CN115974095B - Hollow hierarchical pore composite molecular sieve and preparation method and application thereof - Google Patents
Hollow hierarchical pore composite molecular sieve and preparation method and application thereof Download PDFInfo
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- 239000002808 molecular sieve Substances 0.000 title claims abstract description 134
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 title claims abstract description 133
- 239000002131 composite material Substances 0.000 title claims abstract description 67
- 239000002149 hierarchical pore Substances 0.000 title claims abstract description 28
- 238000002360 preparation method Methods 0.000 title claims abstract description 28
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 45
- 238000003756 stirring Methods 0.000 claims abstract description 36
- 238000001035 drying Methods 0.000 claims abstract description 32
- 238000010438 heat treatment Methods 0.000 claims abstract description 32
- 238000005406 washing Methods 0.000 claims abstract description 32
- 238000001354 calcination Methods 0.000 claims abstract description 25
- 238000001914 filtration Methods 0.000 claims abstract description 18
- 239000002243 precursor Substances 0.000 claims abstract description 17
- 238000001816 cooling Methods 0.000 claims abstract description 9
- 239000000843 powder Substances 0.000 claims abstract description 9
- 238000002156 mixing Methods 0.000 claims abstract description 6
- 238000000197 pyrolysis Methods 0.000 claims description 67
- 239000005011 phenolic resin Substances 0.000 claims description 62
- 229920001568 phenolic resin Polymers 0.000 claims description 62
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 claims description 61
- 239000002699 waste material Substances 0.000 claims description 58
- -1 monocyclic aromatic hydrocarbon Chemical class 0.000 claims description 31
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 30
- 238000000034 method Methods 0.000 claims description 26
- 239000011148 porous material Substances 0.000 claims description 18
- 229910021536 Zeolite Inorganic materials 0.000 claims description 16
- 239000010457 zeolite Substances 0.000 claims description 16
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 15
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 12
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 12
- 239000000463 material Substances 0.000 claims description 10
- LPSKDVINWQNWFE-UHFFFAOYSA-M tetrapropylazanium;hydroxide Chemical group [OH-].CCC[N+](CCC)(CCC)CCC LPSKDVINWQNWFE-UHFFFAOYSA-M 0.000 claims description 9
- 239000012153 distilled water Substances 0.000 claims description 8
- 229910052786 argon Inorganic materials 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- 238000006243 chemical reaction Methods 0.000 claims description 5
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 claims description 4
- 239000003063 flame retardant Substances 0.000 claims description 4
- 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
- 238000000227 grinding Methods 0.000 claims description 2
- 238000009413 insulation Methods 0.000 claims description 2
- 239000002245 particle Substances 0.000 claims description 2
- 239000002904 solvent Substances 0.000 claims description 2
- 238000002791 soaking Methods 0.000 abstract description 9
- 230000003197 catalytic effect Effects 0.000 abstract description 8
- 238000011084 recovery Methods 0.000 abstract description 3
- 239000002910 solid waste Substances 0.000 abstract description 3
- 239000000243 solution Substances 0.000 description 29
- 230000000052 comparative effect Effects 0.000 description 17
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 16
- 239000003054 catalyst Substances 0.000 description 14
- 239000000047 product Substances 0.000 description 12
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 9
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- 229910021529 ammonia Inorganic materials 0.000 description 8
- 239000008367 deionised water Substances 0.000 description 7
- 229910021641 deionized water Inorganic materials 0.000 description 7
- 238000005342 ion exchange Methods 0.000 description 6
- 239000011259 mixed solution Substances 0.000 description 6
- 229920001187 thermosetting polymer Polymers 0.000 description 6
- 238000007233 catalytic pyrolysis Methods 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 238000004064 recycling Methods 0.000 description 4
- 229920005989 resin Polymers 0.000 description 4
- 239000011347 resin Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000008096 xylene Substances 0.000 description 3
- 239000000571 coke Substances 0.000 description 2
- 239000012263 liquid product Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000012690 zeolite precursor Substances 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000004517 catalytic hydrocracking Methods 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 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
- 230000009849 deactivation Effects 0.000 description 1
- 230000007123 defense Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 150000002500 ions Chemical group 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005065 mining Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000004227 thermal cracking Methods 0.000 description 1
- 238000007669 thermal treatment Methods 0.000 description 1
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- Silicates, Zeolites, And Molecular Sieves (AREA)
- Catalysts (AREA)
- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
Abstract
The invention belongs to the technical field of comprehensive utilization of solid wastes, and particularly relates to a hollow hierarchical pore composite molecular sieve, a preparation method and application thereof. The preparation method of the hollow hierarchical pore composite molecular sieve comprises the following steps: s1, mixing a molecular sieve with an etchant, stirring, heating, standing, filtering, washing, drying and calcining to obtain a hollow molecular sieve precursor; s2, placing the prepared hollow molecular sieve precursor into NaOH solution, heating and stirring, cooling to room temperature, washing, drying, adding the obtained powder into NH 4 Cl solution for soaking, heating and stirring, filtering, washing, drying, repeatedly adding NH 4 Cl solution into the dried solution for 2-3 times to obtain the ion-exchanged molecular sieve, and calcining in air atmosphere to obtain the hollow hierarchical pore composite molecular sieve. The hollow porous composite molecular sieve prepared by the invention has the advantages of high catalytic activity, high selectivity, good stability, easy recovery and the like.
