CN108440555B - Method for preparing pyromellitic dianhydride based on graphene sponge body catalysis - Google Patents
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 87
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 84
- VLDPXPPHXDGHEW-UHFFFAOYSA-N 1-chloro-2-dichlorophosphoryloxybenzene Chemical compound ClC1=CC=CC=C1OP(Cl)(Cl)=O VLDPXPPHXDGHEW-UHFFFAOYSA-N 0.000 title claims abstract description 50
- 238000000034 method Methods 0.000 title claims abstract description 29
- 238000006555 catalytic reaction Methods 0.000 title claims abstract description 12
- SQNZJJAZBFDUTD-UHFFFAOYSA-N durene Chemical compound CC1=CC(C)=C(C)C=C1C SQNZJJAZBFDUTD-UHFFFAOYSA-N 0.000 claims abstract description 84
- 239000003054 catalyst Substances 0.000 claims abstract description 50
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims abstract description 48
- 238000010438 heat treatment Methods 0.000 claims abstract description 40
- 239000004530 micro-emulsion Substances 0.000 claims abstract description 37
- 229910052763 palladium Inorganic materials 0.000 claims abstract description 35
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims abstract description 33
- 238000002156 mixing Methods 0.000 claims abstract description 25
- 239000000203 mixture Substances 0.000 claims abstract description 25
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 22
- 239000002243 precursor Substances 0.000 claims abstract description 20
- 238000003756 stirring Methods 0.000 claims abstract description 18
- 238000002360 preparation method Methods 0.000 claims abstract description 15
- 230000005855 radiation Effects 0.000 claims abstract description 14
- 238000001291 vacuum drying Methods 0.000 claims abstract description 14
- 230000008014 freezing Effects 0.000 claims abstract description 13
- 238000007710 freezing Methods 0.000 claims abstract description 13
- 150000003839 salts Chemical class 0.000 claims abstract description 13
- 235000006408 oxalic acid Nutrition 0.000 claims abstract description 11
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 claims abstract description 9
- 230000003197 catalytic effect Effects 0.000 claims abstract description 9
- 239000008367 deionised water Substances 0.000 claims abstract description 9
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 9
- 238000000859 sublimation Methods 0.000 claims abstract description 9
- 230000008022 sublimation Effects 0.000 claims abstract description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 9
- 230000009467 reduction Effects 0.000 claims abstract description 7
- 238000006243 chemical reaction Methods 0.000 claims abstract description 6
- 238000002425 crystallisation Methods 0.000 claims abstract description 5
- 230000008025 crystallization Effects 0.000 claims abstract description 5
- 230000007062 hydrolysis Effects 0.000 claims abstract description 5
- 238000006460 hydrolysis reaction Methods 0.000 claims abstract description 5
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 claims abstract description 5
- 238000001816 cooling Methods 0.000 claims abstract description 3
- 229910052720 vanadium Inorganic materials 0.000 claims description 19
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims description 19
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 16
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 16
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 claims description 16
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical compound [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 claims description 16
- 230000008016 vaporization Effects 0.000 claims description 16
- 239000007788 liquid Substances 0.000 claims description 11
- 238000002844 melting Methods 0.000 claims description 8
- 230000008018 melting Effects 0.000 claims description 8
- 229910052757 nitrogen Inorganic materials 0.000 claims description 8
- 239000004323 potassium nitrate Substances 0.000 claims description 8
- 235000010333 potassium nitrate Nutrition 0.000 claims description 8
- 235000010288 sodium nitrite Nutrition 0.000 claims description 8
- 239000007787 solid Substances 0.000 claims description 8
- 238000009834 vaporization Methods 0.000 claims description 8
- 229910003603 H2PdCl4 Inorganic materials 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- 238000001914 filtration Methods 0.000 claims description 2
- 238000006722 reduction reaction Methods 0.000 description 11
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 6
- 230000003647 oxidation Effects 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- 229910052799 carbon Inorganic materials 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 239000012696 Pd precursors Substances 0.000 description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 3
- 239000001569 carbon dioxide Substances 0.000 description 3
- 229910002092 carbon dioxide Inorganic materials 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 238000005507 spraying Methods 0.000 description 3
- 239000010936 titanium Substances 0.000 description 3
- GWHJZXXIDMPWGX-UHFFFAOYSA-N 1,2,4-trimethylbenzene Chemical compound CC1=CC=C(C)C(C)=C1 GWHJZXXIDMPWGX-UHFFFAOYSA-N 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- 239000000969 carrier Substances 0.000 description 2
