CN116078420A - Catalyst and preparation method thereof, and preparation method and application of aromatic compound - Google Patents
Catalyst and preparation method thereof, and preparation method and application of aromatic compound Download PDFInfo
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- CN116078420A CN116078420A CN202211564159.7A CN202211564159A CN116078420A CN 116078420 A CN116078420 A CN 116078420A CN 202211564159 A CN202211564159 A CN 202211564159A CN 116078420 A CN116078420 A CN 116078420A
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- molecular sieve
- pyrolysis
- epoxy resin
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- 239000003054 catalyst Substances 0.000 title claims abstract description 76
- 150000001491 aromatic compounds Chemical class 0.000 title claims abstract description 41
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- 239000002808 molecular sieve Substances 0.000 claims abstract description 104
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims abstract description 104
- 229910021536 Zeolite Inorganic materials 0.000 claims abstract description 77
- 239000010457 zeolite Substances 0.000 claims abstract description 77
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims abstract description 61
- 239000003822 epoxy resin Substances 0.000 claims abstract description 44
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 44
- CHPZKNULDCNCBW-UHFFFAOYSA-N gallium nitrate Chemical compound [Ga+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O CHPZKNULDCNCBW-UHFFFAOYSA-N 0.000 claims abstract description 38
- 239000002699 waste material Substances 0.000 claims abstract description 36
- 239000007864 aqueous solution Substances 0.000 claims abstract description 19
- 229940044658 gallium nitrate Drugs 0.000 claims abstract description 19
- 238000011084 recovery Methods 0.000 claims abstract description 4
- 238000000197 pyrolysis Methods 0.000 claims description 68
- 238000001354 calcination Methods 0.000 claims description 38
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 26
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 claims description 26
- 229910052733 gallium Inorganic materials 0.000 claims description 26
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 16
- 238000002156 mixing Methods 0.000 claims description 15
- 230000000630 rising effect Effects 0.000 claims description 14
- 229910052786 argon Inorganic materials 0.000 claims description 13
- 238000000034 method Methods 0.000 claims description 12
- -1 monocyclic aromatic hydrocarbon Chemical class 0.000 claims description 12
- 239000002994 raw material Substances 0.000 claims description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 8
- 238000006243 chemical reaction Methods 0.000 claims description 6
- 125000005575 polycyclic aromatic hydrocarbon group Chemical group 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- 239000001301 oxygen Substances 0.000 claims description 4
- 229910052760 oxygen Inorganic materials 0.000 claims description 4
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 claims description 3
- 239000001307 helium Substances 0.000 claims description 3
- 229910052734 helium Inorganic materials 0.000 claims description 3
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 3
- 229920001187 thermosetting polymer Polymers 0.000 claims description 3
- 239000004033 plastic Substances 0.000 claims description 2
- 229920003023 plastic Polymers 0.000 claims description 2
- 229920005989 resin Polymers 0.000 claims description 2
- 239000011347 resin Substances 0.000 claims description 2
- 238000007669 thermal treatment Methods 0.000 claims description 2
- 230000003197 catalytic effect Effects 0.000 abstract description 8
- 239000004566 building material Substances 0.000 abstract description 6
- 239000007788 liquid Substances 0.000 abstract description 4
- 238000004064 recycling Methods 0.000 abstract description 4
- 239000002910 solid waste Substances 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 23
- 238000001035 drying Methods 0.000 description 16
- 239000000243 solution Substances 0.000 description 15
- 238000010438 heat treatment Methods 0.000 description 12
- 239000000047 product Substances 0.000 description 9
- 239000000463 material Substances 0.000 description 8
- 229910052751 metal Inorganic materials 0.000 description 7
- 239000002184 metal Substances 0.000 description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 239000007789 gas Substances 0.000 description 6
- 239000000126 substance Substances 0.000 description 4
- QPUYECUOLPXSFR-UHFFFAOYSA-N 1-methylnaphthalene Chemical compound C1=CC=C2C(C)=CC=CC2=C1 QPUYECUOLPXSFR-UHFFFAOYSA-N 0.000 description 2
- HGUFODBRKLSHSI-UHFFFAOYSA-N 2,3,7,8-tetrachloro-dibenzo-p-dioxin Chemical compound O1C2=CC(Cl)=C(Cl)C=C2OC2=C1C=C(Cl)C(Cl)=C2 HGUFODBRKLSHSI-UHFFFAOYSA-N 0.000 description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 238000007233 catalytic pyrolysis Methods 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 238000005336 cracking Methods 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 239000008096 xylene Substances 0.000 description 2
- 239000007848 Bronsted acid Substances 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- 239000002841 Lewis acid Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 150000007517 lewis acids Chemical class 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G1/00—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal
- C10G1/10—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal from rubber or rubber waste
-
- 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
