomization or aerosol
Change is handled, and obtains Albaloy powder, after detaching dry screening, obtains flakey Albaloy powder through ball-milling treatment again
End is mixed with sheet of copper and flakey Albaloy powder to obtain composite copper powder catalyst in proportion, which urges
Agent is mainly used for using in organic silicon monomer synthesis, and catalyst surface bumps defect is more, and large specific surface area improves main catalytic
The catalytic performance of copper phase, catalysis characteristics are substantially better than common compound copper powder, improve the selectivity of dimethyldichlorosilane, extend
Synthesis reaction period reduces cost, increases economic efficiency.By the above-mentioned prior art it is found that by carrying out piece to main copper catalyst
Shape processing, and there is concave-convex defect in surface, significantly improve copper catalyst catalytic efficiency in organic silicon monomer synthesis, therefore,
The form of metallic catalyst is subjected to bionical processing according to pangolin scales structure, is used for pyromellitic acid anhydride and equal benzene tetramethyl
In the preparation process of acid, also it is expected to obtain preferable catalytic effect.
Invention content
The technical problem to be solved in the present invention is to provide the catalyst of a kind of pyromellitic acid anhydride and Pyromellitic Acid and
The precursor solution of vanadium titanium and polymer solution homogeneous are stirred the microemulsion to form stable suspersion, by micro emulsion by preparation method
Liquid pours into the molds of imitative pangolin scales after curing molding, and freeze-dried and micro etch processing obtains containing both macro and micro
The porous vanadium titanium catalyst of sector of groove, the specific surface area of catalyst is big, and catalytic activity is big, anti-for durol gaseous oxidation
Excellent catalytic effect in pyromellitic acid anhydride and Pyromellitic Acid should be prepared.
In order to solve the above technical problems, the technical scheme is that：
A kind of catalyst preparing pyromellitic acid anhydride and Pyromellitic Acid for durol gas phase oxidation, feature
It is, the catalyst that pyromellitic acid anhydride and Pyromellitic Acid are prepared for durol gas phase oxidation is imitative wears
The porous vanadium titanium catalyst of naze scale structure, the imitative pangolin scales structure is to have reeded fan-shaped flake, described recessed
The height of the fan-shaped flake further groove of slot is not higher than 0.5mm.
The present invention also provides one kind preparing pyromellitic acid anhydride and equal benzene tetramethyl for durol gas phase oxidation
The preparation method of the catalyst of acid, it is characterised in that：Include the following steps：
（1）Oxalic acid is add to deionized water, is heated to being completely dissolved, ammonium metavanadate mixing is added, after being sufficiently mixed, is added
Titanium trichloride solution, high-speed stirred form the precursor solution of the titanium containing vanadium；
（2）By step（1）Polymer solution is added in the precursor solution of the titanium containing vanadium prepared, is formed to stablize after high-speed stirred and be hanged
Floating microemulsion pours into microemulsion in the reeded fan-shaped flake mold of tool of imitative pangolin scales, after low temperature quick freeze,
Vacuum freeze drying is taken out, and the porous vanadium titanium material of imitative pangolin scales structure is obtained；
（3）By step（2）The porous vanadium titanium material of the imitative pangolin scales structure prepared is handled through surface micro etch, is prepared into
To the porous vanadium titanium catalyst of imitative pangolin scales structure；
Wherein, the porous vanadium titanium catalyst of the imitative pangolin scales structure prepares equal benzene for durol gas phase oxidation
Tetracarboxylic acid dianhydride and Pyromellitic Acid.
As a preferred embodiment of the above technical solution, the step（1）In, the ratio of the amount of the substance of oxalic acid and ammonium metavanadate is,
10:1, the mass ratio of the oxalic acid and deionized water is 5:90-100.