Description
Technical Field
The invention belongs to the technical field of comprehensive utilization of solid wastes, and particularly relates to a hollow hierarchical pore composite molecular sieve, a preparation method and application thereof.
Background
In recent years, the recycling of the waste thermosetting plastics is attracting a great deal of attention, and various research results at home and abroad show that the waste thermosetting plastics can be completely recycled by reasonable technical means. The phenolic resin material has a very large proportion in thermosetting resin, and has the advantages of easily obtained raw materials, simple preparation process, excellent performance after the resin is cured and molded, and becomes the thermosetting resin which realizes mass production at first, and is widely applied to various aspects such as electronics and electricity, mining, national defense and the like. In addition, fan blades mainly made of phenolic resin composite materials are in increasing demand year by year due to their excellent heat resistance, electrical resistance, corrosion resistance and the like. However, due to the limitation of the design life of the wind driven generator, the service life of the wind driven generator is often not longer than 20 years. This results in a large number of waste fan blades after the fan is scrapped, and in addition, phenolic resin-based flame retardant materials, adhesives, etc. also face waste problems. Because the waste phenolic resin has complex chemical property and is a thermosetting material, the waste phenolic resin has high heat resistance and can not be melted when being heated, for example, the waste of resources can be caused by adopting the traditional landfill or incineration method, and the environmental pollution is extremely easy to be caused by improper recycling mode. Compared with the traditional treatment mode, the pyrolysis technology is adopted to crack the phenolic resin in an anaerobic environment, valuable coke, pyrolysis oil and gas products can be recovered under the condition of avoiding pollution, and the pyrolysis method has very wide application prospect. However, the liquid products of direct pyrolysis of phenolic resin mainly contain phenols such as phenol, and the liquid products have relatively high oxygen content, corrosiveness and low utilization value and heat value, so that the improvement of pyrolysis oil quality by catalytic means is particularly important for realizing the recycling of waste phenolic resin materials.
Disclosure of Invention
The invention aims to provide a hollow hierarchical pore composite molecular sieve, a preparation method and application thereof. The hollow porous composite molecular sieve prepared by the invention has the advantages of high catalytic activity, high selectivity, good stability, easy recovery and the like.
In order to achieve the above purpose, the present invention adopts the following technical scheme: a preparation method of a hollow hierarchical pore composite molecular sieve comprises the following steps:
S1, mixing a molecular sieve with an etchant, stirring, heating, standing, filtering, washing, drying and calcining to obtain a hollow molecular sieve precursor;
S2, placing the prepared hollow molecular sieve precursor into a NaOH solution, heating and stirring, cooling to room temperature, washing, drying, adding the obtained powder into an NH 4 Cl solution for soaking (the excess of NH 4 Cl ensures that the molecular sieve is completely converted into an ammonia type molecular sieve), heating and stirring, filtering, washing, drying, repeatedly adding the NH 4 Cl solution into the dried solution for 2-3 times to obtain an ion-exchanged molecular sieve, and calcining in an air atmosphere to obtain the hollow hierarchical pore composite molecular sieve.
Preferably, the molecular sieve comprises one of ZSM-22 zeolite, MOR zeolite, USY zeolite.
Preferably, the etchant is 0.1mol/L tetrapropylammonium hydroxide (TPAOH) aqueous solution.