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/08—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y
- B01J29/085—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y containing rare earth elements, titanium, zirconium, hafnium, zinc, cadmium, mercury, gallium, indium, thallium, tin or lead
- B01J29/088—Y-type faujasite
-
- 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
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
- B01J29/405—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively containing rare earth elements, titanium, zirconium, hafnium, zinc, cadmium, mercury, gallium, indium, thallium, tin or lead
-
- 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
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
- B01J29/7049—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing rare earth elements, titanium, zirconium, hafnium, zinc, cadmium, mercury, gallium, indium, thallium, tin or lead
- B01J29/7057—Zeolite Beta
-
- 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
- B01J37/08—Heat treatment
-
- 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
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
- B01J37/088—Decomposition of a metal salt
-
- 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
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/10—After treatment, characterised by the effect to be obtained
- B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
- B01J2229/186—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself not in framework positions
-
- 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
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/30—After treatment, characterised by the means used
- B01J2229/40—Special temperature treatment, i.e. other than just for template removal
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Crystallography & Structural Chemistry (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- General Chemical & Material Sciences (AREA)
- Wood Science & Technology (AREA)
- Life Sciences & Earth Sciences (AREA)
- Catalysts (AREA)
Abstract
The invention belongs to the technical field of comprehensive utilization of solid wastes, and particularly relates to a catalyst, a preparation method thereof, a preparation method of aromatic compounds and application thereof. The preparation method of the catalyst comprises the following steps: the molecular sieve is calcined for the first time, then dispersed into gallium nitrate aqueous solution, dispersed ultrasonically at room temperature, dried and calcined for the second time, and the catalyst is prepared; the molecular sieve is one of ZSM-5 zeolite, Y-zeolite and beta-zeolite. The catalyst prepared by the invention has the advantages of high catalytic activity, good stability, high selectivity, easy recovery and the like, can efficiently catalyze and pyrolyze the waste epoxy resin to generate liquid oil rich in aromatic compounds, and realizes the clean treatment and recycling of the waste epoxy resin including waste epoxy resin fan blades, waste epoxy resin circuit boards and waste epoxy resin building materials.
Description
Technical Field
The invention belongs to the technical field of comprehensive utilization of solid wastes, and particularly relates to a catalyst, a preparation method thereof, a preparation method of aromatic compounds and application thereof.
Background
Disposal of waste epoxy materials has become an emerging issue. In recent years, epoxy resin composite materials have been widely used in the fields of aerospace, automobiles, ships, building materials, and the like, because of their excellent strength and outstanding advantages such as excellent corrosion resistance, fatigue resistance, electromagnetic shielding, and the like. In addition, as the scale growth rate of wind power plants continues to increase, the demand for fan blades based on epoxy resin composites has increased year by year. However, the design life of wind power plants is typically not more than 20 years, and a large amount of fan blade waste is generated after the fans are scrapped. Due to the high carbon emissions, energy consumption and expense of producing epoxy resin materials, it is necessary to utilize the epoxy resin in the waste fan blades as a resource. In addition to fan blades, circuit boards, building materials and the like based on epoxy resins also face the problem of disposal of waste. Because the epoxy resin material has complex chemical properties and is a thermosetting material, the epoxy resin material cannot be dissolved in any organic solvent and cannot be melted when heated, the recycling difficulty is high, and the epoxy resin material is mostly treated by adopting a direct landfill or incineration method at present, so that serious resource waste is caused. In addition, the incineration of the epoxy resin can generate a large amount of pollutants such as dioxin and the like, thereby causing serious influence on the ecological environment. In contrast, pyrolysis technology can avoid the generation of dioxin by cracking epoxy resin in an anaerobic environment, and can recycle valuable coke, pyrolysis oil and gas products, thereby having wide application prospect. However, the main components of the liquid oil in the direct pyrolysis product of the epoxy resin are various phenol products mainly comprising phenol, the oxygen content is too high, the liquid oil has stronger corrosiveness, and the utilization value and the heat value are low. Therefore, it is necessary to improve the quality of the pyrolysis oil of epoxy resin by means of catalysis or the like so as to realize the recycling of the waste epoxy resin material.