- 239000000919 ceramic Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000017525 heat dissipation Effects 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 2
- 229910010271 silicon carbide Inorganic materials 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- XHCLAFWTIXFWPH-UHFFFAOYSA-N [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] Chemical group [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] XHCLAFWTIXFWPH-UHFFFAOYSA-N 0.000 description 1
- 238000002679 ablation Methods 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 230000029936 alkylation Effects 0.000 description 1
- 238000005804 alkylation reaction Methods 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical group [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- 229910052810 boron oxide Inorganic materials 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000013064 chemical raw material Substances 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- JKWMSGQKBLHBQQ-UHFFFAOYSA-N diboron trioxide Chemical group O=BOB=O JKWMSGQKBLHBQQ-UHFFFAOYSA-N 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229920006015 heat resistant resin Polymers 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
- KHMOASUYFVRATF-UHFFFAOYSA-J tin(4+);tetrachloride;pentahydrate Chemical compound O.O.O.O.O.Cl[Sn](Cl)(Cl)Cl KHMOASUYFVRATF-UHFFFAOYSA-J 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- GFNGCDBZVSLSFT-UHFFFAOYSA-N titanium vanadium Chemical compound [Ti].[V] GFNGCDBZVSLSFT-UHFFFAOYSA-N 0.000 description 1
- 229910001935 vanadium oxide Inorganic materials 0.000 description 1
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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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/56—Platinum group metals
- B01J23/64—Platinum group metals with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/648—Vanadium, niobium or tantalum or polonium
- B01J23/6482—Vanadium
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
- B01J35/56—Foraminous structures having flow-through passages or channels, e.g. grids or three-dimensional monoliths
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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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
- B01J37/0018—Addition of a binding agent or of material, later completely removed among others as result of heat treatment, leaching or washing,(e.g. forming of pores; protective layer, desintegrating by heat)
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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
- 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
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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
- 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
- B01J37/343—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 ultrasonic wave energy
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Abstract
The invention provides a method for preparing pyromellitic dianhydride based on graphene sponge body catalysis, which comprises the following steps: adding oxalic acid into deionized water for dissolving, adding ammonium metavanadate for mixing, continuously stirring, and dropwise adding a palladium chloride solution to form a microemulsion; adding the micro emulsion into the graphene oxide solution, uniformly stirring at a high speed to obtain a precursor solution, placing the precursor solution in a low-temperature environment for quick freezing and vacuum drying, and then performing laser radiation reduction treatment to obtain the graphene-based vanadium-palladium porous sponge catalyst; and placing the graphene-based vanadium-palladium porous sponge catalyst in a gas-phase oxidation reaction fixed bed, heating the fixed bed, introducing a mixture of durene and air, performing circulating heat exchange and cooling reaction by using molten salt, trapping, and performing hydrolysis, crystallization and sublimation to obtain the pyromellitic dianhydride. The invention applies the catalyst with high catalytic activity and good thermal stability to the preparation of pyromellitic dianhydride, and the prepared product has high efficiency and good purity.
Description
Technical Field
The invention belongs to the technical field of preparation of pyromellitic dianhydride, and particularly relates to a method for preparing pyromellitic dianhydride based on graphene sponge body catalysis.
Background
Pyromellitic dianhydride is a very important chemical raw material, is mainly used as a monomer of heat-resistant resins such as polyimide, polyimidazole and the like, a powder coating flatting agent intermediate, a medical intermediate, an epoxy resin curing agent and the like, and is a fine chemical product with wide application.
The preparation of the pyromellitic dianhydride at present mainly comprises a pyromellitic oxidation method, a pseudocumene alkylation method, a carbon monoxide method and the like, wherein the preparation of the pyromellitic dianhydride by taking durene as a raw material through a gas-phase oxidation process is a main method, the gas-phase oxidation method only needs one-step air catalytic oxidation, the preparation method is simple, continuous production can be realized, and automatic management is easy.
