CN103447078B - A kind of nano MFI-type molecular sieve with hierarchical pore structure and its preparation method and application - Google Patents
A kind of nano MFI-type molecular sieve with hierarchical pore structure and its preparation method and application Download PDFInfo
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- 239000002808 molecular sieve Substances 0.000 title claims abstract description 171
- 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 164
- 238000002360 preparation method Methods 0.000 title claims abstract description 29
- 239000002149 hierarchical pore Substances 0.000 title claims description 20
- 239000011148 porous material Substances 0.000 claims abstract description 61
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 39
- 239000012452 mother liquor Substances 0.000 claims abstract description 35
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 28
- 125000002091 cationic group Chemical group 0.000 claims abstract description 16
- 238000001035 drying Methods 0.000 claims abstract description 13
- 238000000034 method Methods 0.000 claims abstract description 11
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims abstract description 11
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims abstract description 11
- 210000001367 artery Anatomy 0.000 claims abstract description 9
- -1 molecular sieve compound Chemical class 0.000 claims abstract description 9
- 238000006243 chemical reaction Methods 0.000 claims abstract description 8
- 239000000725 suspension Substances 0.000 claims abstract description 7
- 238000001914 filtration Methods 0.000 claims abstract description 3
- 238000005406 washing Methods 0.000 claims abstract description 3
- 239000013078 crystal Substances 0.000 claims description 21
- 239000008367 deionised water Substances 0.000 claims description 12
- 229910021641 deionized water Inorganic materials 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- 230000015572 biosynthetic process Effects 0.000 claims description 10
- 239000002131 composite material Substances 0.000 claims description 9
- 230000000694 effects Effects 0.000 claims description 9
- 230000007062 hydrolysis Effects 0.000 claims description 7
- 238000006460 hydrolysis reaction Methods 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 7
- 239000002159 nanocrystal Substances 0.000 claims description 7
- LPSKDVINWQNWFE-UHFFFAOYSA-M tetrapropylazanium;hydroxide Chemical compound [OH-].CCC[N+](CCC)(CCC)CCC LPSKDVINWQNWFE-UHFFFAOYSA-M 0.000 claims description 7
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 5
- 229920000767 polyaniline Polymers 0.000 claims description 5
- 229910052710 silicon Inorganic materials 0.000 claims description 5
- 239000010703 silicon Substances 0.000 claims description 5
- 239000010936 titanium Substances 0.000 claims description 5
- 239000000463 material Substances 0.000 claims description 4
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 3
- NJSSICCENMLTKO-HRCBOCMUSA-N [(1r,2s,4r,5r)-3-hydroxy-4-(4-methylphenyl)sulfonyloxy-6,8-dioxabicyclo[3.2.1]octan-2-yl] 4-methylbenzenesulfonate Chemical compound C1=CC(C)=CC=C1S(=O)(=O)O[C@H]1C(O)[C@@H](OS(=O)(=O)C=2C=CC(C)=CC=2)[C@@H]2OC[C@H]1O2 NJSSICCENMLTKO-HRCBOCMUSA-N 0.000 claims description 3
- 239000004411 aluminium Substances 0.000 claims description 3
- 229910052782 aluminium Inorganic materials 0.000 claims description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 3
- 150000001408 amides Chemical class 0.000 claims description 3
- 229920006389 polyphenyl polymer Polymers 0.000 claims description 3
- 238000012545 processing Methods 0.000 claims description 3
- 238000005245 sintering Methods 0.000 claims description 3
- 229910052719 titanium Inorganic materials 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims description 2
- 239000003054 catalyst Substances 0.000 abstract description 9
- 238000007796 conventional method Methods 0.000 abstract description 5
- 238000002425 crystallisation Methods 0.000 abstract description 4
- 230000008025 crystallization Effects 0.000 abstract description 4
- 239000010457 zeolite Substances 0.000 description 24
- 229910021536 Zeolite Inorganic materials 0.000 description 23
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 22
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 9
- 238000001816 cooling Methods 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 4
- 229910052708 sodium Inorganic materials 0.000 description 4
- 239000011734 sodium Substances 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 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 description 3
- 229920006317 cationic polymer Polymers 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 239000002105 nanoparticle Substances 0.000 description 3
- GFLJTEHFZZNCTR-UHFFFAOYSA-N 3-prop-2-enoyloxypropyl prop-2-enoate Chemical compound C=CC(=O)OCCCOC(=O)C=C GFLJTEHFZZNCTR-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 description 2
- 150000001409 amidines Chemical class 0.000 description 2
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical group [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000003795 desorption Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000000703 high-speed centrifugation Methods 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 229920000371 poly(diallyldimethylammonium chloride) polymer Polymers 0.000 description 2