Disclosure of Invention
The invention aims to provide a catalyst, a preparation method thereof, a preparation method of aromatic compounds and application thereof. The metal-supported molecular sieve catalyst which has high catalytic activity, good stability and easy recovery is prepared, and the waste epoxy resin can be subjected to high-efficiency catalytic pyrolysis to generate liquid oil rich in aromatic compounds.
In order to achieve the above purpose, the present invention adopts the following technical scheme: a method for preparing a catalyst comprising the steps of:
the molecular sieve is calcined for the first time, then dispersed into gallium nitrate aqueous solution, dispersed ultrasonically at room temperature, dried and calcined for the second time, and the catalyst is prepared;
the molecular sieve is one of ZSM-5 zeolite, Y-zeolite and beta-zeolite.
Preferably, the mass of gallium element in the gallium nitrate aqueous solution is 0.1-10% of the mass of the molecular sieve.
Preferably, the preparation method of the catalyst at least comprises one of the following (1) to (3):
(1) The first calcination is carried out for 1-12 h under the conditions of air atmosphere environment and 450-550 ℃;
(2) The condition of the second calcination is that the calcination is carried out for 1 to 12 hours under the air atmosphere environment and the temperature of 500 to 550 ℃;
(3) The ultrasonic dispersion time is 2-12 h.
A catalyst prepared by the preparation method of the catalyst.
A process for the preparation of an aromatic compound comprising the steps of:
mixing the raw materials and the catalyst, and performing co-pyrolysis in an oxygen-free environment to prepare the aromatic compound.
Preferably, the method comprises the steps of,the reaction conditions of the co-pyrolysis are as follows: carrying out co-pyrolysis at 500-800 ℃ with the temperature rising rate of 10-10 4 The temperature of the co-pyrolysis is 5-60 s.
Preferably, the method for producing an aromatic compound includes at least one of the following (1) to (4):
(1) The mass ratio of the raw materials to the catalyst is 1: (1-10);
(2) The raw materials are waste epoxy resin;
(3) The grain size of the raw materials is 50-200 meshes;
(4) The anaerobic environment is an atmosphere of nitrogen, argon or helium.
More preferably, the waste epoxy resin comprises at least one of waste epoxy resin fan blades, waste epoxy resin circuit boards and waste epoxy resin building materials.
Preferably, the aromatic compounds include monocyclic aromatic hydrocarbons (benzene, toluene, xylene, etc.) and polycyclic aromatic hydrocarbons (naphthalene, methylnaphthalene, etc.).
Preferably, the catalyst is recovered by calcination after the co-pyrolysis reaction is completed.
The recovery method comprises the following steps: calcining the catalyst in an air atmosphere at 500-550 ℃ for 1-12 h to obtain the regenerated catalyst.
Use of said catalyst for the thermal treatment of waste epoxy resins, oxygen-containing thermosetting resins/plastics.
According to the invention, the catalyst with excellent catalytic performance and good single-ring aromatic hydrocarbon selectivity is prepared by selecting the specific molecular sieve for gallium loading, and the metal gallium element in the catalyst can obviously improve Lewis acid sites while keeping the strong acid Bronsted acid sites of the molecular sieve catalyst in a reaction system, so that the high-efficiency cracking and deoxidizing of raw materials (epoxy resin) are realized, and the oxygen content in pyrolysis oil is greatly reduced. Meanwhile, the gallium metal in the catalyst can realize the adjustment function on the pore structure of the catalyst, and reduce the average pore diameter of the catalyst, so that the selectivity of reaction products such as high-value monocyclic aromatic hydrocarbon (benzene, toluene, xylene) and the like is effectively improved in the catalytic reaction.