As a preferred embodiment of the above technical solution, the step（1）In, the ratio of the amount of the substance of vanadium ion and titanium ion is
0.8-1.2:1。
As a preferred embodiment of the above technical solution, the step（2）In, polymer solution includes water, polyacrylamide, ten
Tetraalkyl polyoxyethylene ether nonionic surfactant, hexadecane and butanol, the myristyl polyoxyethylene ether, n-butanol and
The volume ratio of hexadecane is 1:0.5-0.6:0.15-0.2.
As a preferred embodiment of the above technical solution, the step（2）In, have the height of reeded fan-shaped flake mold further groove
Degree is not higher than 0.5mm, fan-shaped a diameter of 18-20mm, it is fan-shaped to the number of degrees of central angle be 30-45 °, fan-shaped long short arc
Long ratio is 1.5-2, and the thickness for having reeded fan-shaped flake mold is 3-6mm.
As a preferred embodiment of the above technical solution, the step（2）In, the temperature of low temperature quick freeze is -5 ~ -10 DEG C, when
Between be 10-30s, the temperature of vacuum freeze drying is -20 DEG C, time 2-3d.
As a preferred embodiment of the above technical solution, the step（2）In, imitate the porous vanadium titanium material of pangolin scales structure
Aperture size is 50-500nm.
As a preferred embodiment of the above technical solution, the step（3）In, micro etch processing is microwave discharge etching processing, work(
Rate is 200-500W, time 1-30min.
As a preferred embodiment of the above technical solution, the step（3）In, imitate the porous vanadium titanium catalyst of pangolin scales structure
The mean breadth of groove be 5-10 μm, the height of groove is 1-5 μm.
Compared with prior art, the invention has the advantages that：
（1）The primary raw material of the porous vanadium titanium catalyst of imitative pangolin scales structure prepared by the present invention is that vanadium titanium precursors are molten
Liquid, vanadium titanium precursors solution are to generate complex compound first with oxalic acid and ammonium metavanadate（NH4）2 [(VO) 2 (C2O4) 3], be complexed from
The presence of son reduces the displacement of conducting particles, is conducive to titanium ion solution and is uniformly distributed in the surrounding of complex compound to be formed
Stable vanadium titanium precursors solution, vanadium titanium precursors is dissolved in after being mixed with polymer solution, and it is equal that homogeneous forms micro-nano granules
The microemulsion of even Stable distritation, by microemulsion be fitted into mold after instantaneous solidification drying, be prepared hole grain size it is small and be distributed
Uniform porous vanadium titanium material, the mold that pangolin scales are imitated by design are tied in the macroscopic view for macroscopically imitating pangolin scales
Structure, then by the microstructure of microcosmic etching processing imitation pangolin scales, so that the porous vanadium titanium catalyst of preparation is had and wear mountain
The special structure of first scale assigns the larger specific surface area and catalytic activity of catalyst, have special lubricity, for
Prepared by durol gas phase oxidation have good catalytic activity in pyromellitic acid anhydride and Pyromellitic Acid.
（2）The present invention applies to bionics techniques in the preparation process of catalyst, and special biological structure is urged for improving
In the catalytic activity of agent, small-bore and equally distributed catalyst are not only obtained, but also there is special microcosmic and macroscopical ditch
Slot structure assigns catalyst surface special performance, in catalytic action, has very high mobility, further increases catalysis
The catalytic efficiency of agent.
（3）The preparation method of the present invention is simple, and the structure of catalyst, hole are adjusted by adjusting material rate and technological parameter
Diameter size and material adjust specific surface area, active site and the aperture of catalyst, obtain being used for durol gas phase oxidation system
Standby pyromellitic acid anhydride and Pyromellitic Acid catalytic activity height, efficient catalyst.
Specific implementation mode
Below in conjunction with specific embodiment, the present invention will be described in detail, herein illustrative examples and explanation of the invention
For explaining the present invention, but it is not as a limitation of the invention.