Preferably, the preparation method of the hollow multistage pore composite molecular sieve at least comprises one of the following (1) to (5):
(1) The mass ratio of the molecular sieve to the etchant is 1: (10-15);
(2) The addition amount of the NaOH solution is 10-12 times of the total amount of the molecular sieve;
(3) The adding amount of the NH 4 Cl solution is 80-100 ml;
(4) The concentration of the NH 4 Cl solution is 1mol/L;
(5) The concentration of the NaOH solution is 0.1-0.5 mol/L.
Preferably, the preparation method of the hollow multistage pore composite molecular sieve at least comprises one of the following (1) to (6):
(1) The stirring temperature in the step S1 is 50-60 ℃, and the stirring time is 3-5 h;
(2) The heating in the step S1 is to heat to 150-200 ℃;
(3) The standing time in the step S1 is 24-48 hours;
(4) The solvent for washing in the step S1 is distilled water, and the washing times are 3 times;
(5) The drying condition in the step S1 is that the drying is carried out for 6 to 10 hours at the temperature of 100 to 130 ℃;
(6) The calcination condition in the step S1 is that the mixture is heated to 500-600 ℃ at a speed of 5 ℃/min and calcined for 3-5 h.
Preferably, the preparation method of the hollow multistage pore composite molecular sieve at least comprises one of the following (1) to (4):
(1) The heating and stirring conditions in the step S2 are that the heating and stirring are carried out to 70-100 ℃, and the stirring is carried out for 1-8 h at 70-100 ℃;
(2) The washing in the step S2 is carried out for 3-5 times by using water;
(3) The drying in the step S2 is carried out for 6-10 hours at 100-110 ℃;
(4) The calcining temperature in the air atmosphere in the step S2 is 500-600 ℃ and the time is 2-24 h.
The hollow multi-level porous composite molecular sieve is prepared by the preparation method of the hollow multi-level porous composite molecular sieve.
The application of the hollow hierarchical porous composite molecular sieve in preparing monocyclic aromatic hydrocarbon by catalyzing pyrolysis of waste phenolic resin comprises the following steps:
Mixing waste phenolic resin and a hollow hierarchical porous composite molecular sieve, performing co-pyrolysis in an oxygen-free environment at 500-800 ℃, wherein the heating rate is 10-10 4 ℃/s, and the thermal insulation time of the co-pyrolysis is 5-60 s, so as to prepare the monocyclic aromatic hydrocarbon.
Preferably, the application at least comprises one of the following (1) to (4):
(1) The mass ratio of the waste phenolic resin to the hollow hierarchical pore composite molecular sieve is 1: (1-10);
(2) The waste phenolic resin comprises at least one of waste phenolic resin fan blades, waste phenolic resin flame-retardant materials and waste phenolic resin grinding wheels;
(3) The particle size of the waste phenolic resin is 20-100 meshes;
(4) The anaerobic environment is in an atmosphere of nitrogen, argon or helium.
Preferably, the hollow multi-level porous composite molecular sieve is calcined after the co-pyrolysis reaction to obtain the regenerated hollow multi-level porous composite molecular sieve. More preferably, the calcination is carried out under an air atmosphere at a calcination temperature of 500 to 600 ℃ for 1 to 12 hours.
The hollow multi-stage pore composite molecular sieve is processed by a series of steps, so that a hollow multi-stage pore composite structure is formed, the pore structure on the surface of the hollow multi-stage pore composite molecular sieve is optimized, the hollow structure is favorable for promoting mass transportation in the catalytic reaction process, the repeated hydrocracking in small micro-pore channels is inhibited, and the selectivity of high-value monocyclic aromatic hydrocarbon (benzene, toluene and xylene) is improved. Meanwhile, the multistage pore structure can effectively reduce coke generation in the catalytic pyrolysis reaction and inhibit catalyst deactivation, so that high-efficiency pyrolysis and deoxidation of phenolic resin are realized, the oxygen content in pyrolysis oil is greatly reduced, a new thought is provided for clean and efficient recovery of phenolic resin by a chemical approach (mainly thermal cracking), and clean and high-value utilization of waste phenolic resin materials is realized.
Compared with the prior art, the invention has the following beneficial effects:
(1) The hollow multistage pore composite molecular sieve prepared by the invention can be used as a catalyst for high-efficiency catalytic pyrolysis of waste phenolic resin, so that higher single-ring aromatic hydrocarbon selectivity and yield are obtained, and meanwhile, clean disposal and resource utilization of the waste phenolic resin are realized.
