CN115974095A - 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 141
- 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 139
- 239000002131 composite material Substances 0.000 title claims abstract description 73
- 239000002149 hierarchical pore Substances 0.000 title claims abstract description 54
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 45
- 238000010438 heat treatment Methods 0.000 claims abstract description 38
- 238000001035 drying Methods 0.000 claims abstract description 32
- 238000003756 stirring Methods 0.000 claims abstract description 31
- 238000005406 washing Methods 0.000 claims abstract description 29
- 238000001354 calcination Methods 0.000 claims abstract description 28
- 230000003197 catalytic effect Effects 0.000 claims abstract description 26
- 239000012298 atmosphere Substances 0.000 claims abstract description 24
- 238000002156 mixing Methods 0.000 claims abstract description 20
- 239000002243 precursor Substances 0.000 claims abstract description 19
- 238000001914 filtration Methods 0.000 claims abstract description 15
- 238000001816 cooling Methods 0.000 claims abstract description 9
- 239000000843 powder Substances 0.000 claims abstract description 9
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 5
- 238000005530 etching Methods 0.000 claims abstract description 5
- 239000005011 phenolic resin Substances 0.000 claims description 63
- 229920001568 phenolic resin Polymers 0.000 claims description 63
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 claims description 62
- 239000002699 waste material Substances 0.000 claims description 58
- 238000000197 pyrolysis Methods 0.000 claims description 44
- -1 monocyclic aromatic hydrocarbon Chemical class 0.000 claims description 31
- 238000000034 method Methods 0.000 claims description 29
- 239000000243 solution Substances 0.000 claims description 29
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 23
- 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 14
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 12
- 238000006243 chemical reaction Methods 0.000 claims description 10
- 239000000463 material Substances 0.000 claims description 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 9
- LPSKDVINWQNWFE-UHFFFAOYSA-M tetrapropylazanium;hydroxide Chemical compound [OH-].CCC[N+](CCC)(CCC)CCC LPSKDVINWQNWFE-UHFFFAOYSA-M 0.000 claims description 9
- 239000007864 aqueous solution Substances 0.000 claims description 8
- 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
- 239000011148 porous material Substances 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
- 239000002245 particle Substances 0.000 claims description 2
- 239000002904 solvent Substances 0.000 claims description 2
- 238000002791 soaking Methods 0.000 abstract description 9
- 238000011084 recovery Methods 0.000 abstract description 4
- 239000002910 solid waste Substances 0.000 abstract description 3
- 230000000052 comparative effect Effects 0.000 description 15
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 14
- 239000000047 product Substances 0.000 description 14
- 239000003054 catalyst Substances 0.000 description 13
- 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 7
- 239000008367 deionised water Substances 0.000 description 7
- 229910021641 deionized water Inorganic materials 0.000 description 7
- 238000005342 ion exchange Methods 0.000 description 7
- 239000011259 mixed solution Substances 0.000 description 6
- 229920001187 thermosetting polymer Polymers 0.000 description 6
- 238000007233 catalytic pyrolysis 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
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 239000008096 xylene Substances 0.000 description 3
- 239000000571 coke Substances 0.000 description 2
- 230000002779 inactivation Effects 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 230000008929 regeneration Effects 0.000 description 2
- 238000011069 regeneration method Methods 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
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000004517 catalytic hydrocracking Methods 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000007123 defense Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000012263 liquid product Substances 0.000 description 1
- 238000005065 mining Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 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, and 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 etching agent, stirring, heating, standing, filtering, washing, drying and calcining to obtain the hollow molecular sieveA precursor; s2, putting the prepared hollow molecular sieve precursor into NaOH solution, heating and stirring, cooling to room temperature, washing, drying, adding NH into the obtained powder 4 Soaking in Cl solution, heating and stirring, filtering, washing, drying, and repeatedly adding NH 4 And (3) drying the Cl solution for 2-3 times to obtain the ion-exchanged molecular sieve, and then calcining the molecular sieve in an air atmosphere to obtain the hollow hierarchical porous 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, and a preparation method and application thereof.