Embodiment 1：
（1）It is 5 by mass ratio:90 oxalic acid is add to deionized water, and is heated to 50 DEG C, is stirred to being completely dissolved, according to grass
Acid and the ratio of the amount of the substance of ammonium metavanadate are 10:1 is added ammonium metavanadate mixing, and after being sufficiently mixed, titanium trichloride solution is added,
High-speed stirred forms the precursor solution of the titanium containing vanadium under the speed of 2000r/min, wherein the substance of vanadium ion and titanium ion
The ratio of amount is 0.8:1.
（2）By step（1）Polymer solution is added in the precursor solution of the titanium containing vanadium prepared, wherein in polymer solution
It is 90 including volume ratio:10：1:0.5:0.15 water, polyacrylamide, myristyl polyoxyethylene ether non-ionic surface active
Agent, butanol and hexadecane form the microemulsion of stable suspersion under the speed of 20000r/min, microemulsion are fallen after high-speed stirred
In the reeded fan-shaped flake mold of tool for entering imitative pangolin scales, wherein have reeded fan-shaped flake mold further groove
Height is not higher than 0.5mm, fan-shaped a diameter of 18mm, it is fan-shaped to the number of degrees of central angle be 30 °, fan-shaped length arc length ratio
It is 1.5, the thickness for having reeded fan-shaped flake mold is 3mm, true at -20 DEG C at -5 DEG C after low temperature quick freeze 10s
Vacuum freecing-dry 2d takes out, and obtains the porous vanadium titanium material of imitative pangolin scales structure.
（3）By the porous vanadium titanium material of imitative pangolin scales structure under 200W power microwave discharge etching processing 1min,
The porous vanadium titanium catalyst of imitative pangolin scales structure is prepared.
（4）Using durol and air as raw material, in fixed bed reactors, to imitate the porous vanadium of pangolin scales structure
Titanium catalyst is catalyst, and through gas phase oxidation at 350 DEG C, crystallisation by cooling obtains thick pyromellitic acid anhydride,
Pyromellitic Acid is prepared in hydrolysis at 0.2MPa and 90 DEG C.
Embodiment 2：
（1）It is 5 by mass ratio:100 oxalic acid is add to deionized water, and is heated to 60 DEG C, stirring to being completely dissolved, according to
The ratio of the amount of the substance of oxalic acid and ammonium metavanadate is 10:1 is added ammonium metavanadate mixing, and after being sufficiently mixed, it is molten that titanium trichloride is added
Liquid, high-speed stirred forms the precursor solution of the titanium containing vanadium under the speed of 3000r/min, wherein the object of vanadium ion and titanium ion
The ratio of the amount of matter is 1.2:1.
（2）By step（1）Polymer solution is added in the precursor solution of the titanium containing vanadium prepared, wherein in polymer solution
It is 100 including volume ratio: 15：1: 0.6:0.2 water, polyacrylamide, myristyl polyoxyethylene ether non-ionic surface are lived
Property agent, butanol and hexadecane, under the speed of 25000r/min after high-speed stirred formed stable suspersion microemulsion, by microemulsion
It pours into the reeded fan-shaped flake mold of tool of imitative pangolin scales, wherein have reeded fan-shaped flake mold further groove
Height be not higher than 0.5mm, fan-shaped a diameter of 20mm, it is fan-shaped to the number of degrees of central angle be 45 °, fan-shaped length arc length
Than being 2, the thickness for having reeded fan-shaped flake mold is 6mm, at -10 DEG C after low temperature quick freeze 30s, at -20 DEG C
Vacuum freeze drying 3d takes out, and obtains the porous vanadium titanium material of imitative pangolin scales structure.
（3）By the porous vanadium titanium material of imitative pangolin scales structure under 500W power microwave discharge etching processing 30min,
The porous vanadium titanium catalyst of imitative pangolin scales structure is prepared.