(2) The multistage pore molecular sieve catalyst prepared by the method is still difficult to deactivate after being regenerated by pyrolysis circulation for a plurality of times, and the activity of the catalyst can be recovered by a simple means after the catalyst is deactivated, so that the catalyst has high practical value.
(3) The method for preparing the monocyclic aromatic hydrocarbon by the catalytic pyrolysis of the hollow hierarchical porous composite molecular sieve is simple and easy to implement, and can be further popularized and applied to other phenolic resins or other application occasions of thermal treatment of oxygen-containing thermosetting resins/plastics so as to further realize the recycling utilization of organic solid wastes.
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
Preparing a hollow hierarchical pore composite molecular sieve:
S1, pouring 1g of ZSM-22 zeolite molecular sieve into 15ml of 0.1mol/L TPAOH water solution, stirring for 4 hours at 50 ℃, standing the mixed solution at 170 ℃ for 24 hours, filtering the obtained product, washing with distilled water for 3 times, drying at 120 ℃ for 7 hours, heating the obtained sample to 550 ℃ at a speed of 5 ℃/min, and calcining for 4 hours to obtain a hollow ZSM-22 molecular sieve precursor;
s2, putting the obtained hollow ZSM-22 molecular sieve precursor into 10ml of 0.2mol/L NaOH solution, stirring for 2 hours at 80 ℃, cooling to room temperature, washing a sample 3 times by using water, drying for 7 hours at 105 ℃, adding the obtained powder into 100ml of NH 4 Cl solution (NH 4 Cl is excessive and ensures that the molecular sieve is completely converted into an ammonia type molecular sieve), stirring for 8 hours at 80 ℃, filtering, washing with deionized water, drying for 7 hours at 105 ℃, repeating the soaking step with NH 4 Cl for three times, and calcining the molecular sieve subjected to ion exchange at 550 ℃ for 12 hours under an air atmosphere to obtain the hollow multi-stage porous composite molecular sieve.
The method for preparing monocyclic aromatic hydrocarbon by catalyzing pyrolysis of waste phenolic resin comprises the following steps:
The 50-mesh waste phenolic resin fan blade and the hollow multi-level hole composite molecular sieve are mixed according to the mass ratio of 1:10, and performing co-pyrolysis for 30 seconds under the conditions of pyrolysis temperature of 800 ℃ and heating rate of 10 4 ℃/s and pyrolysis atmosphere of argon.
Example 2
Preparing a hollow hierarchical pore composite molecular sieve:
S1, pouring 1g of ZSM-22 zeolite molecular sieve into 10ml of 0.1mol/L TPAOH water solution, stirring for 4 hours at 50 ℃, standing the mixed solution at 170 ℃ for 24 hours, filtering the obtained product, washing with distilled water for 3 times, drying at 120 ℃ for 6 hours, heating the obtained sample to 550 ℃ at a speed of 5 ℃/min, and calcining for 4 hours to obtain a hollow ZSM-22 molecular sieve precursor;
S2, putting the obtained hollow ZSM-22 molecular sieve precursor into 10ml of 0.1mol/L NaOH solution, stirring for 2 hours at 80 ℃, cooling to room temperature, washing a sample 3 times by using water, drying for 6 hours at 105 ℃, adding the obtained powder into 80ml of NH 4 Cl solution (NH 4 Cl is excessive and ensures that the molecular sieve is completely converted into an ammonia type molecular sieve), stirring for 8 hours at 80 ℃, filtering, washing with deionized water, drying for 6 hours at 105 ℃, repeating the soaking step with NH 4 Cl for three times, and calcining the molecular sieve subjected to ion exchange at 550 ℃ for 12 hours under an air atmosphere to obtain the hollow multi-stage porous composite molecular sieve.
The method for preparing monocyclic aromatic hydrocarbon by catalyzing pyrolysis of waste phenolic resin is the same as in example 1.