A pyromellitic dianhydride synthesis catalyst and a preparation method thereof are disclosed in Chinese patent CN 103203244A, the main catalyst active components of the catalyst are vanadium and titanium, the cocatalyst is P, Nb and Sb, spherical inert ceramic balls are used as carriers, after the spherical inert ceramic balls are heated, functional finishing liquid is sprayed on the carriers to obtain blue surface coating type catalysts, and then the blue surface coating type catalysts are roasted in a high-temperature subsection mode to obtain orange yellow spherical catalysts, wherein the mass ratio of V to Ti in the catalysts is 0.1-0.9:0.1-0.9, the mass reference of the catalytic active components is 1, P is 0.01-0.5, Nb is 0.01-1, and Sb is 0.01-0.5, the dosage of vanadium in the catalysts is reduced, and the yield of pyromellitic dianhydride is effectively improved. Chinese patent CN 107537460a discloses a catalyst system for preparing pyromellitic dianhydride by gas phase oxidation of durene, which comprises a main catalyst and a cocatalyst, wherein the main catalyst is vanadium oxide and titanium oxide, the cocatalyst is boron oxide and tin oxide, vanadium and titanium are added into titanium dioxide sol to form vanadium-titanium sol, a proper amount of boric acid and tin tetrachloride pentahydrate are added to form spraying liquid, the spraying liquid is sprayed on a silicon carbide carrier, the silicon carbide carrier is subjected to heat preservation at 250 ℃, and then is roasted and activated at 480 ℃ to obtain the catalyst system, the catalyst system takes a multi-component nano material as a main raw material, and each component in the catalyst has uniform particle size distribution, high purity, high mechanical strength, difficult breakage of an active layer, good heat resistance, and the yield of pyromellitic dianhydride reaches 95% and the purity reaches 95%.
It can be known from the prior art that the existing catalyst based on pyromellitic dianhydride prepared by oxidizing pyromellitic dianhydride as a raw material mostly adopts the mode of spraying an active material on the surface of an inert carrier to improve the mechanical property of the catalyst, the catalyst prepared by the method has low content of active ingredients and limited improvement of catalytic efficiency, so that the yield and the purity of the pyromellitic dianhydride can be remarkably improved when the prepared catalyst with excellent mechanical property and heat dissipation performance is used for preparing the pyromellitic dianhydride.
Disclosure of Invention
The technical problem to be solved by the invention is to provide a method for preparing pyromellitic dianhydride based on graphene sponge body catalysis, which comprises the steps of adding vanadium and palladium precursor microemulsion serving as a template into a graphene oxide solution, preparing a graphene oxide sponge body through quick freezing and vacuum drying, reducing under laser radiation to obtain a catalyst, and applying the catalyst with high catalytic activity and good thermal stability to the preparation of pyromellitic dianhydride, so that the product preparation efficiency is high, and the purity is good.
In order to solve the technical problems, the technical scheme of the invention is as follows:
a method for preparing pyromellitic dianhydride based on graphene sponge body catalysis is characterized by comprising the following steps: the method comprises the following steps:
(1) adding oxalic acid into deionized water, heating until the oxalic acid is completely dissolved, adding ammonium metavanadate, mixing, continuously stirring, dropwise adding a palladium chloride solution, fully mixing, and removing bubbles to form a microemulsion;
(2) adding the micro emulsion into the graphene oxide solution, stirring at a high speed until the micro emulsion is uniformly mixed to obtain a precursor solution, and placing the precursor solution in a low-temperature environment for rapid freezing and vacuum drying treatment to obtain a graphene oxide-based porous sponge body;
(3) reducing the graphene oxide-based porous sponge body prepared in the step (2) by laser radiation to obtain a graphene-based vanadium-palladium porous sponge catalyst;
(4) and (3) placing the graphene-based vanadium-palladium porous sponge catalyst prepared in the step (3) in a gas-phase oxidation reaction fixed bed, heating the gas-phase oxidation reaction fixed bed to the temperature of 320-450 ℃, introducing a mixture of durene and air, performing circulating heat exchange and cooling reaction by using molten salt, trapping, hydrolyzing, crystallizing and sublimating to obtain the pyromellitic dianhydride.