Background
In recent years, the recycling of thermosetting plastic wastes has attracted much attention, and various research results at home and abroad show that complete recycling of the waste thermosetting plastics is possible by reasonable technical means. The phenolic resin material accounts for a large amount of thermosetting resin, and has the advantages of easily obtained raw materials, simple preparation process and excellent performance after the resin is cured and molded, so that the phenolic resin material becomes the thermosetting resin which is firstly produced in a large scale and is widely applied to various aspects of electronics, electrics, mining, national defense and the like. In addition, due to its excellent heat resistance, electric resistance, corrosion resistance, and the like, the demand for fan blades mainly made of phenolic resin composite materials has also increased year by year. However, due to the design life limit of the wind driven generator, the service life of the wind driven generator is usually not more than 20 years. This results in a large amount of waste fan blades after the fan is scrapped, and in addition, phenolic resin-based flame retardant materials, adhesives, and the like also face waste problems. Because the waste phenolic resin has complex chemical properties and is a thermosetting material, the waste phenolic resin has high heat resistance and can not be melted during heating, for example, the waste of resources can be caused by adopting the traditional landfill or incineration method for treatment, and the environment pollution can be easily caused by improper recovery mode. Compared with the traditional treatment mode, the pyrolysis technology is adopted to crack the phenolic resin in an oxygen-free environment, valuable coke, pyrolysis oil and gas products can be recovered under the condition of avoiding pollution, and the method has a very wide application prospect. However, the liquid product obtained by direct pyrolysis of phenolic resin mainly contains phenols such as phenol, and has high oxygen content, corrosiveness and low utilization value and calorific value, so that the quality of pyrolysis oil is improved by a catalytic means, and the method is particularly important for realizing resource utilization of waste phenolic resin materials.
Disclosure of Invention
The invention aims to provide a hollow hierarchical pore composite molecular sieve and 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 purpose, the 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 etching agent, stirring, heating, standing, filtering, washing, drying and calcining to obtain a hollow molecular sieve precursor;
s2, putting the prepared hollow molecular sieve precursor into NaOH solution, heating and stirring, cooling to room temperature, washing, drying, adding NH into the obtained powder 4 Soaking in Cl solution (NH) 4 Cl is excessive to ensure that the molecular sieve is completely converted into the ammonia type molecular sieve), heating, stirring, filtering, washing, drying, and repeatedly adding NH 4 And (3) drying the Cl solution for 2-3 times to obtain the ion-exchanged molecular sieve, and calcining the molecular sieve in an air atmosphere to obtain the hollow hierarchical porous 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 hierarchical pore composite molecular sieve at least comprises one of the following items (1) to (5):
(1) The mass ratio of the molecular sieve to the etching agent 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 NH 4 The addition amount of the Cl solution is 80-100 ml;
(4) The NH 4 The concentration of the 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 hierarchical pore composite molecular sieve at least comprises one of the following items (1) to (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, the heating is carried out 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 drying for 6 to 10 hours at a temperature of between 100 and 130 ℃;
(6) The calcining condition in the step S1 is heating to 500-600 ℃ at the speed of 5 ℃/min, and calcining for 3-5 h.
Preferably, the preparation method of the hollow hierarchical pore composite molecular sieve at least comprises one of the following items (1) to (4):
(1) The conditions of heating and stirring in the step S2 are all heating to 70-100 ℃, and stirring for 1-8 h at 70-100 ℃;
(2) Washing in the step S2 is carried out for 3-5 times by using water;
(3) In the step S2, the drying is carried out for 6 to 10 hours at the temperature of between 100 and 110 ℃;
(4) The calcining temperature in the air atmosphere in the step S2 is 500-600 ℃, and the calcining time is 2-24 h.
The hollow hierarchical pore composite molecular sieve is prepared by the preparation method of the hollow hierarchical pore composite molecular sieve.
The application of the hollow hierarchical pore composite molecular sieve in preparing monocyclic aromatic hydrocarbon by pyrolyzing catalytic waste phenolic resin comprises the following steps:
mixing the waste phenolic resin with the hollow multi-stage pore composite molecular sieve, and performing 500-degree pore mixing in an oxygen-free environmentCo-pyrolysis is carried out at 800 ℃ and the heating rate is 10-10 4 And (3) performing co-pyrolysis at the temperature of 5-60 s to obtain the monocyclic aromatic hydrocarbon.