（4）Using durol and air as raw material, in fixed bed reactors, to imitate the porous vanadium of pangolin scales structure
Titanium catalyst is catalyst, and through gas phase oxidation at 380 DEG C, crystallisation by cooling obtains thick pyromellitic acid anhydride,
Pyromellitic Acid is prepared in hydrolysis at 0.2MPa and 100 DEG C.
Embodiment 3：
（1）It is 5 by mass ratio:95 oxalic acid is add to deionized water, and is heated to 55 DEG C, is stirred to being completely dissolved, according to grass
Acid and the ratio of the amount of the substance of ammonium metavanadate are 10:1 is added ammonium metavanadate mixing, and after being sufficiently mixed, titanium trichloride solution is added,
High-speed stirred forms the precursor solution of the titanium containing vanadium under the speed of 2500r/min, wherein the substance of vanadium ion and titanium ion
The ratio of amount is 0.9:1.
（2）By step（1）Polymer solution is added in the precursor solution of the titanium containing vanadium prepared, wherein in polymer solution
It is 92 including volume ratio:13：1:0.55:0.17 water, polyacrylamide, myristyl polyoxyethylene ether non-ionic surface active
Agent, butanol and hexadecane form the microemulsion of stable suspersion under the speed of 23000r/min, microemulsion are fallen after high-speed stirred
In the reeded fan-shaped flake mold of tool for entering imitative pangolin scales, wherein have reeded fan-shaped flake mold further groove
Height is not higher than 0.5mm, fan-shaped a diameter of 19mm, it is fan-shaped to the number of degrees of central angle be 35 °, fan-shaped length arc length ratio
It is 1.8, the thickness for having reeded fan-shaped flake mold is 5mm, true at -20 DEG C at -8 DEG C after low temperature quick freeze 15s
Vacuum freecing-dry 2.5d takes out, and obtains the porous vanadium titanium material of imitative pangolin scales structure.
（3）By the porous vanadium titanium material of imitative pangolin scales structure under 300W power microwave discharge etching processing 10min,
The porous vanadium titanium catalyst of imitative pangolin scales structure is prepared.
（4）Using durol and air as raw material, in fixed bed reactors, to imitate the porous vanadium of pangolin scales structure
Titanium catalyst is catalyst, and through gas phase oxidation at 360 DEG C, crystallisation by cooling obtains thick pyromellitic acid anhydride,
Pyromellitic Acid is prepared in hydrolysis at 0.2MPa and 95 DEG C.
Embodiment 4：
（1）It is 5 by mass ratio:98 oxalic acid is add to deionized water, and is heated to 53 DEG C, is stirred to being completely dissolved, according to grass
Acid and the ratio of the amount of the substance of ammonium metavanadate are 10:1 is added ammonium metavanadate mixing, and after being sufficiently mixed, titanium trichloride solution is added,
High-speed stirred forms the precursor solution of the titanium containing vanadium under the speed of 2200r/min, wherein the substance of vanadium ion and titanium ion
The ratio of amount is 1.1:1.
（2）By step（1）Polymer solution is added in the precursor solution of the titanium containing vanadium prepared, wherein in polymer solution
It is 98 including volume ratio:13：1:0.58:0.19 water, polyacrylamide, myristyl polyoxyethylene ether non-ionic surface active
Agent, butanol and hexadecane form the microemulsion of stable suspersion under the speed of 21000r/min, microemulsion are fallen after high-speed stirred
In the reeded fan-shaped flake mold of tool for entering imitative pangolin scales, wherein have reeded fan-shaped flake mold further groove
Height is not higher than 0.5mm, fan-shaped a diameter of 19mm, it is fan-shaped to the number of degrees of central angle be 40 °, fan-shaped length arc length ratio
It is 1.9, the thickness for having reeded fan-shaped flake mold is 4.5mm, at -6 DEG C after low temperature quick freeze 25s, at -20 DEG C
Vacuum freeze drying 3d takes out, and obtains the porous vanadium titanium material of imitative pangolin scales structure.