Preferably, in the step (1), the palladium chloride solution is H2PdCl4And (3) solution.
Preferably, in the step (1), the mass ratio of vanadium to palladium in the microemulsion is 0.3-1.5:1, and the solid content is 15-35%.
Preferably, in the step (2), the content of the graphene oxide in the precursor solution is 0.5-15 wt%.
Preferably, in the step (2), the rapid freezing is liquid nitrogen treatment for 5-10s, and the vacuum drying treatment is carried out at-20 ℃ for 24-48 h.
Preferably, in the step (3), the laser radiation is a dual beam with a wavelength of 355nm and 532nm and an energy range of 20-50J/cm2。
Preferably, in the step (3), the time for the reduction treatment by laser radiation is 5 to 30 min.
As a preferable aspect of the above technical solution, in the step (4), a method for preparing a mixture of durene and air includes: heating and melting durene at 90-95 ℃, introducing the durene into a vaporization mixer, mixing the durene with air at the temperature of 190-200 ℃, and continuing heating and vaporizing to obtain the durene.
Preferably, in the step (4), the molten salt is a mixture of potassium nitrate and sodium nitrite with a mass ratio of 1:1, and the temperature of the molten salt is 350-380 ℃.
Preferably, in the step (4), the hydrolysis crystallization conditions are as follows: dissolving the trapped crude pyromellitic dianhydride in acetone solution, filtering, crystallizing at 40-45 deg.C and normal pressure for 6-8h, centrifugally drying, and sublimating at 250 deg.C and-0.09 to-0.1 MPa under vacuum heating.
Compared with the prior art, the invention has the following beneficial effects:
(1) the catalyst in the preparation method of pyromellitic dianhydride is a graphene-based vanadium-palladium porous material with a sponge structure, the vanadium and palladium precursor microemulsion is used as a template, graphene oxide is continuously stacked around the microemulsion to form a cross-linked three-dimensional network, so that vanadium and palladium precursor solutions are uniformly dispersed on the surface of the graphene oxide, the graphene oxide sponge body loaded with vanadium and palladium is prepared by fast freezing and vacuum drying technologies, the graphene oxide is reduced by a double-beam laser irradiation technology, the high energy of laser is used for promoting the cracking of carbon-oxygen double bonds in the graphene oxide to promote the reduction of the graphene oxide into graphene, the reduction degree of a graphene product is high, the preparation process is simple, the time consumption is low, and the graphene in the prepared catalyst is promoted to be formed on two sides of an opening due to the reduction and carbon atom ablation reaction of the graphene, the mechanical property and the toughness of the porous material in the catalyst are improved, so that the graphene-based vanadium-palladium porous sponge catalyst prepared by the invention has the advantages of large specific surface area, uniformly distributed active points, good porous connectivity, good mechanical property and toughness, porosity, capability of improving the heat dissipation performance of the catalyst, capability of improving the mechanical property and the heat resistance of the catalyst by graphene and improvement of the catalytic efficiency of the catalyst in a pyromellitic dianhydride preparation process.
(2) The graphene-based vanadium-palladium porous sponge catalyst is used as a catalyst in the preparation of pyromellitic dianhydride from a mixed raw material of durene and air, active components in the catalyst are vanadium and palladium, the vanadium and the palladium can interact with partial unremoved oxygen groups on a graphene carbon layer, so that the vanadium and the palladium can exist on the graphene carbon layer more stably and are not easy to agglomerate and sinter, the catalytic activity of the vanadium and the palladium combined with the graphene carbon layer on the mixed raw material of durene and air is remarkably improved, the optimal process parameters are obtained by adjusting preparation process parameters, and finally, the pyromellitic dianhydride crude product is subjected to hydrolysis, crystallization and purification treatment to prepare the pyromellitic dianhydride.
(3) The preparation method is simple, controllable, efficient in reaction conditions, non-toxic, pollution-free, good in catalytic effect, mild and efficient in reaction, and suitable for industrial large-scale production.
Detailed Description
The present invention will be described in detail with reference to specific embodiments, which are illustrative of the invention and are not to be construed as limiting the invention.