Preferably, the application at least comprises one of the following items (1) to (4):
(1) The mass ratio of the waste phenolic resin to the hollow hierarchical porous 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 oxygen-free environment is in the atmosphere of nitrogen, argon or helium.
Preferably, the hollow hierarchical porous composite molecular sieve is calcined after the co-pyrolysis reaction to obtain the regenerated hollow hierarchical porous composite molecular sieve. More preferably, the calcination is performed under the conditions of air atmosphere and calcination temperature of 500-600 ℃ for 1-12 h.
The hollow hierarchical pore composite molecular sieve prepared by the method forms a hollow hierarchical pore composite structure through a series of steps, optimizes the pore structure on the surface of the hollow hierarchical pore composite structure, is favorable for promoting the mass transportation in the catalytic reaction process, inhibits the repeated hydrocracking in micro-channels, and improves the selectivity of high-value monocyclic aromatic hydrocarbons (benzene, toluene and xylene). Meanwhile, the multi-stage pore structure can effectively reduce the generation of coke in the catalytic pyrolysis reaction and inhibit the inactivation of a catalyst, so that the high-efficiency cracking and deoxidation of the phenolic resin are realized, the oxygen content in the pyrolysis oil is greatly reduced, a new thought is provided for the clean and high-efficiency recovery of the phenolic resin by a chemical approach (mainly thermal cracking), and the 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 hierarchical pore composite molecular sieve prepared by the invention can be used as a catalyst to be applied to high-efficiency catalytic pyrolysis of waste phenolic resin, so that high monocyclic aromatic selectivity and yield are obtained, and clean disposal and resource utilization of the waste phenolic resin are realized.
(2) The hierarchical pore molecular sieve catalyst prepared by the invention is still not easy to inactivate after being subjected to multiple pyrolysis cycle regeneration, and the activity can be recovered by a simple means after inactivation, so that the hierarchical pore molecular sieve catalyst has higher practical value.
(3) The method for preparing the monocyclic aromatic hydrocarbon by 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 oxygen-containing thermosetting resin/plastic thermal treatment application occasions to further realize resource utilization of organic solid wastes.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be obtained by a person skilled in the art without making any creative effort based on the embodiments in the present invention, belong to the protection scope of the present invention.
In the examples and comparative examples, the experimental methods used were conventional unless otherwise specified, 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 aqueous solution, stirring for 4h at 50 ℃, standing the mixed solution for 24h at 170 ℃, filtering the obtained product, washing for 3 times with distilled water, drying for 7h at 120 ℃, heating the obtained sample to 550 ℃ at the speed of 5 ℃/min, and calcining for 4h 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 the sample for 3 times by using water, drying for 7 hours at 105 ℃, adding the obtained powder into 100ml of 1mol/L NH 4 In Cl solution (NH) 4 Cl excess to ensure complete conversion of the molecular sieve to the ammonia form), stirring at 80 ℃ for 8h, then filtering, washing with deionized water and drying at 105 ℃ for 7h, repeating the above with NH 4 And Cl soaking for three times, and calcining the molecular sieve subjected to ion exchange for 12 hours at 550 ℃ in air atmosphere to obtain the hollow hierarchical porous composite molecular sieve.
The method for preparing the monocyclic aromatic hydrocarbon by pyrolyzing the catalytic waste phenolic resin comprises the following steps:
mixing a 50-mesh waste phenolic resin fan blade and a hollow hierarchical pore composite molecular sieve according to a mass ratio of 1:10, mixing thoroughly, heating at 800 deg.C and 10 deg.C 4 And co-pyrolysis is carried out for 30s under the condition that the pyrolysis atmosphere is 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 aqueous solution, stirring for 4 hours at 50 ℃, standing the mixed solution for 24 hours at 170 ℃, filtering the obtained product, washing the product for 3 times by using distilled water, drying for 6 hours at 120 ℃, heating the obtained sample to 550 ℃ at the 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 the temperature of 80 ℃, cooling to the room temperature, washing the sample for 3 times by using water, drying for 6 hours at the temperature of 105 ℃, adding the obtained powder into 80ml of 1mol/L NH 4 Cl solution (NH) 4 Excess of Cl to ensure complete conversion of the molecular sieve to the molecular sieve ammonia) was stirred at 80 ℃ for 8h, then filtered, washed with deionized water and dried at 105 ℃ for 6h, repeating the above with NH 4 And Cl soaking for three times, and calcining the molecular sieve subjected to ion exchange for 12 hours at 550 ℃ in air atmosphere to obtain the hollow hierarchical porous composite molecular sieve.
