CN114931969B - Ferroferric oxide-ZSM-5 composite material and preparation method and application thereof - Google Patents
Ferroferric oxide-ZSM-5 composite material and preparation method and application thereof Download PDFInfo
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- CN114931969B CN114931969B CN202210642774.9A CN202210642774A CN114931969B CN 114931969 B CN114931969 B CN 114931969B CN 202210642774 A CN202210642774 A CN 202210642774A CN 114931969 B CN114931969 B CN 114931969B
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- 239000002131 composite material Substances 0.000 title claims abstract description 42
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 239000002808 molecular sieve Substances 0.000 claims abstract description 78
- 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 78
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 75
- 239000000243 solution Substances 0.000 claims description 54
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims description 34
- 238000005406 washing Methods 0.000 claims description 31
- 238000006243 chemical reaction Methods 0.000 claims description 25
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 24
- 238000001035 drying Methods 0.000 claims description 23
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 21
- 238000002156 mixing Methods 0.000 claims description 17
- LPSKDVINWQNWFE-UHFFFAOYSA-M tetrapropylazanium;hydroxide Chemical compound [OH-].CCC[N+](CCC)(CCC)CCC LPSKDVINWQNWFE-UHFFFAOYSA-M 0.000 claims description 15
- 238000005530 etching Methods 0.000 claims description 14
- 239000000203 mixture Substances 0.000 claims description 12
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 11
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 10
- 239000008367 deionised water Substances 0.000 claims description 10
- 229910021641 deionized water Inorganic materials 0.000 claims description 10
- 239000011734 sodium Substances 0.000 claims description 10
- 229910052708 sodium Inorganic materials 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 9
- 238000004321 preservation Methods 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 5
- 239000002244 precipitate Substances 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 4
- 239000011259 mixed solution Substances 0.000 claims description 4
- 239000000047 product Substances 0.000 claims description 4
- 230000000630 rising effect Effects 0.000 claims description 4
- -1 polytetrafluoroethylene Polymers 0.000 claims description 3
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 3
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 3
- 239000002105 nanoparticle Substances 0.000 abstract description 16
- 230000003197 catalytic effect Effects 0.000 abstract description 14
- 239000011148 porous material Substances 0.000 abstract description 11
- 238000003547 Friedel-Crafts alkylation reaction Methods 0.000 abstract description 7
- 238000011065 in-situ storage Methods 0.000 abstract description 6
- 239000003054 catalyst Substances 0.000 abstract description 2
- 239000002923 metal particle Substances 0.000 abstract description 2
- 239000003513 alkali Substances 0.000 description 12
- 238000001027 hydrothermal synthesis Methods 0.000 description 8
- 239000012266 salt solution Substances 0.000 description 8
- 238000001354 calcination Methods 0.000 description 7
- 238000005470 impregnation Methods 0.000 description 7
- 150000002505 iron Chemical class 0.000 description 7
- NIPNSKYNPDTRPC-UHFFFAOYSA-N N-[2-oxo-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 NIPNSKYNPDTRPC-UHFFFAOYSA-N 0.000 description 6
- 238000006555 catalytic reaction Methods 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- 238000000926 separation method Methods 0.000 description 5
- 238000005119 centrifugation Methods 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 229910052742 iron Inorganic materials 0.000 description 4
- 239000003921 oil Substances 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 238000001179 sorption measurement Methods 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical group C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000003795 desorption Methods 0.000 description 3
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 3
- 238000011068 loading method Methods 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 2
- 229910021536 Zeolite Inorganic materials 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 230000006378 damage Effects 0.000 description 2
- 238000004108 freeze drying Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000010457 zeolite Substances 0.000 description 2
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 1
- 238000003917 TEM image Methods 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 230000029936 alkylation Effects 0.000 description 1