Example 1:
(1) adding oxalic acid into deionized water, heating to dissolve completely, adding ammonium metavanadate, mixing, stirring, and adding H dropwise2PdCl4And fully mixing the solution, and removing bubbles to form a microemulsion, wherein the mass ratio of vanadium to palladium in the microemulsion is 0.3:1, and the solid content is 15%.
(2) Adding the micro emulsion into the graphene oxide solution, stirring at a high speed until the micro emulsion is uniformly mixed to obtain a precursor solution with the graphene oxide content of 0.5wt%, placing the precursor solution in liquid nitrogen for 5s for quick freezing, and then performing vacuum drying treatment at-20 ℃ for 24h to obtain the graphene oxide-based porous sponge body.
(3) Reducing the graphene oxide-based porous sponge body by double-beam laser radiation with the wavelengths of 355nm and 532nm, wherein the energy range is 20J/cm2And the treatment time is 5min, so as to obtain the graphene-based vanadium-palladium porous sponge catalyst.
(4) Placing a graphene-based vanadium-palladium porous sponge catalyst in a gas-phase oxidation reaction fixed bed, heating the gas-phase oxidation reaction fixed bed to 320 ℃, heating and melting durene at 90 ℃, introducing the durene into a vaporization mixer, mixing the durene with air at 190 ℃, continuing heating and vaporizing to obtain a mixture of durene and air, introducing 20g/m3The mixture of the pyromellitic dianhydride and the air is subjected to circulating heat exchange and temperature reduction reaction by utilizing a mixture molten salt of potassium nitrate and sodium nitrite with the mass ratio of 1:1 at 350 ℃, is trapped, is filtered after being dissolved in an acetone solution, is crystallized for 6 hours at 40 ℃ and normal pressure, is centrifugally dried, and is subjected to sublimation treatment under vacuum heating at 240 ℃ and-0.09 MPa to obtain the pyromellitic dianhydride.
Example 2:
(1) adding oxalic acid into deionized water, heating to dissolve completely, adding ammonium metavanadate, mixing, stirring, and adding H dropwise2PdCl4And fully mixing the solution, and removing bubbles to form a microemulsion, wherein the mass ratio of vanadium to palladium in the microemulsion is 1.5:1, and the solid content is 35%.
(2) Adding the micro emulsion into the graphene oxide solution, stirring at a high speed until the micro emulsion is uniformly mixed to obtain a precursor solution with the graphene oxide content of 15wt%, placing the precursor solution in liquid nitrogen for 10s for rapid freezing, and then performing vacuum drying treatment at-20 ℃ for 48h to obtain the graphene oxide-based porous sponge.
(3) Reducing the graphene oxide-based porous sponge body by double-beam laser radiation with the wavelengths of 355nm and 532nm, wherein the energy range is 50J/cm2And the treatment time is 30min, so as to obtain the graphene-based vanadium-palladium porous sponge catalyst.
(4) Placing a graphene-based vanadium-palladium porous sponge catalyst in a gas-phase oxidation reaction fixed bed, heating the gas-phase oxidation reaction fixed bed to 450 ℃, heating and melting durene at 95 ℃, introducing the durene into a vaporization mixer, mixing the durene with air at 200 ℃, continuing heating and vaporizing to obtain a mixture of durene and air, and introducing 20g/m3The mixture of the pyromellitic dianhydride and the air is subjected to circulating heat exchange and temperature reduction reaction by utilizing a mixture molten salt of potassium nitrate and sodium nitrite with the mass ratio of 1:1 at 380 ℃, is trapped, is filtered after being dissolved in an acetone solution, is crystallized for 8 hours at 45 ℃ and normal pressure, is centrifugally dried, and is subjected to sublimation treatment under vacuum heating at 250 ℃ and-0.1 MPa to obtain the pyromellitic dianhydride.
Example 3:
(1) adding oxalic acid into deionized water, heating to dissolve completely, adding ammonium metavanadate, mixing, stirring, and adding H dropwise2PdCl4And fully mixing the solution, and removing bubbles to form a microemulsion, wherein the mass ratio of vanadium to palladium in the microemulsion is 0.8:1, and the solid content is 20%.