- 229920002401 polyacrylamide Polymers 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- QDZRBIRIPNZRSG-UHFFFAOYSA-N titanium nitrate Chemical compound [O-][N+](=O)O[Ti](O[N+]([O-])=O)(O[N+]([O-])=O)O[N+]([O-])=O QDZRBIRIPNZRSG-UHFFFAOYSA-N 0.000 description 2
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical group [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 230000029936 alkylation Effects 0.000 description 1
- 238000005804 alkylation reaction Methods 0.000 description 1
- 239000005030 aluminium foil Substances 0.000 description 1
- SMZOGRDCAXLAAR-UHFFFAOYSA-N aluminium isopropoxide Chemical compound [Al+3].CC(C)[O-].CC(C)[O-].CC(C)[O-] SMZOGRDCAXLAAR-UHFFFAOYSA-N 0.000 description 1
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910001593 boehmite Inorganic materials 0.000 description 1
- 238000004517 catalytic hydrocracking Methods 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000004231 fluid catalytic cracking Methods 0.000 description 1
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 description 1
- 150000002605 large molecules Chemical class 0.000 description 1
- 230000002045 lasting effect Effects 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- DCKVFVYPWDKYDN-UHFFFAOYSA-L oxygen(2-);titanium(4+);sulfate Chemical compound [O-2].[Ti+4].[O-]S([O-])(=O)=O DCKVFVYPWDKYDN-UHFFFAOYSA-L 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000011973 solid acid Substances 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- 229910000348 titanium sulfate Inorganic materials 0.000 description 1
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
Classifications
-
- 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
Landscapes
- Silicates, Zeolites, And Molecular Sieves (AREA)
Abstract
The invention belongs to catalyst and applied technical field thereof, specifically a kind of easily separated, high hydrothermal stability, multi-stage artery structure nano MFI-type molecular sieve and its preparation method and application.The method step: (1) chooses the nano MFI-type molecular sieve suspension that prepared as mother liquor; (2) in mother liquor, add cationic flocculant to assemble nano molecular sieve; (3) nano molecular sieve loads reactor Hydrothermal Synthesis after assembling, obtains the nano molecular sieve compound of lumpy sizes 100 nanometer to 100 micron.Nano molecular sieve compound, through conventional filtration, washing, drying, roasting, obtains multi-stage artery structure nano MFI-type molecular sieve.Nano MFI-type molecular sieve prepared by the method can realize being separated by filter operation, nano MFI-type molecular sieve has open intergranular pore channel structure, pore volume is large, percent crystallization in massecuite is high, hydrothermal stability is high, in preparing propylene from methanol reaction, show and prepare the higher productivity of propylene of nano MFI-type molecular sieve and stability compared with conventional method.
Description
Technical field
The invention belongs to catalyst and applied technical field thereof, specifically a kind of easily separated, high hydrothermal stability, multi-stage artery structure nano MFI-type zeolite molecular sieve and preparation method thereof and the application in preparing propylene from methanol thereof.
Background technology
MFI type zeolite molecular sieve is a class height silicon micro-pore zeolite of Mobil company 20 century 70 exploitation, the well-regulated duct of tool, can the acidity of modulation and good shape selectivity, as solid acid catalyst in petrochemical industry extensive use.
At present, the MFI-type molecular sieve catalyst of industrial use is mostly be of a size of the large grain size MFI molecular sieve of several microns.Because MFI molecular sieve pore passage is long and narrow, crystallite dimension is comparatively large in addition, and large molecule is comparatively large at crystal inside diffusional resistance, easily generates carbon distribution, causes catalyst life shorter.Relative to the microsized zeolite of routine, it is large that nano molecular sieve has surface area, the feature of the many and short grade in duct of mesopore volume, therefore catalytic activity is often shown high, carbon accumulation resisting ability is strong, the advantages such as stability is lasting, in hydrocracking, fluid catalytic cracking, the alkylation of benzene, the oligomerisation reaction of alkene, preparing gasoline by methanol, in the laboratory research of the reaction such as the synthesis of methylamine, nano molecular sieve all achieves the effect being significantly better than conventional micron molecular sieve, fully demonstrate nano molecular sieve catalyst to raising chemical industry resource utilization and added value of product, the importance of development high-efficiency cleaning production technology.
But compared with the synthesis of conventional micron level MFI molecular sieve, preparation nanometer MFI zeolite is very complicated process.Usually, the nanocrystal of synthesis is all suspended in mother liquor, be separated obtain these nano zeolites all will by ultracentrifugal method, and this is very difficult for industrial extensive preparation, and the nano molecular sieve productive rate that high speed centrifugation obtains is lower.Particularly, nano molecular sieve crystal due to its outer surface comparatively large, cause its activity higher, hydrothermal stability is poor.Above 2 constrain its widespread adoption.