- 238000005804 alkylation reaction Methods 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 150000001491 aromatic compounds Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 150000001555 benzenes Chemical class 0.000 description 1
- 238000004523 catalytic cracking Methods 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000007323 disproportionation reaction Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- MVFCKEFYUDZOCX-UHFFFAOYSA-N iron(2+);dinitrate Chemical compound [Fe+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MVFCKEFYUDZOCX-UHFFFAOYSA-N 0.000 description 1
- 238000006317 isomerization reaction Methods 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 231100000989 no adverse effect Toxicity 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000002407 reforming Methods 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000011343 solid material Substances 0.000 description 1
- 238000010555 transalkylation reaction Methods 0.000 description 1
- 238000009827 uniform distribution Methods 0.000 description 1
Classifications
-
- 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
- B01J29/42—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 iron group metals, noble metals or copper
- B01J29/46—Iron group metals or copper
-
- B01J35/33—
-
- B01J35/615—
-
- B01J35/633—
-
- B01J35/647—
-
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Abstract
The invention provides Fe 3 O 4 ZSM-5 composite material, and a preparation method and application thereof, and relates to the technical field of composite materials. Fe provided by the invention 3 O 4 -ZSM-5 composite material comprising a hollow ZSM-5 molecular sieve and Fe in situ loaded in the cavity of the hollow ZSM-5 molecular sieve 3 O 4 And (3) nanoparticles. The invention uses Fe 3 O 4 The nano particles are encapsulated in the hollow ZSM-5, so that the size of the metal particles is effectively controlled, and the catalytic activity and stability are improved. The catalyst provided by the invention has the advantages of unique pore structure, large surface area, excellent structural stability, high conductivity and the like, and has excellent performance in catalyzing Friedel-crafts alkylation reaction.
Description
Technical Field
The invention relates to the technical field of composite materials, in particular to Fe 3 O 4 -ZSM-5 composite material and a preparation method and application thereof.
Background
ZSM-5 is an important material in zeolite molecular sieves and has been widely used in petroleum and petrochemical industry processes such as catalytic cracking, isomerization of normal paraffins, naphthenes and aromatics, alkylation, disproportionation and transalkylation, reforming, adsorption separation of gases, and the like. However, since the microporous structure of ZSM-5 zeolite greatly reduces mass transfer rate in catalytic reactions involving macromolecules such as aromatic compounds having functional groups, resulting in low catalytic activity, further application thereof is limited.
The preparation of mesoporous ZSM-5 finds a way to solve the problem, and experimental results show that the mesoporous ZSM-5 has better catalytic performance in some acid catalytic reactions. However, in the reaction of catalytic friedel-crafts alkylation, the catalytic performance is poor due to its low reactivity.
Disclosure of Invention
The invention aims to provide Fe 3 O 4 ZSM-5 composite material, preparation method and application thereof, and Fe provided by the invention 3 O 4 The ZSM-5 composite material has higher catalytic activity and stability, and has higher catalytic activity in the catalytic Friedel-crafts alkylation reaction.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides Fe 3 O 4 -ZSM-5 composite material comprising a hollow ZSM-5 molecular sieve and Fe in situ loaded in the cavity of the hollow ZSM-5 molecular sieve 3 O 4 And (3) nanoparticles.
Preferably, the Fe 3 O 4 The loading of the nano particles is 50-70 wt%.
Preferably, the Fe 3 O 4 The particle diameter of the nano particles is 200-300 nm.
The invention provides the Fe with the technical proposal 3 O 4 A method for preparing a ZSM-5 composite material, comprising the steps of:
mixing a ZSM-5 molecular sieve with an alkali solution, and etching to obtain a hollow ZSM-5 molecular sieve;
placing the hollow ZSM-5 molecular sieve in an iron salt solution for impregnation to obtain an iron-loaded ZSM-5 molecular sieve;
roasting the ZSM-5 molecular sieve loaded with the iron element to obtain Fe 3 O 4 -ZSM-5 composite.
Preferably, the alkali solution is a sodium hydroxide solution or a potassium hydroxide solution.
Preferably, the etching temperature is 50-80 ℃; the etching time is 30-60 min.
Preferably, the ferric salt solution is at least one of ferric nitrate solution and ferric chloride solution.
Preferably, the time of the impregnation is 6 to 24 hours.
Preferably, the roasting temperature is 460-520 ℃; the heat preservation time is 4-6 h.