Example 3
Preparing a hollow hierarchical pore composite molecular sieve:
S1, pouring 1g of ZSM-22 zeolite molecular sieve into 15ml of 0.1mol/L TPAOH water solution, stirring for 4 hours at 50 ℃, standing the mixed solution at 170 ℃ for 24 hours, filtering the obtained product, washing with distilled water for 3 times, drying at 120 ℃ for 10 hours, heating the obtained sample to 550 ℃ at a speed of 5 ℃/min, and calcining for 4 hours to obtain a hollow ZSM-22 molecular sieve precursor;
S2, putting the obtained hollow ZSM-22 molecular sieve precursor into 10ml of 0.5mol/L NaOH solution, stirring for 2 hours at 80 ℃, cooling to room temperature, washing a sample with water for 5 times, drying for 10 hours at 105 ℃, adding the obtained powder into 100ml of NH 4 Cl solution (NH 4 Cl is excessive to ensure that the molecular sieve is completely converted into ammonia type molecular sieve), stirring for 8 hours at 80 ℃, filtering, washing with deionized water, drying for 10 hours at 105 ℃, repeating the soaking step with NH 4 Cl for three times, and calcining the molecular sieve subjected to ion exchange at 550 ℃ for 12 hours under an air atmosphere to obtain the hollow multi-stage porous composite molecular sieve.
The method for preparing monocyclic aromatic hydrocarbon by catalyzing pyrolysis of waste phenolic resin is the same as in example 1.
Example 4
Preparing a hollow hierarchical pore composite molecular sieve:
S1, pouring 1g of USY zeolite molecular sieve into 15ml of 0.1mol/L TPAOH water solution, stirring for 4 hours at 50 ℃, standing the mixed solution at 170 ℃ for 24 hours, filtering the obtained product, washing with distilled water for 3 times, drying at 120 ℃ for 7 hours, heating the obtained sample to 550 ℃ at a speed of 5 ℃/min, and calcining for 4 hours to obtain a hollow USY zeolite precursor;
S2, putting the obtained hollow USY molecular sieve precursor into 10ml of 0.2mol/L NaOH solution, stirring for 2 hours at 80 ℃, cooling to room temperature, washing a sample 3 times by using water, drying for 7 hours at 105 ℃, adding the obtained powder into 100ml of NH 4 Cl solution (NH 4 Cl is excessive and ensures that the molecular sieve is completely converted into the ammonia type molecular sieve), stirring for 8 hours at 80 ℃, filtering, washing with deionized water, drying for 7 hours at 105 ℃, repeating the soaking step with NH 4 Cl for three times, and calcining the molecular sieve subjected to ion exchange at 550 ℃ for 12 hours under an air atmosphere to obtain the hollow multi-stage porous composite molecular sieve.
The method for preparing monocyclic aromatic hydrocarbon by catalyzing pyrolysis of waste phenolic resin is the same as in example 1.
Example 5
Preparing a hollow hierarchical pore composite molecular sieve:
s1, pouring 1g of MOR zeolite molecular sieve into 15ml of 0.1mol/L TPAOH water solution, stirring for 4 hours at 50 ℃, standing the mixed solution at 170 ℃ for 24 hours, filtering the obtained product, washing with distilled water for 3 times, drying at 120 ℃ for 7 hours, heating the obtained sample to 550 ℃ at a speed of 5 ℃/min, and calcining for 4 hours to obtain a hollow MOR zeolite precursor;
S2, putting the obtained hollow MOR molecular sieve precursor into 10ml of 0.2mol/L NaOH solution, stirring for 2 hours at 80 ℃, cooling to room temperature, washing a sample 3 times by using water, drying for 7 hours at 105 ℃, adding the obtained powder into 100ml of NH 4 Cl solution (NH 4 Cl is excessive and ensures that the molecular sieve is completely converted into the ammonia type molecular sieve), stirring for 8 hours at 80 ℃, filtering, washing with deionized water, drying for 7 hours at 105 ℃, repeating the soaking step with NH 4 Cl for three times, and calcining the molecular sieve subjected to ion exchange at 550 ℃ for 12 hours under an air atmosphere to obtain the hollow multi-stage porous composite molecular sieve.
The method for preparing monocyclic aromatic hydrocarbon by catalyzing pyrolysis of waste phenolic resin is the same as in example 1.
Example 6
The preparation of the hollow, hierarchical pore composite molecular sieve was the same as in example 1.
The method for preparing monocyclic aromatic hydrocarbon by catalyzing pyrolysis of waste phenolic resin comprises the following steps:
The 50-mesh waste phenolic resin fan blade and the hollow multi-level hole composite molecular sieve are mixed according to the mass ratio of 1:1, and carrying out co-pyrolysis for 30s under the conditions of pyrolysis temperature of 800 ℃, heating rate of 10 4 ℃/s and pyrolysis atmosphere of argon.