Summary of the invention
The object of the present invention is to provide a kind of easily separated, high hydrothermal stability, multi-stage artery structure nano MFI-type zeolite molecular sieve and its preparation method and application, improve the hydrothermal stability of nano MFI-type molecular sieve, the separation and recovery Utilizing question of mass transfer ability, solution nanometer MFI molecular sieve.
Technical scheme of the present invention is:
The invention provides the preparation method of a kind of high hydrothermal stability, easily separated, multi-stage artery structure nano MFI-type zeolite molecular sieve, the method step is:
Choose the nanometer MFI molecular sieve suspension that prepared as required molecular sieve mother liquor, in molecular sieve mother liquor, add cationic flocculant nano molecular sieve in mother liquor is assembled; Nano molecular sieve, after cationic flocculant assembling, loads reactor Hydrothermal Synthesis, obtains being of a size of the assemble nanometer molecular screen composite of 100 nanometers to 100 micron; Nano molecular sieve compound, through conventional filtration, washing, drying, roasting, obtains hierarchical porous structure nanometer MFI molecular sieve.
In the present invention, MFI-type molecular sieve is Silicalite-1, ZSM-5 or TS-1;
In the present invention, the crystalline size of nano MFI-type molecular sieve is 5-500 nanometer;
In the present invention, the preparation process of molecular sieve mother liquor is as follows:
By the 1:0.05-0.5:0.001-0.1:10-100 mixing in molar ratio of silicon source, TPAOH, aluminium source or titanium source, deionized water, after the complete hydrolysis of silicon source, above-mentioned solution is put Hydrothermal Synthesis in a kettle., at 120-150 DEG C of Hydrothermal Synthesis 4-8h, obtain nano MFI-type molecular sieve suspension.
Wherein, aluminium source is aluminum nitrate, aluminum sulfate, sodium metaaluminate, boehmite, aluminium foil or aluminium isopropoxide etc., and titanium source is butyl titanate, titanium sulfate, Titanium Nitrate or titanium tetrachloride.
In the present invention, cationic flocculant is one or more in poly-amidine, polyvinylamine, PAMC, PDDA, softex kw, polyaniline, polyacrylamide;
In the present invention, cationic flocculant addition is the 1%-20% of molecular sieve mother liquor quality, is preferably 2-10%.
In the present invention, the treatment temperature of Hydrothermal Synthesis is 90-200 DEG C, is preferably 110-170 DEG C; The processing time of Hydrothermal Synthesis is 2-160 hour, is preferably 3-24 hour.
In the present invention, sintering temperature is 450-650 DEG C, is preferably 500-600 DEG C; Roasting time is 1-24 hour, is preferably 3-10 hour.
In the present invention, high hydrothermal stability, easily separated, nano MFI-type molecular sieve with hierarchical pore structure are assembled by many nano molecular sieve crystal, crystal grain is piled up each other and is formed a large amount of intergranular pore channels, there is open intergranular pore channel structure, hierarchical porous structure nano molecular sieve assembly is of a size of 100 nanometers to 100 micron, and this size refers to the size (particle diameter) of the aggregate that nano molecular sieve crystal grain is assembled into.Wherein, the implication of multistage pore canal be this material itself had by MFI zeolite molecular sieve micropore, mesoporous between nanometer MFI zeolite molecular sieve crystal, and the macropore composition between nano molecular sieve assembly.In nano MFI-type molecular sieve with hierarchical pore structure, specific area scope is 300-600m
2g
-1; Total pore volume scope is 0.2-2.0cm
3g
-1, micro pore volume scope is 0.01-0.17cm
3g
-1, mesopore volume scope is 0.02-1.0cm
3g
-1, macropore volume scope is 0.02-1.8cm
3g
-1.Wherein, micropore size scope is that 0.5-2nm(micropore size is not containing 2nm), mesoporous pore size scope is 2-50nm, and macropore diameter scope is that 50-2000nm(macropore diameter is not containing 50nm).
In the present invention, high hydrothermal stability, segregative nano MFI-type molecular sieve, wherein, the Si/Al atomic ratio=10-1000 of nano-ZSM-5 type molecular sieve; Si/Ti atomic ratio=the 10-1000 of nano-scale TS-1 type molecular sieve.
In the present invention, hierarchical porous structure nano molecular sieve assembly can realize being separated by filter operation.
The application of described multi-stage artery structure nano MFI-type molecular sieve, in MTP preparing propylene from methanol process, fills in fixed bed reactors by multi-stage artery structure nano MFI-type molecular sieve, and material liquid is the industrial methanol of 40-95wt%, and mass space velocity is 0.3-10h
-1, reaction temperature is 400-550 DEG C.