The invention provides the Fe with the technical proposal 3 O 4 ZSM-5 composite material or Fe prepared by the preparation method according to the technical scheme 3 O 4 Use of a ZSM-5 composite in the catalysis of friedel-crafts alkylation reactions.
The invention provides Fe 3 O 4 -ZSM-5 composite material comprising a hollow ZSM-5 molecular sieve and Fe in situ loaded in the cavity of the hollow ZSM-5 molecular sieve 3 O 4 And (3) nanoparticles. The invention uses Fe 3 O 4 The nano particles are encapsulated in the hollow ZSM-5, so that the size of the metal particles is effectively controlled, and the catalytic activity and stability are improved. The catalyst provided by the invention has the advantages of unique pore structure, large surface area, excellent structural stability, high conductivity and the like, and has excellent performance in catalyzing Friedel-crafts alkylation reaction.
Fe provided by the invention 3 O 4 The ZSM-5 composite material also has a series of excellent characteristics of acid and alkali resistance, corrosion resistance, high temperature resistance, low temperature resistance, biocompatibility and the like.
Drawings
FIG. 1 shows Fe prepared in example 1 3 O 4 -a Transmission Electron Microscope (TEM) image of the ZSM-5 composite;
FIG. 2 is a diagram of Fe prepared in example 1 3 O 4 -nitrogen adsorption and desorption isotherm plot of ZSM-5 composite;
FIG. 3 is a diagram of Fe prepared in example 1 3 O 4 -hysteresis loop of ZSM-5 composite.
Detailed Description
The invention provides Fe 3 O 4 -ZSM-5 composite material comprising a hollow ZSM-5 molecular sieve and Fe in situ loaded in the cavity of the hollow ZSM-5 molecular sieve 3 O 4 And (3) nanoparticles.
In the present invention, the Fe 3 O 4 The loading of the nanoparticles is preferably 50 to 70wt%, more preferably 59wt%. In the present invention, the Fe 3 O 4 The loading of the nanoparticle refers to Fe 3 O 4 Nano particles occupy Fe 3 O 4 -the mass percentage of the ZSM-5 composite material. In the present invention, the Fe 3 O 4 The particle diameter of the nanoparticle is preferably 200 to 300nm, more preferably 250nm.
In the present invention, the hollow ZSM-5 molecular sieve preferably has an average pore diameter of 100nm or less, more preferably 50nm; the pores of the hollow ZSM-5 molecular sieve are through holes; the pore volume of the hollow ZSM-5 molecular sieve is preferably 0.2-0.3 cm 3 Preferably 0.24cm 3 /g。
In the present invention, the Fe 3 O 4 The total pore volume of the ZSM-5 composite is preferably from 0.2 to 0.3cm 3 Preferably 0.24cm 3 /g; wherein the micropore volume is preferably 0 to 0.15cm 3 Preferably 0.1cm 3 /g; the total volume of the mesopores and macropores is preferably 0 to 0.15cm 3 Preferably 0.14cm 3 /g; the surface area is preferably 300 to 400m 2 /g, more preferably 380m 2 /g; the micropore area is preferably 100 to 200m 2 /g, more preferably 187m 2 /g; the external surface area is preferably 100 to 200m 2 Per gram, more preferably 193m 2 /g。
The invention also provides the Fe in the technical proposal 3 O 4 A method for preparing a ZSM-5 composite material, comprising the steps of:
mixing a ZSM-5 molecular sieve with an alkali solution, and etching to obtain a hollow ZSM-5 molecular sieve;
placing the hollow ZSM-5 molecular sieve in an iron salt solution for impregnation to obtain an iron-loaded ZSM-5 molecular sieve;
roasting the ZSM-5 molecular sieve loaded with the iron element to obtain Fe 3 O 4 -ZSM-5 composite.
The invention mixes ZSM-5 molecular sieve and alkali solution, and etches to obtain hollow ZSM-5 molecular sieve. In a specific embodiment of the present invention, the ZSM-5 molecular sieve is in the form of a benzene ring having a size of 0.5. Mu.m.times.0.4. Mu.m.times.0.2. Mu.m. In the invention, the ZSM-5 molecular sieve is of a hollow porous structure, and micropores, mesopores and macropores are uniformly distributed in the ZSM-5 hollow porous structure. The ZSM-5 molecular sieve has a unique hollow multistage pore structure, provides rich catalytic active sites in various catalytic reactions, enhances medium transmission and electron transfer capacity, and is beneficial to the catalytic reactions.