（3）By the porous vanadium titanium material of imitative pangolin scales structure under 450W power microwave discharge etching processing 20min,
The porous vanadium titanium catalyst of imitative pangolin scales structure is prepared.
（4）Using durol and air as raw material, in fixed bed reactors, to imitate the porous vanadium of pangolin scales structure
Titanium catalyst is catalyst, and through gas phase oxidation at 350 DEG C, crystallisation by cooling obtains thick pyromellitic acid anhydride,
Pyromellitic Acid is prepared in hydrolysis at 0.2MPa and 90 DEG C.
Embodiment 5：
（1）It is 5 by mass ratio:90 oxalic acid is add to deionized water, and is heated to 60 DEG C, is stirred to being completely dissolved, according to grass
Acid and the ratio of the amount of the substance of ammonium metavanadate are 10:1 is added ammonium metavanadate mixing, and after being sufficiently mixed, titanium trichloride solution is added,
High-speed stirred forms the precursor solution of the titanium containing vanadium under the speed of 2000r/min, wherein the substance of vanadium ion and titanium ion
The ratio of amount is 1.2:1.
（2）By step（1）Polymer solution is added in the precursor solution of the titanium containing vanadium prepared, wherein in polymer solution
It is 90 including volume ratio:15：1:0.5:0.2 water, polyacrylamide, myristyl polyoxyethylene ether non-ionic surface active
Agent, butanol and hexadecane form the microemulsion of stable suspersion under the speed of 20000r/min, microemulsion are fallen after high-speed stirred
In the reeded fan-shaped flake mold of tool for entering imitative pangolin scales, wherein have reeded fan-shaped flake mold further groove
Height is not higher than 0.5mm, fan-shaped a diameter of 20mm, it is fan-shaped to the number of degrees of central angle be 30 °, fan-shaped length arc length ratio
It is 2, the thickness for having reeded fan-shaped flake mold is 3mm, true at -20 DEG C at -10 DEG C after low temperature quick freeze 10s
Vacuum freecing-dry 3d takes out, and obtains the porous vanadium titanium material of imitative pangolin scales structure.
（3）By the porous vanadium titanium material of imitative pangolin scales structure under 200W power microwave discharge etching processing 30min,
The porous vanadium titanium catalyst of imitative pangolin scales structure is prepared.
（4）Using durol and air as raw material, in fixed bed reactors, to imitate the porous vanadium of pangolin scales structure
Titanium catalyst is catalyst, and through gas phase oxidation at 350 DEG C, crystallisation by cooling obtains thick pyromellitic acid anhydride,
Pyromellitic Acid is prepared in hydrolysis at 0.2MPa and 100 DEG C.
Embodiment 6：
（1）It is 5 by mass ratio:100 oxalic acid is add to deionized water, and is heated to 50 DEG C, stirring to being completely dissolved, according to
The ratio of the amount of the substance of oxalic acid and ammonium metavanadate is 10:1 is added ammonium metavanadate mixing, and after being sufficiently mixed, it is molten that titanium trichloride is added
Liquid, high-speed stirred forms the precursor solution of the titanium containing vanadium under the speed of 3000r/min, wherein the object of vanadium ion and titanium ion
The ratio of the amount of matter is 0.8:1.
（2）By step（1）Polymer solution is added in the precursor solution of the titanium containing vanadium prepared, wherein in polymer solution
It is 100 including volume ratio:10：1: 0.6:0.15 water, polyacrylamide, myristyl polyoxyethylene ether non-ionic surface are lived
Property agent, butanol and hexadecane, under the speed of 25000r/min after high-speed stirred formed stable suspersion microemulsion, by microemulsion
It pours into the reeded fan-shaped flake mold of tool of imitative pangolin scales, wherein have reeded fan-shaped flake mold further groove
Height be not higher than 0.5mm, fan-shaped a diameter of 18mm, it is fan-shaped to the number of degrees of central angle be 45 °, fan-shaped length arc length
Than being 1.5, the thickness for having reeded fan-shaped flake mold is 6mm, at -5 DEG C after low temperature quick freeze 30s, at -20 DEG C
Vacuum freeze drying 2d takes out, and obtains the porous vanadium titanium material of imitative pangolin scales structure.