The present invention has following beneficial effect:
1, the preparation method of high hydrothermal stability of the present invention, easily separated nano MFI-type molecular sieve catalyst, first prepares nano molecular sieve mother liquor; Then, utilize the long-chain cationic polymers such as poly-amidine, polyaniline, polyvinylamine, PAMC, PDDA, softex kw, polyacrylamide, electronegative nano molecular sieve is assembled; The nano molecular sieve solution assembled is added in reactor, continues crystallization under hydrothermal conditions.Make to grow mutually between nano molecular sieve crystal, realize chemical bond, cationic polymer plays the double action of assembling masterplate and pore creating material wherein.
2, the nano molecular sieve prepared by the inventive method is adopted can to realize being separated by filter operation, prepared nanometer MFI molecular sieve has open intergranular pore channel structure, pore volume is large, percent crystallization in massecuite is high, hydrothermal stability is high, in preparing propylene from methanol reaction, show and prepare the higher productivity of propylene of nanometer MFI molecular sieve and catalyst stability compared with conventional method.
3, the nanometer MFI molecular sieve pore volume adopting the inventive method to prepare can reach 2.0cm
3/ g, with traditional MFI-type molecular sieve (0.175cm
3/ g) compare and be significantly increased.
Accompanying drawing explanation
Fig. 1 is the XRD spectra of the product that the embodiment of the present invention 1 is synthesized.
Fig. 2 is the SEM picture of the product that the embodiment of the present invention 1 is synthesized.
Fig. 3 a is nitrogen adsorption, the desorption curve of the product that the embodiment of the present invention 1 is synthesized.
Fig. 3 b is the product B JH method differential pore volume pore size distribution curve that the embodiment of the present invention 1 is synthesized.Wherein, V-volume; D-aperture.
Fig. 4 be the embodiment of the present invention 1 synthesize product and Conventional nano ZSM-5 suspension contrast photo.Wherein, left side is the ZSM-5 that the embodiment of the present invention 1 is synthesized; Right side is Conventional nano ZSM-5.
Fig. 5 is that the product that the embodiment of the present invention 1 is synthesized compares with nano-ZSM-5 molecular sieve catalytic performance in preparing propylene from methanol reacts prepared by conventional method.
Detailed description of the invention
Below by embodiment in detail the present invention is described in detail.
Embodiment 1
In the present embodiment, the preparation method of high hydrothermal stability, easily separated, nano-ZSM-5 type zeolite molecular sieve:
First, preparation comprises the mother liquor of nanoscale ZSM-5 molecular sieve: by the 1:0.32:0.02:29 mixing in molar ratio of ethyl orthosilicate, TPAOH, sodium metaaluminate, deionized water, after ethyl orthosilicate complete hydrolysis, above-mentioned solution is put Hydrothermal Synthesis in a kettle., at 130 DEG C of Hydrothermal Synthesis 6h, obtain nano-ZSM-5 molecular sieve mother liquor.In above-mentioned molecular sieve mother liquor, add polyphenyl acid amides (polyphenyl acid amides addition is 5% of molecular sieve mother liquor quality), after 2 hours, add reactor 12000 revs/min of lower high-speed stirred, at 160 DEG C, Hydrothermal Synthesis 6 hours, makes nano-ZSM-5 molecular sieve compound.Gained molecular screen composite, after the molecular sieve filter of routine filters, repeatedly cleans for several times in the deionized water of 100 DEG C, drying 12 hours under 100 DEG C of conditions.After drying, sample is in Muffle furnace, 550 DEG C of roastings 6 hours (programming rate is 2 DEG C/min, with stove cooling).
Fig. 1 is the XRD collection of illustrative plates of products obtained therefrom, therefrom can find out that product has typical MFI type zeolite molecular sieve structure, and sample has higher degree of crystallinity.
Fig. 2 is the SEM pattern of products obtained therefrom, therefrom can find out that nano molecular sieve aggregate is made up of the type ZSM 5 molecular sieve crystal of many Nano grades, have higher intercrystalline pore rate between crystal.In the present embodiment, total pore volume is 0.69cm
3g
-1.The micropore pore volume that ZSM-5 zeolite molecular sieve has itself is 0.12cm
3g
-1, the mesoporous pore volume between nano-sized ZSM-5 zeolite molecular sieve crystal is 0.45cm
3g
-1, the macropore pore volume between nano molecular sieve assembly is 0.12cm
3g
-1.Wherein, micropore size scope is 0.5-0.7nm, and mesoporous pore size scope is 2-10nm, and macropore diameter scope is 60-150nm.