In the present invention, the preparation method of the ZSM-5 molecular sieve preferably comprises: mixing tetrapropylammonium hydroxide solution, water, sodium metaaluminate and ethyl orthosilicate, and performing hydrothermal reaction to obtain a reaction solution; and (3) carrying out solid-liquid separation on the reaction solution, and washing, drying and calcining the obtained solid substance in sequence to obtain the ZSM-5 molecular sieve.
In the invention, tetrapropylammonium hydroxide solution, water, sodium metaaluminate and ethyl orthosilicate are preferably mixed for hydrothermal reaction to obtain a reaction solution. In the present invention, the Tetraethoxysilane (TEOS), tetrapropylammonium hydroxide (TPAOH) in tetrapropylammonium hydroxide solution, sodium metaaluminate (NaAlO) 2 ) The molar ratio of water to water is preferably 6:1 to 3:0.09 to 0.12:300 to 400, more preferably 6:1.995 to 2.25:0.12:460. In the invention, the mass concentration of the tetrapropylammonium hydroxide solution is preferably 25%; the solvent of the tetrapropylammonium hydroxide solution is preferably water. In the present invention, the water is preferably deionized water. The invention limits the dosage of the raw materials in the range, and the benzene ring-shaped ZSM-5 molecular sieve with good appearance and structure, uniform size and uniform distribution can be obtained after hydrothermal reaction.
In the present invention, the method for mixing tetrapropylammonium hydroxide solution, water, sodium metaaluminate and ethyl orthosilicate preferably comprises: water, sodium metaaluminate and ethyl orthosilicate are added to the tetrapropylammonium hydroxide solution in sequence. In the invention, after one raw material is added, the other raw material is added at intervals, so that the reaction can be gradually carried out, the completion of each step of reaction can be ensured, and the occurrence of uncontrollable side reaction can be avoided. In the present invention, the mixing is preferably performed under stirring. In the present invention, the interval is preferably 10 to 60 minutes.
In a specific embodiment of the invention, a tetrapropylammonium hydroxide solution and water are subjected to first mixing to obtain a first mixture; performing second mixing on the first mixture and sodium metaaluminate to obtain a second mixture; and thirdly mixing the second mixture with ethyl orthosilicate. In the invention, the time of the first mixing is 30min; the second mixing time is 2h; the third mixing time is 6-12 h. In the present invention, the purpose of the first mixing is to provide a template for the synthesis of the ZSM-5 molecular sieve; the purpose of the second mixing is to provide an aluminum source for the synthesis of the molecular sieve; the purpose of the third mix is to provide a source of silicon for the synthesis of the molecular sieve.
In the present invention, the hydrothermal reaction is preferably performed in a closed vessel; the closed container is preferably a polytetrafluoroethylene lining autoclave. The invention adopts the closed container to prevent the solvent or intermediate product from volatilizing in the reaction. Preferably, the high-pressure reaction kettle with the polytetrafluoroethylene lining has better high-temperature resistance and non-tackiness, and has no adverse effect on the reaction.
In the present invention, the temperature of the hydrothermal reaction is preferably 100 to 180 ℃, more preferably 150 to 160 ℃; the time of the hydrothermal reaction is preferably 12 to 36 hours, more preferably 12 to 24 hours. In the hydrothermal reaction process, crystallization reaction occurs. The present invention is limited to the above-described hydrothermal reaction conditions, and can ensure that the reaction proceeds sufficiently.