The method for preparing monocyclic aromatic hydrocarbon by pyrolyzing the catalytic waste phenolic resin is the same as that 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 aqueous solution, stirring for 4h at 50 ℃, standing the mixed solution for 24h at 170 ℃, filtering the obtained product, washing the product for 3 times by using distilled water, drying for 10h at 120 ℃, heating the obtained sample to 550 ℃ at the speed of 5 ℃/min, and calcining for 4h 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 2h at 80 ℃, cooling to room temperature, washing the sample for 5 times by using water, drying for 10h at 105 ℃, adding the obtained powder into 100ml of 1mol/L NH 4 Cl solution (NH) 4 Cl excess to ensure complete conversion of the molecular sieve to the ammonia form), stirring at 80 ℃ for 8h, then filtering, washing with deionized water and drying at 105 ℃ for 10h, repeating the above with NH 4 And Cl soaking for three times, and calcining the molecular sieve subjected to ion exchange for 12 hours at 550 ℃ in air atmosphere to obtain the hollow hierarchical porous composite molecular sieve.
The method for preparing monocyclic aromatic hydrocarbon by pyrolyzing the catalytic waste phenolic resin is the same as that 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 aqueous solution, stirring for 4h at 50 ℃, standing the mixed solution for 24h at 170 ℃, filtering the obtained product, washing 3 times with distilled water, drying for 7h at 120 ℃, heating the obtained sample to 550 ℃ at the speed of 5 ℃/min, and calcining for 4h to obtain a hollow USY molecular sieve precursor;
s2, putting the obtained hollow USY molecular sieve precursor into 10ml of 0.2mol/L NaOH solution, stirring for 2h at 80 ℃, cooling to room temperature, washing the sample for 3 times by using water, drying for 7h at 105 ℃, adding the obtained powder into 100ml of 1mol/L NH 4 In Cl solution (NH) 4 Excess of Cl to ensure complete conversion of the molecular sieve to the molecular sieve ammonia) was stirred at 80 ℃ for 8h, then filtered, washed with deionized water and dried at 105 ℃ for 7h, repeating the above with NH 4 Three times of Cl soaking step, ion exchange is carried outCalcining the exchanged molecular sieve for 12h at 550 ℃ in an air atmosphere to prepare the hollow hierarchical porous composite molecular sieve.
The method for preparing monocyclic aromatic hydrocarbon by pyrolyzing the catalytic waste phenolic resin is the same as that 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 aqueous solution, stirring for 4h at 50 ℃, standing the mixed solution for 24h at 170 ℃, filtering the obtained product, washing 3 times with distilled water, drying for 7h at 120 ℃, heating the obtained sample to 550 ℃ at the speed of 5 ℃/min, and calcining for 4h to obtain a hollow MOR molecular sieve precursor;
s2, putting the obtained hollow MOR molecular sieve precursor into 10ml of 0.2mol/L NaOH solution, stirring for 2h at 80 ℃, cooling to room temperature, washing the sample for 3 times by using water, drying for 7h at 105 ℃, adding the obtained powder into 100ml of 1mol/L NH 4 Cl solution (NH) 4 Excess of Cl to ensure complete conversion of the molecular sieve to the molecular sieve ammonia) was stirred at 80 ℃ for 8h, then filtered, washed with deionized water and dried at 105 ℃ for 7h, repeating the above with NH 4 And (3) Cl soaking for three times, and calcining the molecular sieve subjected to ion exchange for 12 hours at 550 ℃ in air atmosphere to prepare the hollow hierarchical porous composite molecular sieve.
The method for preparing monocyclic aromatic hydrocarbon by pyrolyzing the catalytic waste phenolic resin is the same as that in example 1.
Example 6
The hollow hierarchical pore composite molecular sieve was prepared as in example 1.
The method for preparing the monocyclic aromatic hydrocarbon by pyrolyzing the catalytic waste phenolic resin comprises the following steps:
mixing a 50-mesh waste phenolic resin fan blade and a hollow hierarchical pore composite molecular sieve according to a mass ratio of 1:1, fully mixing, and heating at the temperature of 800 ℃ and the heating rate of 10 4 And co-pyrolysis is carried out for 30s under the condition that the pyrolysis atmosphere is argon.