In the present embodiment, nano MFI-type molecular sieve with hierarchical pore structure is assembled under the effect of cationic flocculant by nano molecular sieve crystal, nanocrystal piles up formation intergranular pore channel each other, has open intergranular pore channel structure, and hierarchical porous structure nano molecular sieve assembly is of a size of 300-500nm.
Fig. 3 a is nitrogen adsorption, the desorption curve of products obtained therefrom, can find out, the specific area (BET) of the nano-ZSM-5 molecular sieve obtained is 380.28m
2g
-1.Fig. 3 b is the pore size distribution curve of products obtained therefrom, can find out, the nano-ZSM-5 molecular sieve obtained has multi-stage artery structure.
Fig. 4 be the embodiment of the present invention 1 synthesize product and Conventional nano ZSM-5 suspension contrast photo.Therefrom can find out, the nano-ZSM-5 type molecular sieve of conventional method synthesis is suspended in the middle of solution, even if still can not be separated completely through high speed centrifugation (12000 revs/min × 2 hours).Products obtained therefrom of the present invention, because nano molecular sieve crystal is assembled through cationic polymer, is deposited on bottom solution, by suction filtration and separable.
Embodiment 2
In the present embodiment, the preparation method of high hydrothermal stability, easily separated, nano-ZSM-5 type zeolite molecular sieve:
First, preparation comprises the mother liquor of nano-ZSM-5 molecular sieve: by the 1:0.32:0.02:29 mixing in molar ratio of ethyl orthosilicate, TPAOH, sodium metaaluminate, deionized water, after ethyl orthosilicate complete hydrolysis, above-mentioned solution is put Hydrothermal Synthesis in a kettle., at 130 DEG C of Hydrothermal Synthesis 6h, obtain nano-ZSM-5 molecular sieve mother liquor.Diallyl dimethyl ammoniumchloride (diallyl dimethyl ammoniumchloride addition is 7.5% of molecular sieve mother liquor quality) is added in above-mentioned molecular sieve mother liquor, 12000 revs/min of lower high-speed stirred after 2 hours, add reactor, at 130 DEG C, Hydrothermal Synthesis 12 hours, makes nano-ZSM-5 molecular sieve compound.Gained molecular screen composite, after the molecular sieve filter of routine filters, repeatedly cleans for several times in the deionized water of 100 DEG C, drying 12 hours under 100 DEG C of conditions.After drying, sample is in Muffle furnace, 600 DEG C of roastings 3 hours (programming rate is 2 DEG C/min, with stove cooling).The specific area (BET) of the nano-ZSM-5 molecular sieve obtained is 356.28m
2g
-1, total pore volume is 1.06cm
3g
-1.The micropore pore volume that ZSM-5 zeolite molecular sieve has itself is 0.08cm
3g
-1, the mesoporous pore volume between nano-sized ZSM-5 zeolite molecular sieve crystal is 0.45cm
3g
-1, the macropore pore volume between nano molecular sieve assembly is 0.53cm
3g
-1.Wherein, micropore size scope is 0.5-0.65nm, and mesoporous pore size scope is 2-20nm, and macropore diameter scope is 500-2000nm.
In the present embodiment, nano MFI-type molecular sieve with hierarchical pore structure is assembled under the effect of cationic flocculant by nano molecular sieve crystal, nanocrystal piles up formation intergranular pore channel each other, has open intergranular pore channel structure, and hierarchical porous structure nano molecular sieve assembly is of a size of 50-100 micron.
Embodiment 3
In the present embodiment, the preparation method of high hydrothermal stability, easily separated, nano-ZSM-5 type zeolite molecular sieve:
First, preparation comprises the mother liquor of nano-ZSM-5 molecular sieve: by the 1:0.32:0.02:29 mixing in molar ratio of ethyl orthosilicate, TPAOH, sodium metaaluminate, deionized water, after ethyl orthosilicate complete hydrolysis, above-mentioned molecular sieve mother liquor is put Hydrothermal Synthesis in a kettle., at 130 DEG C of Hydrothermal Synthesis 6h, obtain nano-ZSM-5 molecular sieve mother liquor.Softex kw (softex kw addition is 3% of molecular sieve mother liquor quality) is added in above-mentioned solution, after 2 hours, reactor is added, at 120 DEG C 12000 revs/min of lower high-speed stirred, Hydrothermal Synthesis 24 hours, makes nano-ZSM-5 molecular sieve compound.Gained molecular screen composite, after the molecular sieve filter of routine filters, repeatedly cleans for several times in the deionized water of 100 DEG C, drying 12 hours under 100 DEG C of conditions.After drying, sample is in Muffle furnace, 500 DEG C of roastings 12 hours (programming rate is 2 DEG C/min, with stove cooling).The specific area (BET) of the nano-ZSM-5 molecular sieve obtained is 589.28m
2g
-1, total pore volume is 1.72cm
3g
-1.The micropore pore volume that ZSM-5 zeolite molecular sieve has itself is 0.10cm
3g
-1, the mesoporous pore volume between nano-sized ZSM-5 zeolite molecular sieve crystal is 0.52cm
3g
-1, the macropore pore volume between nano molecular sieve assembly is 1.10cm
3g
-1.Wherein, micropore size scope is 0.5-0.7nm, and mesoporous pore size scope is 10-30nm, and macropore diameter scope is 100-500nm.