After the reaction solution is obtained, the invention preferably carries out solid-liquid separation on the reaction solution, and the obtained solid substances are washed, dried and calcined in sequence to obtain the ZSM-5 molecular sieve. In the present invention, the solid-liquid separation method is preferably centrifugation; the rotation speed of the centrifugation is preferably 5000-9000 rpm; the time of the centrifugation is preferably 3 to 5 minutes. The invention can ensure complete separation of the precipitate and the solution by adopting the centrifugation conditions. In the present invention, the washing liquid is preferably water; the washing is preferably a centrifugal washing; the rotation speed of the centrifugal washing is preferably 5000-9000 rpm; the time of each centrifugal washing is preferably 3-5 min; the number of times of the centrifugal washing is preferably 1 to 3. In the present invention, the temperature of the drying is preferably 100 ℃; the drying time is preferably 12 hours. The invention can ensure thorough drying of moisture by adopting the drying conditions. In the present invention, the temperature of the calcination is preferably 500 to 750 ℃, more preferably 550 to 600 ℃; the calcination time is preferably 3 to 6 hours, more preferably 4 to 5 hours. In the present invention, the heating rate from the drying temperature to the calcining temperature is preferably 3 to 10 ℃/min, more preferably 3 ℃/min. The invention removes the template tetrapropylammonium hydroxide by calcination.
After the ZSM-5 molecular sieve is prepared, the ZSM-5 molecular sieve and the alkali solution are mixed and etched to obtain the hollow ZSM-5 molecular sieve. In the present invention, the alkali solution is preferably a sodium hydroxide solution or a potassium hydroxide solution; the concentration of the alkali solution is preferably 0.02 to 0.5mol/L, more preferably 0.2mol/L. In the present invention, the mass ratio of the ZSM-5 molecular sieve to the alkali solution is preferably 30 to 50mL/g, more preferably 30mL/g. The invention adopts the alkali solution with the concentration to obtain the multi-stage pore canal molecular sieve with a large number of micropores, mesopores and a small number of macropores which coexist, and can keep the zeolite structure.
In the present invention, the etching temperature is preferably 50 to 80 ℃, more preferably 65 to 70 ℃; the etching time is preferably 30 to 60 minutes, more preferably 30 minutes. In the present invention, the etching is preferably performed in an oil bath. The invention can make the alkali etching more fully and completely by adopting the etching conditions.
Preferably, after the etching, the obtained solid material is washed and dried in sequence to obtain the hollow ZSM-5 molecular sieve. In the present invention, the washing liquid is preferably water; the washing is preferably a centrifugal washing; the rotation speed of the centrifugal washing is preferably 5000-9000 rpm; the time of each centrifugal washing is preferably 3-5 min; the number of times of the centrifugal washing is preferably 1 to 3. In the present invention, the temperature of the drying is preferably 100 ℃; the drying time is preferably 12 hours.
In the invention, the hollow ZSM-5 molecular sieve has a hollow structure and a porous structure; the hollow ZSM-5 molecular sieve preferably has a size of 0.5. Mu.m.times.0.4. Mu.m.times.0.2. Mu.m; the pore diameter of the hollow ZSM-5 molecular sieve is 0-2 nm of micropores, 5-50 nm of mesopores and larger than 50nm of macropores.
After the hollow ZSM-5 molecular sieve is obtained, the hollow ZSM-5 molecular sieve is placed in an iron salt solution for impregnation, and the ZSM-5 molecular sieve loaded with iron element is obtained. In the present invention, the iron salt solution is preferably at least one of an iron nitrate solution and an iron chloride solution. In the present invention, the mass concentration of the iron salt solution is preferably 10 to 15mmol/L, more preferably 12.4mmol/L. In the present invention, the preparation method of the iron salt solution preferably includes: the ferric salt and water are mixed to obtain a ferric salt solution. In the present invention, the water is preferably deionized water. In the present invention, the mass ratio of the hollow ZSM-5 molecular sieve to the iron salt is preferably 1:400-500, more preferably 1:435.
In the present invention, the time of the impregnation is preferably 6 to 24 hours, more preferably 10 to 12 hours. In the present invention, the impregnation is preferably performed under room temperature conditions. The invention can ensure the load and the dispersion of Fe metal.