Compared with the prior art, the invention has the following beneficial effects:
(1) The catalyst prepared by compounding the specific molecular sieve and the gallium metal can realize better catalytic effect, improve the yield of aromatic compounds, and have higher selectivity for high-value reaction products such as monocyclic aromatic hydrocarbon and the like.
(2) According to the invention, the gallium metal supported molecular sieve catalyst is applied to the high-efficiency catalytic pyrolysis of the waste epoxy resin, so that the higher aromatic compound selectivity and yield are obtained, and meanwhile, the clean disposal and the recycling utilization of the waste epoxy resin are realized.
(3) The catalyst prepared by the invention still has good catalytic activity after being regenerated by pyrolysis cycle for multiple times, and has higher practical value.
Detailed Description
The technical solutions of the embodiments of the present invention will be clearly and completely described below in conjunction with the embodiments of the present invention, and it is apparent that the described embodiments are only some embodiments of the present invention, not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
In the examples and comparative examples, the experimental methods used were conventional methods, and the materials, reagents and the like used were commercially available, unless otherwise specified.
Example 1
Calcining a ZSM-5 zeolite molecular sieve at 550 ℃ for 3 hours under an air atmosphere, uniformly dispersing the ZSM-5 zeolite molecular sieve into a gallium nitrate aqueous solution containing gallium which is 1% of the mass of the ZSM-5 zeolite molecular sieve (ensuring that the molecular sieve is completely wetted by the solution), performing ultrasonic dispersion at room temperature for 5 hours, directly drying the ZSM-5 zeolite molecular sieve, and calcining the ZSM-5 zeolite molecular sieve at 500 ℃ for 6 hours under the air atmosphere to obtain a catalyst;
fully mixing waste epoxy resin fan blades with 100 meshes and a catalyst according to the mass ratio of 1:10, and heating at pyrolysis temperature of 600 ℃ and temperature rising rate of 10 4 And (3) carrying out co-pyrolysis for 20s under the condition of argon in a pyrolysis atmosphere at the temperature of/s to obtain the aromatic compound.
The relative content of various chemicals in the pyrolysis product is analyzed by a gas chromatograph-mass spectrometer, and the relative content of aromatic compounds in the pyrolysis product is calculated to be 56.3%, wherein the relative content of monocyclic aromatic hydrocarbon is 25.5%, and the relative content of polycyclic aromatic hydrocarbon is 30.8%. See table 1.
Example 2
Calcining a ZSM-5 zeolite molecular sieve at 450 ℃ for 3 hours under an air atmosphere, uniformly dispersing the ZSM-5 zeolite molecular sieve into a gallium nitrate aqueous solution containing gallium which is 1% of the mass of the ZSM-5 zeolite molecular sieve (ensuring that the molecular sieve is completely wetted by the solution), performing ultrasonic dispersion at room temperature for 5 hours, directly drying the ZSM-5 zeolite molecular sieve, and calcining the ZSM-5 zeolite molecular sieve at 550 ℃ for 6 hours under the air atmosphere to obtain a catalyst;
fully mixing 100-mesh waste epoxy resin fan blades and a catalyst according to a mass ratio of 1:1, and heating at a pyrolysis temperature of 600 ℃ at a temperature rising rate of 10 4 And (3) carrying out co-pyrolysis for 20s under the condition of nitrogen in a pyrolysis atmosphere at the temperature of C/s to obtain the aromatic compound.
Example 3
Calcining a ZSM-5 zeolite molecular sieve at 550 ℃ for 3 hours under an air atmosphere, uniformly dispersing the ZSM-5 zeolite molecular sieve into a gallium nitrate aqueous solution containing gallium which is 1% of the molecular sieve in mass (ensuring that the molecular sieve is completely wetted by the solution), performing ultrasonic dispersion at room temperature for 5 hours, directly drying the molecular sieve, and calcining the molecular sieve at 500 ℃ for 6 hours under the air atmosphere to prepare a catalyst;
fully mixing 100-mesh waste epoxy resin fan blades and a catalyst according to a mass ratio of 1:5, and heating at a pyrolysis temperature of 600 ℃ at a temperature rising rate of 10 4 And (3) carrying out co-pyrolysis for 20s under the condition of the temperature of the pyrolysis gas/s and the helium gas as the pyrolysis atmosphere to obtain the aromatic compound.