In the present embodiment, nano MFI-type molecular sieve with hierarchical pore structure is assembled under the effect of cationic flocculant by nano molecular sieve crystal, nanocrystal piles up formation intergranular pore channel each other, has open intergranular pore channel structure, and hierarchical porous structure nano molecular sieve assembly is of a size of 10-50 micron.
Embodiment 4
In the present embodiment, the preparation method of high hydrothermal stability, easily separated, nano-scale TS-1 type zeolite molecular sieve:
First, preparation comprises the mother liquor of nano-scale TS-1 molecular sieve: by the 1:0.32:0.01:29 mixing in molar ratio of ethyl orthosilicate, TPAOH, butyl titanate, deionized water, after ethyl orthosilicate complete hydrolysis, above-mentioned solution is put Hydrothermal Synthesis in a kettle., at 130 DEG C of Hydrothermal Synthesis 6h, obtain nano-scale TS-1 molecular sieve mother liquor.In above-mentioned molecular sieve mother liquor, add polyaniline (polyaniline addition is 5.5% of molecular sieve mother liquor quality), after 2 hours, add reactor 12000 revs/min of lower high-speed stirred, at 150 DEG C, Hydrothermal Synthesis 12 hours, makes nano-scale TS-1 molecular screen composite.Gained molecular screen composite, after the molecular sieve filter of routine filters, repeatedly cleans for several times in the deionized water of 100 DEG C, drying 12 hours under 100 DEG C of conditions.After drying, sample is in Muffle furnace, 550 DEG C of roastings 3 hours (programming rate is 2 DEG C/min, with stove cooling).The specific area (BET) of the nano-scale TS-1 molecular sieve obtained is 383.56m
2g
-1, total pore volume is 1.77m
3g
-1.The micropore pore volume that nano-scale TS-1 type zeolite molecular sieve itself has is 0.12cm
3g
-1, the mesoporous pore volume between nano-scale TS-1 type zeolite molecular sieve crystal is 0.45cm
3g
-1, the macropore pore volume between nano molecular sieve assembly is 1.2cm
3g
-1.Wherein, micropore size scope is 0.5-0.7nm, and mesoporous pore size scope is 2-20nm, and macropore diameter scope is 200-500nm.
In the present embodiment, nano MFI-type molecular sieve with hierarchical pore structure is assembled under the effect of cationic flocculant by nano molecular sieve crystal, nanocrystal piles up formation intergranular pore channel each other, has open intergranular pore channel structure, and hierarchical porous structure nano molecular sieve assembly is of a size of 20-30 micron.
Embodiment 5
In the present embodiment, the preparation method of high hydrothermal stability, easily separated, nanometer silicalite-1 type zeolite molecular sieve:
First, preparation comprises the mother liquor of nanoscale silicalite-1 molecular sieve: by the 1:0.32:29 mixing in molar ratio of Ludox, TPAOH, deionized water, after ethyl orthosilicate complete hydrolysis, above-mentioned molecular sieve mother liquor is put Hydrothermal Synthesis in a kettle., at 120 DEG C of Hydrothermal Synthesis 6h, obtain nanometer silicalite-1 molecular sieve mother liquor.Softex kw (softex kw addition is 5% of molecular sieve mother liquor quality) is added in above-mentioned solution, 10000 revs/min of lower high-speed stirred after 2 hours, add reactor, at 120 DEG C, Hydrothermal Synthesis 24 hours, makes nanometer silicalite-1 molecular screen composite.Gained molecular screen composite, after the molecular sieve filter of routine filters, repeatedly cleans for several times in the deionized water of 100 DEG C, drying 12 hours under 100 DEG C of conditions.After drying, sample is in Muffle furnace, 500 DEG C of roastings 12 hours (programming rate is 2 DEG C/min, with stove cooling).The specific area (BET) of the nanometer silicalite-1 molecular sieve obtained is 467.67m
2g
-1, total pore volume is 1.85m
3g
-1.The micropore pore volume that nanoscale silicalite-1 molecular sieve itself has is 0.13cm
3g
-1, the mesoporous pore volume between nanoscale silicalite-1 molecular sieve crystal is 0.52cm
3g
-1, the macropore pore volume between nano molecular sieve assembly is 1.20cm
3g
-1.Wherein, micropore size scope is 0.5-0.7nm, and mesoporous pore size scope is 5-20nm, and macropore diameter scope is 70-120nm.