Preferably, after the impregnation, the obtained solid substances are washed and dried in sequence to obtain the ZSM-5 molecular sieve loaded with the iron element. In the present invention, the washing liquid is preferably water; the washing is preferably a centrifugal washing; the rotation speed of the centrifugal washing is preferably 5000-9000 rpm; the time of each centrifugal washing is preferably 3-5 min; the number of times of the centrifugal washing is preferably 1 to 3. In the present invention, the drying is preferably freeze-drying; the drying time is preferably 12 hours. The invention adopts freeze drying to prevent Fe caused by high temperature drying 3 O 4 The particles are heated to aggregate.
After obtaining the ZSM-5 molecular sieve loaded with the iron element, the invention carries out the ZSM-5 molecular sieve loaded with the iron elementRoasting to obtain Fe 3 O 4 -ZSM-5 composite. In the present invention, the temperature of the calcination is preferably 460 to 520 ℃, more preferably 480 to 500 ℃; the heat preservation time is preferably 4-6 hours. In the present invention, the atmosphere for the calcination is preferably air.
In the present invention, the temperature rise rate from room temperature to the baking temperature is preferably 5 to 10 ℃/min, more preferably 6 to 8 ℃/min.
In the present invention, the firing is preferably performed in a muffle furnace. The invention forms Fe in situ in the cavity of the hollow ZSM-5 molecular sieve by roasting 3 O 4 And (3) nanoparticles.
The preparation method provided by the invention is simple, the reaction time is short, the raw material cost is low, the method is suitable for industrial mass production, the environment is not polluted, and the prepared Fe is 3 O 4 The ZSM-5 composite material has high specific surface area, hierarchical porous structure and high catalytic activity. Fe prepared by the invention 3 O 4 The ZSM-5 composite material still maintains the crystal structure of the ZSM-5 molecular sieve, and large-scale structural damage does not occur.
The invention also provides the Fe in the technical proposal 3 O 4 ZSM-5 composite material or Fe prepared by the preparation method according to the technical scheme 3 O 4 Use of a ZSM-5 composite in the catalysis of friedel-crafts alkylation reactions. The invention uses magnetic Fe 3 O 4 The nano particles are encapsulated in a ZSM-5 cavity, so that Fe is effectively controlled 3 O 4 The size of the nano particles improves the catalytic activity and stability, and has high catalytic activity in the catalytic Friedel-crafts alkylation reaction.
The technical solutions of the present invention will be clearly and completely described in the following in connection with the embodiments of the present invention. It will be apparent that the described embodiments are only some, but not all, embodiments of the invention. 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.
Example 1
1) Mixing 12g of tetrapropylammonium hydroxide with 47g of deionized water, and stirring for 30min; then adding 0.0656g of sodium metaaluminate and stirring for 2 hours; finally, 8.32g of ethyl orthosilicate were added, sealed and stirred at room temperature for 12h.
2) Transferring the mixed solution into a polytetrafluoroethylene-lined high-pressure reaction kettle, and reacting at 150 ℃ for 24 hours to prepare a reaction solution.
3) Taking out the reaction solution, naturally cooling at room temperature, centrifuging at 9000rpm for 3min to obtain precipitate, washing for three times, and drying in a 100 ℃ oven for 12h; then placing the mixture in a muffle furnace for roasting for 4 hours at 550 ℃ to obtain the ZSM-5 molecular sieve, wherein the temperature rising rate of the muffle furnace is 3 ℃/min.
4) And etching the ZSM-5 molecular sieve with 0.2mol/L sodium hydroxide solution for 30min under the oil bath condition of 65 ℃, centrifugally washing for three times, and then placing the obtained product in a 100 ℃ oven for drying for 12h to obtain the hollow ZSM-5 molecular sieve.
5) Taking 0.3g of ferric nitrate, and adding the ferric nitrate into 100mL of deionized water to prepare a ferric nitrate solution; immersing 0.05g of hollow ZSM-5 molecular sieve in 30mL of ferric nitrate solution at room temperature for 12h; and (3) centrifugally washing for three times, and then placing the mixture in a freeze dryer for drying for 12 hours to obtain the ZSM-5 molecular sieve loaded with the iron element.
6) Placing the ZSM-5 molecular sieve loaded with the iron element into a muffle furnace for roasting, wherein the roasting temperature is 480 ℃, the heat preservation time is 4 hours, and the heating rate is 5 ℃/min, so as to obtain Fe 3 O 4 -ZSM-5 composite.