Example 4
Calcining a ZSM-5 zeolite molecular sieve at 550 ℃ for 3 hours under an air atmosphere, uniformly dispersing the ZSM-5 zeolite molecular sieve into a gallium nitrate aqueous solution containing gallium which is 0.1% of the mass of the ZSM-5 zeolite molecular sieve (ensuring that the molecular sieve is completely wetted by the solution), performing ultrasonic dispersion for 5 hours at room temperature, directly drying the ZSM-5 zeolite molecular sieve, and calcining the ZSM-5 zeolite molecular sieve at 500 ℃ for 6 hours under the air atmosphere to obtain a catalyst;
fully mixing 100-mesh waste epoxy resin fan blades and a catalyst according to a mass ratio of 1:10, and heating at a pyrolysis temperature of 600 ℃ at a temperature rising rate of 10 4 And (3) carrying out co-pyrolysis for 20s under the condition of argon in a pyrolysis atmosphere at the temperature of/s to obtain the aromatic compound.
Example 5
Calcining a ZSM-5 zeolite molecular sieve at 550 ℃ for 3 hours under an air atmosphere, uniformly dispersing the ZSM-5 zeolite molecular sieve into a gallium nitrate aqueous solution containing gallium which is equivalent to 5% of the mass of the ZSM-5 zeolite molecular sieve (ensuring that the molecular sieve is completely wetted by the solution), performing ultrasonic dispersion at room temperature for 5 hours, directly drying the ZSM-5 zeolite molecular sieve, and calcining the ZSM-5 zeolite molecular sieve at 500 ℃ for 6 hours under the air atmosphere to obtain a catalyst;
fully mixing 100-mesh waste epoxy resin fan blades and a catalyst according to a mass ratio of 1:10, and heating at a pyrolysis temperature of 600 ℃ at a temperature rising rate of 10 4 And (3) carrying out co-pyrolysis for 20s under the condition of argon in a pyrolysis atmosphere at the temperature of/s to obtain the aromatic compound.
Example 6
Calcining a ZSM-5 zeolite molecular sieve at 550 ℃ for 3 hours under an air atmosphere, uniformly dispersing the ZSM-5 zeolite molecular sieve into a gallium nitrate aqueous solution containing gallium which is equivalent to 10% of the mass of the ZSM-5 zeolite molecular sieve (ensuring that the molecular sieve is completely wetted by the solution), performing ultrasonic dispersion at room temperature for 5 hours, directly drying the ZSM-5 zeolite molecular sieve, and calcining the ZSM-5 zeolite molecular sieve at 500 ℃ for 6 hours under the air atmosphere to obtain a catalyst;
fully mixing 100-mesh waste epoxy resin fan blades and a catalyst according to a mass ratio of 1:10, and heating at a pyrolysis temperature of 600 ℃ at a temperature rising rate of 10 4 And (3) carrying out co-pyrolysis for 20s under the condition of argon in a pyrolysis atmosphere at the temperature of/s to obtain the aromatic compound.
Example 7
Calcining the Y-zeolite molecular sieve at 550 ℃ for 3 hours in an air atmosphere, uniformly dispersing the Y-zeolite molecular sieve into a gallium nitrate aqueous solution containing gallium which is 1% of the mass of the Y-zeolite molecular sieve (ensuring that the molecular sieve is completely wetted by the solution), performing ultrasonic dispersion at room temperature for 5 hours, directly drying the Y-zeolite molecular sieve, and calcining the Y-zeolite molecular sieve at 500 ℃ for 6 hours in the air atmosphere to obtain a catalyst;
100 meshes ofThe waste epoxy resin fan blade and the catalyst are fully mixed according to the mass ratio of 1:10, and the temperature rising rate is 10 at the pyrolysis temperature of 600 DEG C 4 And (3) carrying out co-pyrolysis for 20s under the condition of argon in a pyrolysis atmosphere at the temperature of/s to obtain the aromatic compound.