In the present embodiment, nano MFI-type molecular sieve with hierarchical pore structure is assembled under the effect of cationic flocculant by nano molecular sieve crystal, nanocrystal piles up formation intergranular pore channel each other, has open intergranular pore channel structure, and hierarchical porous structure nano molecular sieve assembly is of a size of 200-500nm.
Embodiment 6
In the present embodiment, the catalytic effect adopting the nano-ZSM-5 molecular sieve prepared of the present invention to react for preparing propylene from methanol is described, and the catalytic effect of the nano molecular sieve synthesized with conventional method contrasts.
Molecular sieve 20g embodiment 1 prepared fills in fixed bed reactors, with the industrial methanol of mass concentration 90% for raw material, and methanol quality air speed 3h
-1, under 500 DEG C of reaction temperatures, carry out catalytic reaction evaluation.
As shown in Figure 5, the nano-ZSM-5 molecular sieve prepared by the method can realize being separated by filter operation result; Prepared nano-ZSM-5 molecular sieve has open intergranular pore channel structure, and pore volume is large, and percent crystallization in massecuite is high, and hydrothermal stability is high, and in preparing propylene from methanol reaction, the relative conventional nano ZSM-5 molecular sieve of this catalyst, has longer life-span and higher productivity of propylene.The strengthening effect of mass transmitting of this raising owing to nano molecular sieve hydrothermal stability and intracrystalline pore.
Claims (7)
1. the preparation method of a nano MFI-type molecular sieve with hierarchical pore structure, it is characterized in that, nano MFI-type molecular sieve with hierarchical pore structure is assembled under the effect of cationic flocculant by nano molecular sieve crystal, nanocrystal piles up formation intergranular pore channel each other, have open intergranular pore channel structure, hierarchical porous structure nano molecular sieve assembly is of a size of 100 nanometers to 100 micron;
In nano MFI-type molecular sieve with hierarchical pore structure, specific area scope is 300-600 m
2g
-1; Total pore volume scope is 0.2-2.0 cm
3g
-1, micro pore volume scope is 0.01-0.17 cm
3g
-1, mesopore volume scope is 0.02-1.0 cm
3g
-1, macropore volume scope is 0.02-1.8 cm
3g
-1; Wherein, micropore size scope is 0.5-2nm, and mesoporous pore size scope is 2-50 nm, and macropore diameter scope is 50-2000 nm;
The preparation method of described nano MFI-type molecular sieve with hierarchical pore structure, preparation process is as follows:
(1) the nano MFI-type molecular sieve suspension that prepared is chosen as mother liquor;
Wherein, MFI-type molecular sieve is Silicalite-1, ZSM-5 or TS-1;
Wherein, the crystalline size of nano MFI-type molecular sieve is 5-500 nanometers;
(2) in mother liquor, add cationic flocculant to assemble nano molecular sieve in mother liquor, cationic flocculant addition is the 1%-20% of molecular sieve mother liquor quality; Wherein:
Described cationic flocculant is polyphenyl acid amides, diallyl dimethyl ammoniumchloride or polyaniline;
(3) nano molecular sieve is after cationic flocculant assembling, loads reactor Hydrothermal Synthesis, obtains being of a size of the assemble nanometer molecular screen composite of 100 nanometers to 100 micron; Wherein:
The treatment temperature of Hydrothermal Synthesis is 90-200 DEG C, and the processing time of Hydrothermal Synthesis is 2-160 hour;
(4) nano molecular sieve compound is through conventional filtration, washing, drying, roasting, obtains nano MFI-type molecular sieve with hierarchical pore structure;
In step (1), the preparation process of molecular sieve mother liquor is as follows:
By the 1:0.05-0.5:0.001-0.1:10-100 mixing in molar ratio of silicon source, TPAOH, aluminium source or titanium source, deionized water, after the complete hydrolysis of silicon source, above-mentioned solution is put Hydrothermal Synthesis in a kettle., at 120-150 DEG C of Hydrothermal Synthesis 4-8h, obtain nano MFI-type molecular sieve suspension.
2. according to the preparation method of nano MFI-type molecular sieve with hierarchical pore structure according to claim 1, it is characterized in that, in step (2), cationic flocculant addition is preferably the 2-10% of molecular sieve mother liquor quality.
3. according to the preparation method of nano MFI-type molecular sieve with hierarchical pore structure according to claim 1, it is characterized in that, in step (3), the treatment temperature of Hydrothermal Synthesis is preferably 110-170 DEG C, and the processing time of Hydrothermal Synthesis is preferably 3-24 hour.