Example 7
The hollow hierarchical pore composite molecular sieve was prepared as in example 1.
The method for preparing the monocyclic aromatic hydrocarbon by pyrolyzing the catalytic waste phenolic resin comprises the following steps:
mixing a 50-mesh waste phenolic resin fan blade and a hollow hierarchical pore composite molecular sieve according to a mass ratio of 1:5, fully mixing, and heating at the temperature of 800 ℃ and the heating rate of 10 4 And co-pyrolysis is carried out for 30s under the condition that the pyrolysis atmosphere is argon.
Example 8
The hollow hierarchical pore composite molecular sieve was prepared as in example 1.
The method for preparing the monocyclic aromatic hydrocarbon by pyrolyzing the catalytic waste phenolic resin comprises the following steps:
mixing a 50-mesh waste phenolic resin fan blade and a hollow hierarchical pore composite molecular sieve according to a mass ratio of 1:10, fully mixing, and heating at the pyrolysis temperature of 500 ℃ and the heating rate of 10 4 And co-pyrolysis is carried out for 30s under the condition that the pyrolysis atmosphere is helium.
Example 9
The hollow hierarchical pore composite molecular sieve was prepared as in example 1.
The method for preparing the monocyclic aromatic hydrocarbon by pyrolyzing the catalytic waste phenolic resin comprises the following steps:
mixing a 50-mesh waste phenolic resin fan blade and a hollow hierarchical pore composite molecular sieve according to a mass ratio of 1:10, mixing thoroughly, heating at 700 deg.C and 10 deg.C 4 And carrying out co-pyrolysis for 30s under the conditions that the temperature/s and the pyrolysis atmosphere are nitrogen.
Example 10
The hollow hierarchical pore composite molecular sieve was prepared as in example 1.
The method for preparing the monocyclic aromatic hydrocarbon by pyrolyzing the catalytic waste phenolic resin comprises the following steps:
mixing a 50-mesh waste phenolic resin fan blade and a hollow hierarchical pore composite molecular sieve according to a mass ratio of 1:10, and carrying out co-pyrolysis for 30s under the conditions that the pyrolysis temperature is 800 ℃, the heating rate is 10 ℃/s and the pyrolysis atmosphere is nitrogen.
Example 11
The hollow hierarchical pore composite molecular sieve was prepared as in example 1.
The method for preparing the monocyclic aromatic hydrocarbon by pyrolyzing the catalytic waste phenolic resin comprises the following steps:
mixing 50-mesh waste phenolic resin fan blades and a hollow multi-stage hole composite molecular sieve according to a mass ratio of 1:10, and carrying out co-pyrolysis for 30s under the conditions that the pyrolysis temperature is 800 ℃, the heating rate is 100 ℃/s and the pyrolysis atmosphere is nitrogen.
Example 12
The hollow hierarchical pore composite molecular sieve was prepared as in example 1.
The method for preparing the monocyclic aromatic hydrocarbon by pyrolyzing the catalytic waste phenolic resin comprises the following steps:
mixing a 50-mesh waste phenolic resin flame-retardant material and a hollow hierarchical pore composite molecular sieve according to a mass ratio of 1:10, mixing thoroughly, heating at 800 deg.C and 10 deg.C 4 And co-pyrolysis is carried out for 30s under the condition that the pyrolysis atmosphere is nitrogen.
Example 13
The difference between the example and the example 1 is that the hollow hierarchical pore composite molecular sieve selected in the pyrolysis process of the catalytic waste phenolic resin is a hollow hierarchical pore composite molecular sieve catalyst which is recycled after four catalytic pyrolysis reactions.
The other preparation process is the same as that of example 1.
The relative content of various chemicals in the pyrolysis product is analyzed by a gas chromatography-mass spectrometer, and the relative content of the monocyclic aromatic compound in the pyrolysis product is calculated to be 59.8 percent, wherein the relative content of benzene is 36.2 percent, the relative content of toluene is 17.4 percent, and the relative content of xylene is 5.6 percent. The hollow hierarchical pore composite molecular sieve type catalyst prepared by the invention is still not easy to inactivate after repeated pyrolysis cycle regeneration.