Example 7
The preparation of the hollow, hierarchical pore composite molecular sieve was the same as in example 1.
The method for preparing monocyclic aromatic hydrocarbon by catalyzing pyrolysis of waste phenolic resin comprises the following steps:
The 50-mesh waste phenolic resin fan blade and the hollow multi-level hole composite molecular sieve are mixed according to the mass ratio of 1:5, fully mixing, and carrying out co-pyrolysis for 30 seconds under the conditions of the pyrolysis temperature of 800 ℃ and the heating rate of 10 4 ℃/s and the pyrolysis atmosphere of argon.
Example 8
The preparation of the hollow, hierarchical pore composite molecular sieve was the same as in example 1.
The method for preparing monocyclic aromatic hydrocarbon by catalyzing pyrolysis of waste phenolic resin comprises the following steps:
The 50-mesh waste phenolic resin fan blade and the hollow multi-level hole composite molecular sieve are mixed according to the mass ratio of 1:10, and performing co-pyrolysis for 30 seconds under the conditions that the pyrolysis temperature is 500 ℃ and the heating rate is 10 4 ℃/s and the pyrolysis atmosphere is helium.
Example 9
The preparation of the hollow, hierarchical pore composite molecular sieve was the same as in example 1.
The method for preparing monocyclic aromatic hydrocarbon by catalyzing pyrolysis of waste phenolic resin comprises the following steps:
The 50-mesh waste phenolic resin fan blade and the hollow multi-level hole composite molecular sieve are mixed according to the mass ratio of 1:10, and performing co-pyrolysis for 30 seconds under the conditions of the pyrolysis temperature of 700 ℃ and the heating rate of 10 4 ℃/s and the pyrolysis atmosphere of nitrogen.
Example 10
The preparation of the hollow, hierarchical pore composite molecular sieve was the same as in example 1.
The method for preparing monocyclic aromatic hydrocarbon by catalyzing pyrolysis of waste phenolic resin comprises the following steps:
the 50-mesh waste phenolic resin fan blade and the hollow multi-level hole composite molecular sieve are mixed according to the mass ratio of 1:10, and performing co-pyrolysis for 30s under the conditions of pyrolysis temperature of 800 ℃ and heating rate of 10 ℃/s and pyrolysis atmosphere of nitrogen.
Example 11
The preparation of the hollow, hierarchical pore composite molecular sieve was the same as in example 1.
The method for preparing monocyclic aromatic hydrocarbon by catalyzing pyrolysis of waste phenolic resin comprises the following steps:
The 50-mesh waste phenolic resin fan blade and the hollow multi-level hole composite molecular sieve are mixed according to the mass ratio of 1:10, and performing co-pyrolysis for 30s under the conditions of pyrolysis temperature of 800 ℃ and heating rate of 100 ℃/s and pyrolysis atmosphere of nitrogen.
Example 12
The preparation of the hollow, hierarchical pore composite molecular sieve was the same as in example 1.
The method for preparing monocyclic aromatic hydrocarbon by catalyzing pyrolysis of waste phenolic resin comprises the following steps:
The 50-mesh waste phenolic resin flame-retardant material and the hollow multi-level porous composite molecular sieve are mixed according to the mass ratio of 1:10, and performing co-pyrolysis for 30 seconds under the conditions of pyrolysis temperature of 800 ℃ and heating rate of 10 4 ℃/s and pyrolysis atmosphere of nitrogen.
Example 13
The difference between this example and example 1 is that the hollow multi-stage pore composite molecular sieve selected in the pyrolysis process of the catalytic waste phenolic resin is a hollow multi-stage pore composite molecular sieve catalyst recovered and reused after four catalytic pyrolysis reactions.
Other preparation procedures were the same as 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 the monocyclic aromatic compound in the pyrolysis product is calculated to be 59.8%, wherein the relative content of benzene is 36.2%, the relative content of toluene is 17.4%, and the relative content of xylene is 5.6%. The hollow hierarchical pore composite molecular sieve type catalyst prepared by the method is not easy to deactivate after being regenerated by pyrolysis circulation for a plurality of times.
Comparative example 1
The only difference between this comparative example and example 1 is that no catalyst was added during the pyrolysis of the waste phenolic resin to prepare the monocyclic aromatic hydrocarbon.