Example 8
Calcining the beta-zeolite molecular sieve at 550 ℃ for 3 hours in an air atmosphere, uniformly dispersing the beta-zeolite molecular sieve into a gallium nitrate aqueous solution containing gallium which is 1% of the mass of the beta-zeolite molecular sieve (ensuring that the molecular sieve is completely wetted by the solution), performing ultrasonic dispersion at room temperature for 5 hours, directly drying the beta-zeolite molecular sieve, and calcining the beta-zeolite molecular sieve at 500 ℃ for 6 hours in the air atmosphere to obtain a catalyst;
fully mixing 100-mesh waste epoxy resin fan blades and a catalyst according to a mass ratio of 1:10, and heating at a pyrolysis temperature of 600 ℃ at a temperature rising rate of 10 4 And (3) carrying out co-pyrolysis for 20s under the condition of argon in a pyrolysis atmosphere at the temperature of/s to obtain the aromatic compound.
Example 9
Calcining a ZSM-5 zeolite molecular sieve at 550 ℃ for 3 hours under an air atmosphere, uniformly dispersing the ZSM-5 zeolite molecular sieve into a gallium nitrate aqueous solution containing gallium which is 1% of the mass of the ZSM-5 zeolite molecular sieve (ensuring that the molecular sieve is completely wetted by the solution), performing ultrasonic dispersion at room temperature for 5 hours, directly drying the ZSM-5 zeolite molecular sieve, and calcining the ZSM-5 zeolite molecular sieve at 500 ℃ for 6 hours under the air atmosphere to obtain a catalyst;
fully mixing 100-mesh waste epoxy resin fan blades and a catalyst according to a mass ratio of 1:10, and heating at a pyrolysis temperature of 500 ℃ at a temperature rising rate of 10 4 And (3) carrying out co-pyrolysis for 20s under the condition of argon in a pyrolysis atmosphere at the temperature of/s to obtain the aromatic compound.
Example 10
Calcining a ZSM-5 zeolite molecular sieve at 550 ℃ for 3 hours under an air atmosphere, uniformly dispersing the ZSM-5 zeolite molecular sieve into a gallium nitrate aqueous solution containing gallium which is 1% of the mass of the ZSM-5 zeolite molecular sieve (ensuring that the molecular sieve is completely wetted by the solution), performing ultrasonic dispersion at room temperature for 5 hours, directly drying the ZSM-5 zeolite molecular sieve, and calcining the ZSM-5 zeolite molecular sieve at 500 ℃ for 6 hours under the air atmosphere to obtain a catalyst;
fully mixing 100-mesh waste epoxy resin fan blades and a catalyst according to a mass ratio of 1:10, and carrying out pyrolysis at 800 DEG CRate of temperature rise 10 4 And (3) carrying out co-pyrolysis for 20s under the condition of nitrogen in a pyrolysis atmosphere at the temperature of C/s to obtain the aromatic compound.
Example 11
Calcining a ZSM-5 zeolite molecular sieve at 550 ℃ for 3 hours under an air atmosphere, uniformly dispersing the ZSM-5 zeolite molecular sieve into a gallium nitrate aqueous solution containing gallium which is 1% of the mass of the ZSM-5 zeolite molecular sieve (ensuring that the molecular sieve is completely wetted by the solution), performing ultrasonic dispersion at room temperature for 5 hours, directly drying the ZSM-5 zeolite molecular sieve, and calcining the ZSM-5 zeolite molecular sieve at 500 ℃ for 6 hours under the air atmosphere to obtain a catalyst;
fully mixing the waste epoxy resin building material with 50 meshes and the catalyst according to the mass ratio of 1:10, and heating at the pyrolysis temperature of 600 ℃ at the temperature rising rate of 10 4 And (3) carrying out co-pyrolysis for 20s under the condition of argon in a pyrolysis atmosphere at the temperature of/s to obtain the aromatic compound.