（3）By the porous vanadium titanium material of imitative pangolin scales structure under 500W power microwave discharge etching processing 1min,
The porous vanadium titanium catalyst of imitative pangolin scales structure is prepared.
（4）Using durol and air as raw material, in fixed bed reactors, to imitate the porous vanadium of pangolin scales structure
Titanium catalyst is catalyst, and through gas phase oxidation at 380 DEG C, crystallisation by cooling obtains thick pyromellitic acid anhydride,
Pyromellitic Acid is prepared in hydrolysis at 0.2MPa and 90 DEG C.
After testing, the aperture size of the porous vanadium titanium catalyst for the imitative pangolin scales structure that prepared by embodiment 1-6, low-light
The result of groove width and height is as follows：
| Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 | Embodiment 6 | |
| Aperture size（nm） | 50 | 500 | 400 | 150 | 200 | 350 |
| The mean breadth (μm) of groove | 5 | 10 | 8 | 7 | 6 | 9 |
| The height (μm) of groove | 1 | 5 | 3 | 4 | 2 | 3 |
The porous vanadium titanium catalyst of imitative pangolin scales structure prepared by embodiment 1-6 is used for durol gas phase oxidation system
In the technique of standby pyromellitic acid anhydride and Pyromellitic Acid, catalytic efficiency is up to 98%, and product yield is up to 96%.
The above-described embodiments merely illustrate the principles and effects of the present invention, and is not intended to limit the present invention.It is any ripe
The personage for knowing this technology can all carry out modifications and changes to above-described embodiment without violating the spirit and scope of the present invention.Cause
This, institute is complete without departing from the spirit and technical ideas disclosed in the present invention by those of ordinary skill in the art such as
At all equivalent modifications or change, should by the present invention claim be covered.
Claims (10)
1. a kind of catalyst preparing pyromellitic acid anhydride and Pyromellitic Acid for durol gas phase oxidation, special
Sign is, described to prepare pyromellitic acid anhydride and the catalyst of Pyromellitic Acid for durol gas phase oxidation be imitative
The porous vanadium titanium catalyst of pangolin scales structure, the imitative pangolin scales structure is to have reeded fan-shaped flake, described
The height of the fan-shaped flake further groove of groove is not higher than 0.5mm.
2. a kind of system for the catalyst preparing pyromellitic acid anhydride and Pyromellitic Acid for durol gas phase oxidation
Preparation Method, it is characterised in that：Include the following steps：
（1）Oxalic acid is add to deionized water, is heated to being completely dissolved, ammonium metavanadate mixing is added, after being sufficiently mixed, is added
Titanium trichloride solution, high-speed stirred form the precursor solution of the titanium containing vanadium；
（2）By step（1）Polymer solution is added in the precursor solution of the titanium containing vanadium prepared, is formed to stablize after high-speed stirred and be hanged
Floating microemulsion pours into microemulsion in the reeded fan-shaped flake mold of tool of imitative pangolin scales, after low temperature quick freeze,
Vacuum freeze drying is taken out, and the porous vanadium titanium material of imitative pangolin scales structure is obtained；
（3）By step（2）The porous vanadium titanium material of the imitative pangolin scales structure prepared is handled through surface micro etch, is prepared into
To the porous vanadium titanium catalyst of imitative pangolin scales structure；
Wherein, the porous vanadium titanium catalyst of the imitative pangolin scales structure prepares equal benzene for durol gas phase oxidation
Tetracarboxylic acid dianhydride and Pyromellitic Acid.