The method for preparing monocyclic aromatic hydrocarbon by catalyzing pyrolysis of waste phenolic resin comprises the following steps:
And carrying out co-pyrolysis on the waste phenolic resin fan blades with 50 meshes for 30 seconds under the conditions of pyrolysis temperature of 800 ℃ and heating rate of 10 4 ℃/s and argon as pyrolysis atmosphere.
Comparative example 2
The only difference of this comparative example compared to example 1 is the lack of operation of step S1 in the preparation of the molecular sieve.
The preparation method comprises the following steps:
the ZSM-22 zeolite molecular sieve was put into 10ml of 0.2mol/L NaOH solution and stirred at 80℃for 2 hours, after cooling to room temperature, the sample was washed 3 times with water and dried at 105℃for 7 hours, the resulting powder was added to 100ml of NH 4 Cl solution (NH 4 Cl excess, ensuring complete conversion of the molecular sieve to ammonia type molecular sieve), stirred at 80℃for 8 hours, then washed with deionized water and dried at 105℃for 7 hours, the above-mentioned soaking step with NH 4 Cl was repeated three times, and the ion exchanged molecular sieve was calcined at 550℃for 12 hours under an air atmosphere to obtain a molecular sieve.
The method for preparing monocyclic aromatic hydrocarbon by catalyzing pyrolysis of waste phenolic resin is referred to in example 1.
Comparative example 3
The only difference of this comparative example compared to example 1 is that the prepared hollow ZSM-22 molecular sieve precursor was not NaOH treated during the preparation of the hollow, hierarchical pore composite molecular sieve.
Preparing a hollow hierarchical pore composite molecular sieve:
S1, pouring 1g of ZSM-22 zeolite molecular sieve into 15ml of 0.1mol/L TPAOH water solution, stirring for 4 hours at 50 ℃, standing the mixed solution at 170 ℃ for 24 hours, filtering the obtained product, washing with distilled water for 3 times, drying at 120 ℃ for 7 hours, heating the obtained sample to 550 ℃ at a speed of 5 ℃/min, and calcining for 4 hours to obtain a hollow ZSM-22 molecular sieve precursor;
S2, adding the obtained hollow ZSM-22 molecular sieve precursor into 100ml of NH 4 Cl solution with 1mol/L (NH 4 Cl is excessive and ensures that the molecular sieve is completely converted into ammonia type molecular sieve), stirring for 8 hours at 80 ℃, filtering, washing with deionized water, drying for 7 hours at 105 ℃, repeating the soaking step with NH 4 Cl for three times, and calcining the molecular sieve subjected to ion exchange at 550 ℃ for 12 hours in an air atmosphere to obtain the hollow multi-level pore composite molecular sieve.
The method for preparing monocyclic aromatic hydrocarbon by catalyzing pyrolysis of waste phenolic resin is referred to in example 1.
Comparative example 4
The only difference between this comparative example and example 1 is that ZSM-5 zeolite molecular sieve was selected instead of ZSM-22 zeolite molecular sieve.
The preparation method is described in example 1.
Comparative example 5
The only difference between this comparative example and example 1 is that the ZSM-22 zeolite molecular sieve was replaced with a Y-type molecular sieve.
The preparation method is described in example 1.
Effect example 1
The relative contents of various chemicals in the pyrolysis products of examples 1 to 13 and comparative examples 1 to 5 were analyzed by a gas chromatograph-mass spectrometer, and the relative contents of the monocyclic aromatic compounds in the pyrolysis products, benzene, toluene, and xylene in the monocyclic aromatic compounds were calculated, respectively. The data results are shown in table 1.
TABLE 1
From the data in table 1, it can be known that the hollow multi-level pore composite molecular sieve catalyst prepared by the embodiment of the invention can realize better catalytic activity, and meanwhile, through a specific preparation method, waste phenolic resin can be better catalyzed and decomposed to obtain higher-content monocyclic aromatic hydrocarbon, which can reach 63.4% at most, and the utilization degree of the waste phenolic resin is greatly improved.
In the comparative example 1, no catalyst is added in the pyrolysis process of the waste phenolic resin, and the content of monocyclic aromatic hydrocarbon in the obtained catalytic product is lower and is only 10.8%; comparative example 2 lacks step S1 during the preparation of the catalyst, and the catalyst prepared does not have a hollow porous structure, resulting in lower catalytic activity; comparative example 3 the catalyst prepared without NaOH solution treatment had inferior catalytic performance to the example.