Example 12
Calcining a ZSM-5 zeolite molecular sieve at 550 ℃ for 3 hours under an air atmosphere, uniformly dispersing the ZSM-5 zeolite molecular sieve into a gallium nitrate aqueous solution containing gallium which is equivalent to 10% of the mass of the ZSM-5 zeolite molecular sieve (ensuring that the molecular sieve is completely wetted by the solution), performing ultrasonic dispersion at room temperature for 5 hours, directly drying the ZSM-5 zeolite molecular sieve, and calcining the ZSM-5 zeolite molecular sieve at 500 ℃ for 6 hours under the air atmosphere to obtain a catalyst;
fully mixing the waste epoxy resin building material with 200 meshes and the catalyst according to the mass ratio of 1:10, and heating at the pyrolysis temperature of 600 ℃ at the temperature rising rate of 10 4 And (3) carrying out co-pyrolysis for 20s under the condition of argon in a pyrolysis atmosphere at the temperature of/s to obtain the aromatic compound.
Example 13
Calcining a ZSM-5 zeolite molecular sieve at 550 ℃ for 3 hours under an air atmosphere, uniformly dispersing the ZSM-5 zeolite molecular sieve into a gallium nitrate aqueous solution containing gallium which is 1% of the mass of the ZSM-5 zeolite molecular sieve (ensuring that the molecular sieve is completely wetted by the solution), performing ultrasonic dispersion at room temperature for 5 hours, directly drying the ZSM-5 zeolite molecular sieve, and calcining the ZSM-5 zeolite molecular sieve at 500 ℃ for 6 hours under the air atmosphere to obtain a catalyst;
fully mixing 100-mesh waste epoxy resin fan blades and a catalyst according to a mass ratio of 1:10, and carrying out co-pyrolysis for 20s under the conditions that the pyrolysis temperature is 600 ℃, the heating rate is 10 ℃/s and the pyrolysis atmosphere is argon, so as to prepare the aromatic compound.
Example 14
Calcining a ZSM-5 zeolite molecular sieve at 550 ℃ for 3 hours under an air atmosphere, uniformly dispersing the ZSM-5 zeolite molecular sieve into a gallium nitrate aqueous solution containing gallium which is 1% of the mass of the ZSM-5 zeolite molecular sieve (ensuring that the molecular sieve is completely wetted by the solution), performing ultrasonic dispersion at room temperature for 5 hours, directly drying the ZSM-5 zeolite molecular sieve, and calcining the ZSM-5 zeolite molecular sieve at 500 ℃ for 6 hours under the air atmosphere to obtain a catalyst;
fully mixing 100-mesh waste epoxy resin fan blades and a catalyst according to a mass ratio of 1:10, and heating at a pyrolysis temperature of 600 ℃ at a temperature rising rate of 10 2 And (3) carrying out co-pyrolysis for 20s under the condition of argon in a pyrolysis atmosphere at the temperature of/s to obtain the aromatic compound.
Comparative example 1
The only difference of this comparative example compared to example 1 is that no catalyst was added to the pyrolysis process.
The preparation method is described in example 1.
Comparative example 2
The only difference between this comparative example and example 1 is that the catalyst was a ZSM-5 zeolite molecular sieve which had not been gallium loaded.
The preparation method is described in example 1.
Comparative example 3
The only difference between this comparative example and example 1 is that the molecular sieve selected was MCM-41 molecular sieve.
The preparation method is described in example 1.
Comparative example 4
The only difference between this comparative example and example 1 is that the molecular sieve selected was ZSM-22 molecular sieve.
The preparation method is described in example 1.
Comparative example 5
The difference between this comparative example and example 1 is that the content of gallium element is 12% of the mass of ZSM-5 molecular sieve.
The preparation method is described in example 1.
Comparative example 6
The only difference in this comparative example compared to example 1 is that the temperature of the co-pyrolysis is 400 ℃.
The preparation method is described in example 1.
Comparative example 7
The only difference between this comparative example and example 1 is that the catalyst preparation process is not calcined after drying.
The preparation method is described in example 1.
The relative content of various chemicals in the pyrolysis product is analyzed by a gas chromatograph-mass spectrometer, and the relative content of aromatic compounds in the pyrolysis product is calculated to be 36.4%, wherein the relative content of monocyclic aromatic hydrocarbon is 8.2%, and the relative content of polycyclic aromatic hydrocarbon is 28.2%.