(2) Adding the micro emulsion into the graphene oxide solution, stirring at a high speed until the micro emulsion is uniformly mixed to obtain a precursor solution with the graphene oxide content of 5wt%, placing the precursor solution in liquid nitrogen for treatment for 7s for rapid freezing, and then performing vacuum drying treatment at-20 ℃ for 36h to obtain the graphene oxide-based porous sponge.
(3) Subjecting graphene oxide-based porous sponge to double-beam laser radiation reduction with wavelengths of 355nm and 532nmThe energy range is 35J/cm2And the treatment time is 15min, so as to obtain the graphene-based vanadium-palladium porous sponge catalyst.
(4) Placing graphene-based vanadium-palladium porous sponge catalyst in a gas-phase oxidation reaction fixed bed, heating the gas-phase oxidation reaction fixed bed to 380 ℃, heating and melting durene at 92 ℃, introducing the durene into a vaporization mixer, mixing the durene with air at 195 ℃, continuing heating and vaporizing to obtain a mixture of durene and air, introducing 20g/m3The mixture of the pyromellitic dianhydride and the air is subjected to circulating heat exchange and temperature reduction reaction by utilizing a mixture molten salt of potassium nitrate and sodium nitrite with the mass ratio of 1:1 at 360 ℃, is trapped, is filtered after being dissolved in an acetone solution, is crystallized for 7 hours at 42 ℃ and normal pressure, is centrifugally dried, and is subjected to sublimation treatment under vacuum heating at 245 ℃ and-0.09 MPa to obtain the pyromellitic dianhydride.
Example 4:
(1) adding oxalic acid into deionized water, heating to dissolve completely, adding ammonium metavanadate, mixing, stirring, and adding H dropwise2PdCl4And fully mixing the solution, and removing bubbles to form a microemulsion, wherein the mass ratio of vanadium to palladium in the microemulsion is 1.2:1, and the solid content is 18%.
(2) Adding the micro emulsion into the graphene oxide solution, stirring at a high speed until the micro emulsion is uniformly mixed to obtain a precursor solution with the graphene oxide content of 8wt%, placing the precursor solution in liquid nitrogen for 8s for rapid freezing, and then performing vacuum drying treatment at-20 ℃ for 24h to obtain the graphene oxide-based porous sponge.
(3) Reducing the graphene oxide-based porous sponge body by double-beam laser radiation with the wavelengths of 355nm and 532nm, wherein the energy range is 30J/cm2And the treatment time is 20min, so as to obtain the graphene-based vanadium-palladium porous sponge catalyst.
(4) Placing graphene-based vanadium-palladium porous sponge catalyst in a gas-phase oxidation reaction fixed bed, heating the gas-phase oxidation reaction fixed bed to 420 ℃, heating and melting durene at 93 ℃, introducing the durene into a vaporization mixer, mixing the durene with air at 190 ℃,heating and vaporizing to obtain mixture of durene and air, and introducing 20g/m3The mixture of the pyromellitic dianhydride and the air is subjected to circulating heat exchange and temperature reduction reaction by utilizing a mixture molten salt of potassium nitrate and sodium nitrite with the mass ratio of 1:1 at 365 ℃, is trapped, is filtered after being dissolved in an acetone solution, is crystallized for 7.5 hours at 42 ℃ and normal pressure, is centrifugally dried, and is subjected to sublimation treatment under vacuum heating at 245 ℃ and-0.1 MPa to obtain the pyromellitic dianhydride.
Example 5:
(1) adding oxalic acid into deionized water, heating to dissolve completely, adding ammonium metavanadate, mixing, stirring, and adding H dropwise2PdCl4And fully mixing the solution, and removing bubbles to form a microemulsion, wherein the mass ratio of vanadium to palladium in the microemulsion is 0.3:1, and the solid content is 35%.
(2) Adding the micro emulsion into the graphene oxide solution, stirring at a high speed until the micro emulsion is uniformly mixed to obtain a precursor solution with the graphene oxide content of 0.5wt%, placing the precursor solution in liquid nitrogen for 10s for quick freezing, and then performing vacuum drying treatment at-20 ℃ for 24h to obtain the graphene oxide-based porous sponge body.