The ZSM-5 and Y-type molecular sieves are respectively selected for replacing the ZSM-22 molecular sieves in comparative example 4 and comparative example 5, and the content of monocyclic aromatic hydrocarbon obtained by pyrolyzing the waste phenolic resin is lower than that of the embodiment, so that the effect of producing the monocyclic aromatic hydrocarbon by catalyzing and pyrolyzing the phenolic resin can be realized only by the hollow multistage porous composite molecular sieve prepared by the processes of hollow treatment, alkalization treatment and the like of the specific type of molecular sieve.
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 (6)
1. The application of the hollow multi-level pore composite molecular sieve in preparing monocyclic aromatic hydrocarbon by catalyzing pyrolysis of waste phenolic resin is characterized in that the method for preparing monocyclic aromatic hydrocarbon by catalyzing pyrolysis of waste phenolic resin comprises the following steps:
Mixing waste phenolic resin and a hollow hierarchical porous composite molecular sieve, performing co-pyrolysis in an oxygen-free environment at 500-800 ℃, wherein the heating rate is 10-10 4 ℃/s, and the thermal insulation time of the co-pyrolysis is 5-60 s, so as to prepare monocyclic aromatic hydrocarbon;
The preparation method of the hollow hierarchical pore composite molecular sieve comprises the following steps:
S1, mixing a molecular sieve with an etchant, stirring, heating, standing, filtering, washing, drying and calcining to obtain a hollow molecular sieve precursor; the molecular sieve comprises one of ZSM-22 zeolite, MOR zeolite and USY zeolite, and the etchant is tetrapropylammonium hydroxide water solution with the concentration of 0.1 mol/L;
S2, placing the prepared hollow molecular sieve precursor into a NaOH solution, heating and stirring, cooling to room temperature, washing, drying, adding the obtained powder into an NH 4 Cl solution, heating and stirring, filtering, washing, drying, repeatedly adding the NH 4 Cl solution into the dried solution for 2-3 times to obtain an ion-exchanged molecular sieve, and calcining in an air atmosphere to obtain the hollow hierarchical pore composite molecular sieve.
2. The use according to claim 1, comprising at least one of the following (1) - (5):
(1) The mass ratio of the molecular sieve to the etchant is 1: (10-15);
(2) The addition amount of the NaOH solution is 10-12 times of the total amount of the molecular sieve;
(3) The adding amount of the NH 4 Cl solution is 80-100 ml;
(4) The concentration of the NH 4 Cl solution is 1mol/L;
(5) The concentration of the NaOH solution is 0.1-0.5 mol/L.
3. The use according to claim 1, comprising at least one of the following (1) - (6):
(1) The stirring temperature in the step S1 is 50-60 ℃, and the stirring time is 3-5 h;
(2) In the step S1, heating is performed to 150-200 ℃;
(3) The standing time in the step S1 is 24-48 h;
(4) The solvent for washing in the step S1 is distilled water, and the washing times are 3 times;
(5) The drying condition in the step S1 is that the drying is carried out for 6-10 hours at the temperature of 100-130 ℃;
(6) And the calcination condition in the step S1 is that the material is heated to 500-600 ℃ at a speed of 5 ℃/min and calcined for 3-5 h.
4. The use according to claim 1, comprising at least one of the following (1) - (4):
(1) The heating and stirring conditions in the step S2 are that the heating and stirring are carried out to 70-100 ℃, and the stirring is carried out for 1-8 hours at 70-100 ℃;
(2) The washing in the step S2 is carried out for 3-5 times by using water;
(3) In the step S2, drying is carried out for 6-10 hours at the temperature of 100-110 ℃;
(4) And in the step S2, the calcination temperature in the air atmosphere is 500-600 ℃ and the calcination time is 2-24 hours.
5. The use according to claim 1, comprising at least one of the following (1) - (4):
(1) The mass ratio of the waste phenolic resin to the hollow hierarchical pore composite molecular sieve is 1: (1-10);
(2) The waste phenolic resin comprises at least one of waste phenolic resin fan blades, waste phenolic resin flame-retardant materials and waste phenolic resin grinding wheels;
(3) The particle size of the waste phenolic resin is 20-100 meshes;
(4) The anaerobic environment is in an atmosphere of nitrogen, argon or helium.
6. The use according to claim 1, wherein the hollow, multi-stage pore composite molecular sieve is calcined after the co-pyrolysis reaction to obtain a regenerated hollow, multi-stage pore composite molecular sieve.
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