Comparative example 1
Compared with example 1, the comparative example is different only in that no catalyst is added in the process of preparing monocyclic aromatic hydrocarbon by catalyzing pyrolysis of waste phenolic resin.
The method for preparing the monocyclic aromatic hydrocarbon by pyrolyzing the catalytic waste phenolic resin comprises the following steps:
50-mesh waste phenolic resin fan blades are heated at the pyrolysis temperature of 800 ℃ and the heating rate of 10 4 And co-pyrolysis is carried out for 30s under the condition that the pyrolysis atmosphere is argon.
Comparative example 2
The comparative example differs from example 1 only in that the preparation of the molecular sieve lacks the operation of step S1.
The preparation method comprises the following steps:
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, and the resulting powder was added to 100ml of 1mol/L NH 4 Cl solution (NH) 4 Cl excess to ensure complete conversion of the molecular sieve to the ammonia form), stirring at 80 ℃ for 8h, then filtering, washing with deionized water and drying at 105 ℃ for 7h, repeating the above with NH 4 And (3) Cl soaking for three times, and calcining the molecular sieve subjected to ion exchange for 12 hours at 550 ℃ in an air atmosphere to prepare the molecular sieve.
The method for preparing monocyclic aromatic hydrocarbon by pyrolyzing catalytic waste phenolic resin refers to example 1.
Comparative example 3
The present comparative example differs from example 1 only in that the hollow hierarchical pore composite molecular sieve is prepared without subjecting the prepared hollow ZSM-22 molecular sieve precursor to NaOH treatment.
Preparing a hollow hierarchical pore composite molecular sieve:
s1, pouring 1g of ZSM-22 zeolite molecular sieve into 15ml of 0.1mol/L TPAOH aqueous solution, stirring for 4h at 50 ℃, standing the mixed solution for 24h at 170 ℃, filtering the obtained product, washing for 3 times with distilled water, drying for 7h at 120 ℃, heating the obtained sample to 550 ℃ at the speed of 5 ℃/min, and calcining for 4h to obtain a hollow ZSM-22 molecular sieve precursor;
s2, adding the obtained hollow ZSM-22 molecular sieve precursor into 100ml of 1mol/L NH 4 Cl solution (NH) 4 Cl excess ensures that the molecular sieve is completely converted into ammoniaType molecular sieve), stirred at 80 ℃ for 8h, then filtered, washed with deionized water and dried at 105 ℃ for 7h, repeating the above with NH 4 And Cl soaking for three times, and calcining the molecular sieve subjected to ion exchange for 12 hours at 550 ℃ in air atmosphere to obtain the hollow hierarchical porous composite molecular sieve.
The method for preparing monocyclic aromatic hydrocarbon by pyrolyzing catalytic waste phenolic resin refers to example 1.
Comparative example 4
The only difference compared to example 1 is that the ZSM-22 zeolite molecular sieve was replaced with a ZSM-5 zeolite molecular sieve.
The preparation method refers to example 1.
Comparative example 5
The only difference compared to example 1 is that the ZSM-22 zeolite molecular sieve was replaced with a Y-type molecular sieve.
The preparation process is referred to 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 chromatography-mass spectrometer, and the relative contents of monocyclic aromatic compounds and the relative contents of benzene, toluene and xylene in the monocyclic aromatic compounds in the pyrolysis products were calculated, respectively. Data results are shown in table 1.
TABLE 1
The data in table 1 show that the hollow hierarchical pore composite molecular sieve catalyst prepared in the embodiment of the invention can realize better catalytic activity, and meanwhile, the specific preparation method can better catalyze and decompose the waste phenolic resin to obtain higher-content monocyclic aromatic hydrocarbon which can reach 63.4% at most, thereby greatly improving the utilization degree of the waste phenolic resin.
Comparative example 1 no catalyst was added during pyrolysis of waste phenolic resin, and the content of monocyclic aromatic hydrocarbon in the obtained catalytic product was low, only 10.8%; comparative example 2 step S1 was omitted in the preparation of the catalyst, and the prepared catalyst did not have a hollow porous structure, resulting in a lower catalytic activity; comparative example 3 the catalyst was prepared without NaOH solution treatment, and the catalyst obtained had inferior catalytic performance to that of the examples.