3. one kind according to claim 2 prepares pyromellitic acid anhydride and equal benzene for durol gas phase oxidation
The preparation method of the catalyst of tetracarboxylic acid, it is characterised in that：The step（1）In, the amount of the substance of oxalic acid and ammonium metavanadate
Than being 10:1, the mass ratio of the oxalic acid and deionized water is 5:90-100.
4. one kind according to claim 2 prepares pyromellitic acid anhydride and equal benzene for durol gas phase oxidation
The preparation method of the catalyst of tetracarboxylic acid, it is characterised in that：The step（1）In, the amount of the substance of vanadium ion and titanium ion
Than for 0.8-1.2:1.
5. one kind according to claim 2 prepares pyromellitic acid anhydride and equal benzene for durol gas phase oxidation
The preparation method of the catalyst of tetracarboxylic acid, it is characterised in that：The step（2）In, polymer solution includes water, polyacrylamide
Amine, myristyl polyoxyethylene ether nonionic surfactant, hexadecane and butanol, the myristyl polyoxyethylene ether, just
The volume ratio of butanol and hexadecane is 1:0.5-0.6:0.15-0.2.
6. one kind according to claim 2 prepares pyromellitic acid anhydride and equal benzene for durol gas phase oxidation
The preparation method of the catalyst of tetracarboxylic acid, it is characterised in that：The step（2）In, have reeded fan-shaped flake mold concave
The height of slot is not higher than 0.5mm, fan-shaped a diameter of 18-20mm, it is fan-shaped to the number of degrees of central angle be 30-45 °, it is fan-shaped
Length arc length ratio is 1.5-2, and the thickness for having reeded fan-shaped flake mold is 3-6mm.
7. one kind according to claim 2 prepares pyromellitic acid anhydride and equal benzene for durol gas phase oxidation
The preparation method of the catalyst of tetracarboxylic acid, it is characterised in that：The step（2）In, the temperature of low temperature quick freeze is -5 ~ -10
DEG C, the temperature of time 10-30s, vacuum freeze drying are -20 DEG C, time 2-3d.
8. one kind according to claim 2 prepares pyromellitic acid anhydride and equal benzene for durol gas phase oxidation
The preparation method of the catalyst of tetracarboxylic acid, it is characterised in that：The step（2）In, imitate the porous vanadium titanium of pangolin scales structure
The aperture size of material is 50-500nm.
9. one kind according to claim 2 prepares pyromellitic acid anhydride and equal benzene for durol gas phase oxidation
The preparation method of the catalyst of tetracarboxylic acid, it is characterised in that：The step（3）In, micro etch processing is at microwave discharge etching
Reason, power 200-500W, time 1-30min.