(3) Reducing the graphene oxide-based porous sponge body by double-beam laser radiation with the wavelengths of 355nm and 532nm, wherein the energy range is 50J/cm2And the treatment time is 5min, so as to obtain the graphene-based vanadium-palladium porous sponge catalyst.
(4) Placing a graphene-based vanadium-palladium porous sponge catalyst in a gas-phase oxidation reaction fixed bed, heating the gas-phase oxidation reaction fixed bed to 450 ℃, heating and melting durene at 90 ℃, introducing the durene into a vaporization mixer, mixing the durene with air at 200 ℃, continuing heating and vaporizing to obtain a mixture of durene and air, and introducing 20g/m3The mixture of durene and air is subjected to circulating heat exchange and temperature reduction reaction by utilizing a mixture molten salt of potassium nitrate and sodium nitrite with the mass ratio of 1:1 at 350 ℃, is trapped, is filtered after being dissolved in an acetone solution, is crystallized for 6 hours at 45 ℃ and normal pressure, is centrifugally dried, and is subjected to vacuum drying at 250 ℃ and-0.09 MPaHeating for sublimation treatment to obtain pyromellitic dianhydride.
Example 6:
(1) adding oxalic acid into deionized water, heating to dissolve completely, adding ammonium metavanadate, mixing, stirring, and adding H dropwise2PdCl4And fully mixing the solution, and removing bubbles to form a microemulsion, wherein the mass ratio of vanadium to palladium in the microemulsion is 1.5:1, and the solid content is 15%.
(2) Adding the micro emulsion into the graphene oxide solution, stirring at a high speed until the micro emulsion is uniformly mixed to obtain a precursor solution with the graphene oxide content of 15wt%, placing the precursor solution in liquid nitrogen for 5s for quick freezing, and then performing vacuum drying treatment at-20 ℃ for 48h to obtain the graphene oxide-based porous sponge.
(3) Reducing the graphene oxide-based porous sponge body by double-beam laser radiation with the wavelengths of 355nm and 532nm, wherein the energy range is 20J/cm2And the treatment time is 30min, so as to obtain the graphene-based vanadium-palladium porous sponge catalyst.
(4) Placing a graphene-based vanadium-palladium porous sponge catalyst in a gas-phase oxidation reaction fixed bed, heating the gas-phase oxidation reaction fixed bed to 320 ℃, heating and melting durene at 95 ℃, introducing the durene into a vaporization mixer, mixing the durene with air at 190 ℃, continuing heating and vaporizing to obtain a mixture of durene and air, and introducing 20g/m3The mixture of the pyromellitic dianhydride and the air is subjected to circulating heat exchange and temperature reduction reaction by utilizing a mixture molten salt of potassium nitrate and sodium nitrite with the mass ratio of 1:1 at 380 ℃, is trapped, is filtered after being dissolved in an acetone solution, is crystallized for 8 hours at 40 ℃ and normal pressure, is centrifugally dried, and is subjected to sublimation treatment under vacuum heating at 240 ℃ and-0.1 MPa to obtain the pyromellitic dianhydride.
The results of the examination of the mass yields and the carbon dioxide contents of pyromellitic dianhydride prepared in examples 1 to 6 are as follows:
| example 1 | Example 2 | Example 3 | Example 4 | Example 5 | Example 6 | |
| Mass yield (%) | 89 | 96 | 94 | 93 | 95 | 95 |
| Carbon dioxide content (%) | 0.56 | 0.64 | 0.57 | 0.61 | 0.62 | 0.61 |
As can be seen from the table, the pyromellitic dianhydride prepared by the graphene-based vanadium-palladium porous sponge catalyst has high quality yield, less generated carbon dioxide content and higher product purity.
The foregoing embodiments are merely illustrative of the principles and utilities of the present invention and are not intended to limit the invention. Any person skilled in the art can modify or change the above-mentioned embodiments without departing from the spirit and scope of the present invention. Accordingly, it is intended that all equivalent modifications or changes which can be made by those skilled in the art without departing from the spirit and technical spirit of the present invention be covered by the claims of the present invention.