Test example I, content measurement
The relative contents of various chemicals in the pyrolysis products of examples 1 to 14 and comparative examples 1 to 6 were analyzed by a gas chromatograph-mass spectrometer, and the relative contents of aromatic compounds, monocyclic aromatic hydrocarbons and polycyclic aromatic hydrocarbons in the pyrolysis products were calculated. The results are shown in Table 1.
The relative amounts of aromatic, monocyclic aromatic, and polycyclic aromatic hydrocarbons in the groups of Table 1
From the data in Table 1, it can be seen that examples 1 to 14 of the present invention have higher yields of aromatic compounds, up to 56.3%, and higher selectivities to monocyclic aromatic hydrocarbons.
Comparative example 1, in which no catalyst was added, yielded an aromatic compound content of only 1.6% and a monocyclic aromatic hydrocarbon content of only 0.3% thereof; the catalyst of comparative example 2, which does not carry gallium metal, contained only 8.8% of monocyclic aromatic hydrocarbon although the aromatic compound content was high; the catalyst prepared in comparative example 3 and comparative example 4 has poor catalytic effect by selecting other types of molecular sieves to carry out gallium metal loading; the catalyst prepared in comparative example 5 has too high gallium metal content, and the yield of aromatic compounds obtained by the final reaction is lowered; the co-pyrolysis temperature selected in comparative example 6 is lower and the final catalytic aromatic content is significantly lower than in the examples; comparative example 7 in the preparation of the catalyst, the calcination operation was not performed after drying, and the catalyst prepared had catalytic performance and selectivity to monocyclic aromatic hydrocarbon were inferior to those of the examples.
The above embodiments are merely illustrative of the principles of the present invention and its effectiveness, and are not intended to limit the invention. Modifications and variations may be made to the above-described embodiments by those skilled in the art without departing from the spirit and scope of the invention. Accordingly, it is intended that all equivalent modifications and variations of the invention be covered by the claims, which are within the ordinary skill of the art, be within the spirit and scope of the present disclosure.
Claims (10)
1. A method for preparing a catalyst, comprising the steps of:
the molecular sieve is calcined for the first time, then dispersed into gallium nitrate aqueous solution, dispersed ultrasonically at room temperature, dried and calcined for the second time, and the catalyst is prepared;
the molecular sieve is one of ZSM-5 zeolite, Y-zeolite and beta-zeolite.
2. The method for preparing the catalyst according to claim 1, wherein the mass of gallium element in the gallium nitrate aqueous solution is 0.1-10% of the mass of the molecular sieve.
3. The method for preparing a catalyst according to claim 1, comprising at least one of the following (1) to (3):
(1) The first calcination is carried out for 1-12 h under the conditions of air atmosphere environment and 450-550 ℃;
(2) The condition of the second calcination is that the calcination is carried out for 1 to 12 hours under the air atmosphere environment and the temperature of 500 to 550 ℃;
(3) The ultrasonic dispersion time is 2-12 h.
4. A catalyst prepared by the method for preparing a catalyst according to any one of claims 1 to 3.
5. A process for the preparation of an aromatic compound, comprising the steps of:
the aromatic compound is prepared by mixing the raw materials and the catalyst according to claim 4 and performing co-pyrolysis in an oxygen-free environment.
6. The method for producing an aromatic compound according to claim 5, wherein the reaction conditions for the co-pyrolysis are: carrying out co-pyrolysis at 500-800 ℃ with the temperature rising rate of 10-10 4 The temperature of the co-pyrolysis is 5-60 s.
7. The method for producing an aromatic compound according to claim 5, wherein the method comprises at least one of the following (1) to (4):
(1) The mass ratio of the raw materials to the catalyst is 1: (1-10);
(2) The raw materials are waste epoxy resin;
(3) The grain size of the raw materials is 50-200 meshes;
(4) The anaerobic environment is an atmosphere of nitrogen, argon or helium.
8. The method for producing an aromatic compound according to claim 5, wherein the aromatic compound comprises a monocyclic aromatic hydrocarbon and a polycyclic aromatic hydrocarbon.
9. The method for producing an aromatic compound according to claim 5, wherein the catalyst is recovered by calcination after the end of the co-pyrolysis reaction.
10. Use of the catalyst according to claim 4 for the recovery of waste epoxy resins, oxygen-containing thermosetting resins/plastics thermal treatments.
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