A kind of pyromellitic acid anhydride and equal is prepared 10. according to claim 2 for durol gas phase oxidation
The preparation method of the catalyst of benzene tetracarboxylic acid, it is characterised in that：The step（3）In, imitate the porous vanadium of pangolin scales structure
The mean breadth of the groove of titanium catalyst is 5-10 μm, and the height of groove is 1-5 μm.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN111379159A (en) * | 2020-05-22 | 2020-07-07 | 无锡浦惠恒业纺织科技有限公司 | Hydrogen peroxide catalytic system based on polycarboxylic acid or anhydride compound and application of hydrogen peroxide catalytic system in low-temperature pretreatment of textiles |
| CN111960939A (en) * | 2020-08-18 | 2020-11-20 | 连云港鹏辰特种新材料有限公司 | Preparation method for preparing pyromellitic acid based on catalytic oxidation-hydrolysis-fractional crystallization |
| 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 (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0405508A2 (en) * | 1989-06-27 | 1991-01-02 | Nippon Steel Chemical Co., Ltd. | Process for producing pyromellitic dianhydride |
| US5225572A (en) * | 1989-06-27 | 1993-07-06 | Nippon Steel Chemical Co., Ltd. | Process for producing pyromellitic dianhydride |
| CN1104643A (en) * | 1993-02-25 | 1995-07-05 | 电化学工业有限公司（国际） | Process for preparing pyromellitic dianhydride |
| US5792719A (en) * | 1995-05-24 | 1998-08-11 | Consortium Fur Elektrochenische Industrie Gmbh | Supported catalyst for gas-phase oxidation reactions |
| DE19717344A1 (en) * | 1997-04-24 | 1998-10-29 | Consortium Elektrochem Ind | Production of catalyst for selective oxidation of aromatic hydrocarbon |
| CN102000596A (en) * | 2010-11-15 | 2011-04-06 | 常熟市联邦化工有限公司 | Catalyst for preparing pyromellitic dianhydride from durene through gaseous catalytic oxidation and preparation method thereof |
| CN106540679A (en) * | 2016-11-04 | 2017-03-29 | 常州新日催化剂有限公司 | Equal acid anhydride catalyst of double sections of beds and preparation method thereof |
| CN107649119A (en) * | 2017-09-30 | 2018-02-02 | 常熟理工学院 | Colloidal sol sintering process prepares the low vanadium catalyst of equal acid anhydride |
-
2018
- 2018-04-24 CN CN201810370897.5A patent/CN108404988A/en not_active Withdrawn
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0405508A2 (en) * | 1989-06-27 | 1991-01-02 | Nippon Steel Chemical Co., Ltd. | Process for producing pyromellitic dianhydride |
| US5225572A (en) * | 1989-06-27 | 1993-07-06 | Nippon Steel Chemical Co., Ltd. | Process for producing pyromellitic dianhydride |
| CN1104643A (en) * | 1993-02-25 | 1995-07-05 | 电化学工业有限公司（国际） | Process for preparing pyromellitic dianhydride |
| US5792719A (en) * | 1995-05-24 | 1998-08-11 | Consortium Fur Elektrochenische Industrie Gmbh | Supported catalyst for gas-phase oxidation reactions |
| DE19717344A1 (en) * | 1997-04-24 | 1998-10-29 | Consortium Elektrochem Ind | Production of catalyst for selective oxidation of aromatic hydrocarbon |
| CN102000596A (en) * | 2010-11-15 | 2011-04-06 | 常熟市联邦化工有限公司 | Catalyst for preparing pyromellitic dianhydride from durene through gaseous catalytic oxidation and preparation method thereof |
| CN106540679A (en) * | 2016-11-04 | 2017-03-29 | 常州新日催化剂有限公司 | Equal acid anhydride catalyst of double sections of beds and preparation method thereof |
| CN107649119A (en) * | 2017-09-30 | 2018-02-02 | 常熟理工学院 | Colloidal sol sintering process prepares the low vanadium catalyst of equal acid anhydride |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN111379159A (en) * | 2020-05-22 | 2020-07-07 | 无锡浦惠恒业纺织科技有限公司 | Hydrogen peroxide catalytic system based on polycarboxylic acid or anhydride compound and application of hydrogen peroxide catalytic system in low-temperature pretreatment of textiles |
| CN111960939A (en) * | 2020-08-18 | 2020-11-20 | 连云港鹏辰特种新材料有限公司 | Preparation method for preparing pyromellitic acid based on catalytic oxidation-hydrolysis-fractional crystallization |
| CN111960939B (en) * | 2020-08-18 | 2021-12-28 | 连云港鹏辰特种新材料有限公司 | Preparation method for preparing pyromellitic acid based on catalytic oxidation-hydrolysis-fractional crystallization |
| 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 |
| CN114425325B (en) * | 2020-09-28 | 2024-05-28 | 中国石油化工股份有限公司 | Catalyst for preparing pyromellitic anhydride by oxidizing pyromellitic benzene and preparation method and application thereof |
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