Claims (7)
1. A method for preparing pyromellitic dianhydride based on graphene sponge body catalysis is characterized by comprising the following steps: the method comprises the following steps:
(1) adding oxalic acid into deionized water, heating until the oxalic acid is completely dissolved, adding ammonium metavanadate, mixing, continuously stirring, dropwise adding a palladium chloride solution, fully mixing, and removing bubbles to form a microemulsion;
(2) adding the micro emulsion into the graphene oxide solution, stirring at a high speed until the micro emulsion is uniformly mixed to obtain a precursor solution, and placing the precursor solution in a low-temperature environment for rapid freezing and vacuum drying treatment to obtain a graphene oxide-based porous sponge body;
(3) reducing the graphene oxide-based porous sponge body prepared in the step (2) by laser radiation to obtain a graphene-based vanadium-palladium porous sponge catalyst;
(4) placing the graphene-based vanadium-palladium porous sponge catalyst prepared in the step (3) in a gas-phase oxidation reaction fixed bed, heating the gas-phase oxidation reaction fixed bed to the temperature of 320-450 ℃, introducing a mixture of durene and air, performing a circulating heat exchange cooling reaction by using molten salt, trapping, performing hydrolysis, crystallization and sublimation to obtain the pyromellitic dianhydride;
in the step (2), the rapid freezing is liquid nitrogen treatment for 5-10s, the vacuum drying treatment temperature is-20 ℃, the time is 24-48h, in the step (3), the laser radiation is double beams, the wavelength is 355nm and 532nm, and the energy range is 20-50J/cm2The time of laser radiation reduction treatment is 5-30 min.
2. The graphene sponge catalytic system according to claim 1The method for preparing the pyromellitic dianhydride is characterized by comprising the following steps: in the step (1), the palladium chloride solution is H2PdCl4And (3) solution.
3. The method for preparing pyromellitic dianhydride based on graphene sponge body catalysis according to claim 1, wherein the method comprises the following steps: in the step (1), the mass ratio of vanadium to palladium in the microemulsion is 0.3-1.5:1, and the solid content is 15-35%.
4. The method for preparing pyromellitic dianhydride based on graphene sponge body catalysis according to claim 1, wherein the method comprises the following steps: in the step (2), the content of the graphene oxide in the precursor solution is 0.5-15 wt%.
5. The method for preparing pyromellitic dianhydride based on graphene sponge body catalysis according to claim 1, wherein the method comprises the following steps: in the step (4), the preparation method of the mixture of durene and air comprises the following steps: heating and melting durene at 90-95 ℃, introducing the durene into a vaporization mixer, mixing the durene with air at the temperature of 190-200 ℃, and continuing heating and vaporizing to obtain the durene.
6. The method for preparing pyromellitic dianhydride based on graphene sponge body catalysis according to claim 1, wherein the method comprises the following steps: in the step (4), the molten salt is a mixture of potassium nitrate and sodium nitrite with a mass ratio of 1:1, and the temperature of the molten salt is 350-380 ℃.
7. The method for preparing pyromellitic dianhydride based on graphene sponge body catalysis according to claim 1, wherein the method comprises the following steps: in the step (4), the hydrolysis crystallization conditions are as follows: dissolving the trapped crude pyromellitic dianhydride in acetone solution, filtering, crystallizing at 40-45 deg.c and normal pressure for 6-8 hr, centrifugal drying, and vacuum heating at 250 deg.c and-0.09-0.1 MPa for sublimation.
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| CN102336761A (en) * | 2010-12-17 | 2012-02-01 | 常熟市联邦化工有限公司 | Method for capturing and purifying pyromellitic dianhydride |
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| US6084109A (en) * | 1998-07-31 | 2000-07-04 | Chinese Petroleum Corp. | Process for the preparation of pyromellitic dianhydride |
| CN102336761A (en) * | 2010-12-17 | 2012-02-01 | 常熟市联邦化工有限公司 | Method for capturing and purifying pyromellitic dianhydride |
| CN102626648A (en) * | 2012-03-20 | 2012-08-08 | 常熟市联邦化工有限公司 | Preparation of pyromellitic dianhydride (PMDA) multi-component oxide catalyst through catalytic gas phase oxidation method |
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