4. according to the preparation method of nano MFI-type molecular sieve with hierarchical pore structure according to claim 1, it is characterized in that, in step (4), sintering temperature is 450-650 DEG C, and roasting time is 1-24 hour.
5. according to the preparation method of nano MFI-type molecular sieve with hierarchical pore structure according to claim 1, it is characterized in that, in step (4), sintering temperature is preferably 500-600 DEG C, and roasting time is preferably 3-10 hour.
6. according to the preparation method of nano MFI-type molecular sieve with hierarchical pore structure according to claim 1, it is characterized in that, the Si/Al atomic ratio=10-1000 of nano-ZSM-5 type molecular sieve; Si/Ti atomic ratio=the 10-1000 of nano-scale TS-1 type molecular sieve.
7. according to the application of nano MFI-type molecular sieve with hierarchical pore structure according to claim 1, it is characterized in that, in MTP preparing propylene from methanol process, multi-stage artery structure nano MFI-type molecular sieve is filled in fixed bed reactors, material liquid is the industrial methanol of 40-95wt%, and mass space velocity is 0.3-10 h
-1, reaction temperature is 400-550 DEG C.
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| CN106145151B (en) * | 2015-04-28 | 2018-11-30 | 中国石油化工股份有限公司 | A kind of multi-stage porous Titanium Sieve Molecular Sieve and its synthetic method |
| CN106276957B (en) * | 2015-05-29 | 2019-03-26 | 武汉理工大学 | A kind of mesoporous multi-stage porous pure silicon molecular sieve Silicalite-1 monocrystalline of ordered big hole-with opal structural and its synthetic method |
| CN106276958B (en) * | 2015-05-29 | 2019-01-25 | 武汉理工大学 | A kind of mesoporous multi-stage porous titanium-silicon molecular sieve TS-1 monocrystalline of ordered big hole-with opal structural and its synthetic method |
| EP3722272B1 (en) | 2015-10-21 | 2023-08-30 | Exelus, Inc. | Process of making olefins or alkylate by reaction of methanol and/or dme or by reaction of methanol and/or dme and butane |
| CN106044793A (en) * | 2016-08-05 | 2016-10-26 | 江苏天诺新材料科技股份有限公司 | Method for synthesis of nanometer ZSM-5 molecular sieve from mother liquor flocculate |
| CN107840346B (en) * | 2016-09-21 | 2019-07-19 | 中国石油化工股份有限公司 | A kind of application of the preparation method of silica zeolite, processing method and silica zeolite, catalyst and catalyst |
| CN107840345B (en) * | 2016-09-21 | 2019-07-19 | 中国石油化工股份有限公司 | A kind of application of the preparation method of silica zeolite, processing method and silica zeolite, catalyst and catalyst |
| CN109704355A (en) * | 2017-10-25 | 2019-05-03 | 北京思达安新材料科技有限公司 | A kind of porous zeotile and preparation method |
| CN108793183B (en) * | 2017-12-15 | 2021-04-13 | 中国科学院大连化学物理研究所 | Method for separating mother liquor of titanium-silicon molecular sieve |
| CN108080020B (en) * | 2018-01-10 | 2020-09-25 | 中国科学院广州能源研究所 | Fe-based molecular sieve catalyst for Fischer-Tropsch-oligomerization coupling reaction and preparation method and application thereof |
| CN113694959A (en) * | 2020-05-22 | 2021-11-26 | 南京工业大学 | Catalyst for preparing nonene by propylene oligomerization reaction and preparation method thereof |
| CN111977667A (en) * | 2020-08-11 | 2020-11-24 | 海南泽能科技有限公司 | High-heteroatom-content hierarchical pore MFI type molecular sieve, and preparation method and application thereof |
| CN114804141B (en) * | 2021-01-29 | 2023-07-11 | 中国石油化工股份有限公司 | Nanocluster mesoporous ZSM-5 molecular sieve and preparation method thereof |
| CN113072079B (en) * | 2021-05-26 | 2021-12-24 | 常州大学 | Synthesis method of twist-shaped porous ZSM-5 zeolite assembled by nano square conical particles |
| CN116354359A (en) * | 2021-12-28 | 2023-06-30 | 中国石油天然气股份有限公司 | Pure silicon MFI structure molecular sieve and preparation method thereof |
| CN114804139B (en) * | 2022-04-14 | 2023-09-22 | 南京工业大学 | Preparation method of multi-channel MFI type molecular sieve membrane |
| CN115448324B (en) * | 2022-09-27 | 2023-06-27 | 吉林大学 | MFI structure molecular sieve hierarchical pore material and preparation method thereof |
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