Fe prepared in this example 3 O 4 The ZSM-5 composite material comprises a hollow ZSM-5 molecular sieve and Fe in-situ loaded in a cavity of the hollow ZSM-5 molecular sieve 3 O 4 The characterization results of the morphology and structure of the nano particles are shown in figures 1-3.
FIG. 1 shows Fe prepared in example 1 3 O 4 Transmission Electron Microscopy (TEM) images of the ZSM-5 composite material, circular Fe can be seen 3 O 4 The magnetic monomer is encapsulated within a ZSM-5 cavity.
FIG. 2 is a diagram of Fe prepared in example 1 3 O 4 -nitrogen adsorption and desorption isotherm plot of ZSM-5 composite. The invention is thatPrepared Fe 3 O 4 The ZSM-5 composite material is high-catalytic-activity iron ion exchange mesoporous ZSM-5, and keeps consistent with the adsorption and desorption curve of the mesoporous ZSM-5, thus illustrating the Fe prepared by the invention 3 O 4 The ZSM-5 composite material still maintains good mesoporous performance, and the large-scale destruction of the structure does not occur.
FIG. 3 is a diagram of Fe prepared in example 1 3 O 4 -hysteresis loop of ZSM-5 composite. The relevant magnetic parameters of the material can be seen, wherein the amount of magnetic saturation is 42emu/g.
Fe prepared in this example 3 O 4 The total pore volume of the ZSM-5 composite was 0.24cm 3 /g, including 0.1cm 3 Per gram of micropore volume and 0.14cm 3 Mesoporous (macro) pore volume per gram; surface area of 380m 2 /g, which includes 187m 2 Micropore area per gram and 193m 2 External surface area per gram. In addition, experiments prove that the Fe prepared in the embodiment 3 O 4 The ZSM-5 composite material still maintains a sound structure in a 2mol/L sodium hydroxide solution and a 20wt% hydrofluoric acid solution and a 2mol/L hydrochloric acid solution, and has excellent acid and alkali resistance. The structure is intact at 1100 ℃ for 1h and at-68 ℃, and the high temperature resistance and the low temperature resistance are excellent.
Example 2
1) Mixing 5.41g of tetrapropylammonium hydroxide with 20g of deionized water, and stirring for 30min; then adding 0.025g of sodium metaaluminate and stirring for 2 hours; finally, 4.16g of ethyl orthosilicate were added, sealed and stirred at room temperature for 12h.
2) Transferring the mixed solution into a polytetrafluoroethylene-lined high-pressure reaction kettle, and reacting at 150 ℃ for 24 hours to prepare a reaction solution.
3) Taking out the reaction solution, naturally cooling at room temperature, centrifuging at 9000rpm for 3min to obtain precipitate, washing for three times, and drying in a 100 ℃ oven for 12h; then placing the mixture in a muffle furnace for roasting for 4 hours at 550 ℃ to obtain the ZSM-5 molecular sieve, wherein the temperature rising rate of the muffle furnace is 3 ℃/min.
4) And etching the ZSM-5 molecular sieve with 0.2mol/L sodium hydroxide solution for 30min under the oil bath condition of 65 ℃, centrifugally washing for three times, and then placing the obtained product in a 100 ℃ oven for drying for 12h to obtain the hollow ZSM-5 molecular sieve.
5) Taking 0.3g of ferric nitrate, and adding the ferric nitrate into 100mL of deionized water to prepare a ferric nitrate solution; immersing 0.05g of hollow ZSM-5 molecular sieve in 30mL of ferric nitrate solution at room temperature for 12h; and (3) centrifugally washing for three times, and then placing the mixture in a freeze dryer for drying for 12 hours to obtain the ZSM-5 molecular sieve loaded with the iron element.
6) Placing the ZSM-5 molecular sieve loaded with the iron element into a muffle furnace for roasting, wherein the roasting temperature is 480 ℃, the heat preservation time is 4 hours, and the heating rate is 5 ℃/min, so as to obtain Fe 3 O 4 -ZSM-5 composite.