The ZSM-5 and the Y-type molecular sieves are respectively selected to replace the ZSM-22 molecular sieves in the comparative example 4 and the comparative example 5, and the content of monocyclic aromatic hydrocarbon obtained by pyrolyzing the waste phenolic resin is lower than that in the example, so that the better effect of catalyzing and pyrolyzing the phenolic resin to produce the monocyclic aromatic hydrocarbon can be realized only by the hollow hierarchical pore composite molecular sieve prepared by subjecting a specific type of molecular sieve to hollow treatment, alkalization treatment and the like.
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 (10)
1. The preparation method of the hollow hierarchical pore composite molecular sieve is characterized by comprising the following steps:
s1, mixing a molecular sieve with an etching agent, stirring, heating, standing, filtering, washing, drying and calcining to obtain a hollow molecular sieve precursor;
s2, putting the prepared hollow molecular sieve precursor into NaOH solution, heating and stirring, cooling to room temperature, washing, drying, adding NH into the obtained powder 4 Adding into Cl solution, heating and stirring, filtering, washing, drying, and repeatedly adding NH 4 And (3) drying the Cl solution for 2-3 times to obtain the ion-exchanged molecular sieve, and then calcining the molecular sieve in an air atmosphere to obtain the hollow hierarchical porous composite molecular sieve.
2. The method of claim 1, wherein the molecular sieve comprises one of ZSM-22 zeolite, MOR zeolite, USY zeolite.
3. The method for preparing the hollow hierarchical pore composite molecular sieve according to claim 1, wherein the etchant is 0.1mol/L tetrapropylammonium hydroxide aqueous solution.
4. The method for preparing the hollow hierarchical pore composite molecular sieve according to claim 1, characterized by comprising at least one of the following (1) to (5):
(1) The mass ratio of the molecular sieve to the etching agent 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 NH 4 The addition amount of the Cl solution is 80-100 ml;
(4) The NH 4 The concentration of the Cl solution is 1mol/L;
(5) The concentration of the NaOH solution is 0.1-0.5 mol/L.
5. The method for preparing the hollow hierarchical pore composite molecular sieve according to claim 1, characterized by comprising at least 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) In the step S1, the heating is carried out 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 drying for 6 to 10 hours at a temperature of between 100 and 130 ℃;
(6) The calcining condition in the step S1 is heating to 500-600 ℃ at the speed of 5 ℃/min, and calcining for 3-5 h.
6. The method for preparing the hollow hierarchical porous composite molecular sieve according to claim 1, characterized by comprising at least one of the following (1) to (4):
(1) The conditions of heating and stirring in the step S2 are all heating to 70-100 ℃, and stirring for 1-8 h at 70-100 ℃;
(2) Washing in the step S2 is carried out for 3-5 times by using water;
(3) In the step S2, the drying is carried out for 6 to 10 hours at the temperature of between 100 and 110 ℃;
(4) The calcining temperature in the air atmosphere in the step S2 is 500-600 ℃, and the calcining time is 2-24 h.
7. The hollow hierarchical pore composite molecular sieve prepared by the preparation method of the hollow hierarchical pore composite molecular sieve as claimed in any one of claims 1 to 6.
8. The application of the hollow hierarchical pore composite molecular sieve of claim 7 in preparation of monocyclic aromatic hydrocarbon by pyrolysis of catalytic waste phenolic resin, wherein the method for preparing monocyclic aromatic hydrocarbon by pyrolysis of catalytic waste phenolic resin comprises the following steps:
mixing the waste phenolic resin with a hollow multi-stage pore composite molecular sieve, and carrying out co-pyrolysis at 500-800 ℃ in an oxygen-free environment at the heating rate of 10-10 4 And (3) performing co-pyrolysis at the temperature of 5-60 s to obtain the monocyclic aromatic hydrocarbon.
9. The use according to claim 8, comprising at least one of the following (1) to (4):
(1) The mass ratio of the waste phenolic resin to the hollow hierarchical porous 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 oxygen-free environment is in the atmosphere of nitrogen, argon or helium.
10. The use of claim 8, wherein the hollow hierarchical pore composite molecular sieve is calcined after the co-pyrolysis reaction to obtain a regenerated hollow hierarchical pore composite molecular sieve.
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