Example 3
1) Mixing 5.41g of tetrapropylammonium hydroxide with 20g of deionized water, and stirring for 30min; then adding 0.0328g of sodium metaaluminate and stirring for 2h; finally, 4.16g of ethyl orthosilicate were added, sealed and stirred at room temperature for 12h.
2) Transferring the mixed solution into a polytetrafluoroethylene-lined high-pressure reaction kettle, and reacting at 150 ℃ for 24 hours to prepare a reaction solution.
3) Taking out the reaction solution, naturally cooling at room temperature, centrifuging at 9000rpm for 3min to obtain precipitate, washing for three times, and drying in a 100 ℃ oven for 12h; then placing the mixture in a muffle furnace for roasting for 4 hours at 550 ℃ to obtain the ZSM-5 molecular sieve, wherein the temperature rising rate of the muffle furnace is 3 ℃/min.
4) And etching the ZSM-5 molecular sieve with 0.2mol/L sodium hydroxide solution for 30min under the oil bath condition of 65 ℃, centrifugally washing for three times, and then placing the obtained product in a 100 ℃ oven for drying for 12h to obtain the hollow ZSM-5 molecular sieve.
5) Taking 0.3g of ferric nitrate, and adding the ferric nitrate into 100mL of deionized water to prepare a ferric nitrate solution; immersing 0.05g of hollow ZSM-5 molecular sieve in 30mL of ferric nitrate solution at room temperature for 12h; and (3) centrifugally washing for three times, and then placing the mixture in a freeze dryer for drying for 12 hours to obtain the ZSM-5 molecular sieve loaded with the iron element.
6) Placing the ZSM-5 molecular sieve loaded with the iron element into a muffle furnace for roasting, wherein the roasting temperature is 480 ℃, the heat preservation time is 4 hours, and the heating rate is 5 ℃/min, so as to obtain Fe 3 O 4 -ZSM-5 composite.
The foregoing is merely a preferred embodiment of the present invention and it should be noted that modifications and adaptations to those skilled in the art may be made without departing from the principles of the present invention, which are intended to be comprehended within the scope of the present invention.
Claims (1)
1. Fe (Fe) 3 O 4 The preparation method of the ZSM-5 composite material comprises the following steps:
1) Mixing 12g of tetrapropylammonium hydroxide with 47g of deionized water, and stirring for 30min; then adding 0.0656g of sodium metaaluminate and stirring for 2 hours; finally, 8.32g of ethyl orthosilicate is added, sealed and stirred for 12 hours at room temperature;
2) Transferring the mixed solution into a high-pressure reaction kettle with a polytetrafluoroethylene lining, and reacting at 150 ℃ for 24 hours to prepare a reaction solution;
3) Taking out the reaction solution, naturally cooling at room temperature, centrifuging at 9000rpm for 3min to obtain precipitate, washing for three times, and drying in a 100 ℃ oven for 12h; then placing the mixture in a muffle furnace for roasting for 4 hours at 550 ℃ to obtain the ZSM-5 molecular sieve, wherein the temperature rising rate of the muffle furnace is 3 ℃/min;
4) Etching the ZSM-5 molecular sieve with 0.2mol/L sodium hydroxide solution for 30min under the oil bath condition of 65 ℃, centrifugally washing for three times, and then placing the obtained product in a 100 ℃ oven for drying for 12h to obtain a hollow ZSM-5 molecular sieve;
5) Taking 0.3g of ferric nitrate, and adding the ferric nitrate into 100mL of deionized water to prepare a ferric nitrate solution; immersing 0.05g of hollow ZSM-5 molecular sieve in 30mL of ferric nitrate solution at room temperature for 12h; centrifuging, washing for three times, and placing in a freeze dryer for drying for 12 hours to obtain the ZSM-5 molecular sieve loaded with the iron element;
6) Placing the ZSM-5 molecular sieve loaded with the iron element into a muffle furnace for roasting, wherein the roasting temperature is 480 ℃, the heat preservation time is 4 hours, and the heating rate is 5 ℃/min, so as to obtain Fe 3 O 4 -ZSM-5 composite.
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