CN113830781B - EUO molecular sieve and synthesis method and application thereof - Google Patents
EUO molecular sieve and synthesis method and application thereof Download PDFInfo
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- 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 117
- 239000002808 molecular sieve Substances 0.000 title claims abstract description 116
- 238000001308 synthesis method Methods 0.000 title claims abstract description 20
- 239000013078 crystal Substances 0.000 claims abstract description 48
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims abstract description 7
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 7
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910052796 boron Inorganic materials 0.000 claims abstract description 7
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 7
- 239000010703 silicon Substances 0.000 claims abstract description 7
- 239000010936 titanium Substances 0.000 claims abstract description 3
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 3
- 239000000203 mixture Substances 0.000 claims description 33
- UMESNHVJZFCGBV-UHFFFAOYSA-N 2-methyl-4-[(2-methylphenyl)methylidene]-1,3-oxazol-5-one Chemical compound O=C1OC(C)=NC1=CC1=CC=CC=C1C UMESNHVJZFCGBV-UHFFFAOYSA-N 0.000 claims description 32
- 239000003795 chemical substances by application Substances 0.000 claims description 26
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 24
- 238000002425 crystallisation Methods 0.000 claims description 21
- 230000008025 crystallization Effects 0.000 claims description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 18
- 238000000034 method Methods 0.000 claims description 17
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims description 16
- 238000006243 chemical reaction Methods 0.000 claims description 15
- 230000015572 biosynthetic process Effects 0.000 claims description 13
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 13
- 239000004327 boric acid Substances 0.000 claims description 13
- 238000003786 synthesis reaction Methods 0.000 claims description 13
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 12
- JKWMSGQKBLHBQQ-UHFFFAOYSA-N diboron trioxide Chemical compound O=BOB=O JKWMSGQKBLHBQQ-UHFFFAOYSA-N 0.000 claims description 12
- 239000000377 silicon dioxide Substances 0.000 claims description 11
- 239000003513 alkali Substances 0.000 claims description 10
- 235000012239 silicon dioxide Nutrition 0.000 claims description 10
- 229910052810 boron oxide Inorganic materials 0.000 claims description 8
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 8
- JMXKSZRRTHPKDL-UHFFFAOYSA-N titanium ethoxide Chemical group [Ti+4].CC[O-].CC[O-].CC[O-].CC[O-] JMXKSZRRTHPKDL-UHFFFAOYSA-N 0.000 claims description 6
- IAQQDIGGISSSQO-UHFFFAOYSA-N 2-(4-fluorophenyl)piperidine Chemical compound C1=CC(F)=CC=C1C1NCCCC1 IAQQDIGGISSSQO-UHFFFAOYSA-N 0.000 claims description 5
- -1 n-octyl Chemical group 0.000 claims description 5
- STYCVOUVPXOARC-UHFFFAOYSA-M trimethyl(octyl)azanium;hydroxide Chemical compound [OH-].CCCCCCCC[N+](C)(C)C STYCVOUVPXOARC-UHFFFAOYSA-M 0.000 claims description 5
- 239000002585 base Substances 0.000 claims description 3
- 125000001453 quaternary ammonium group Chemical group 0.000 claims description 3
- 150000003242 quaternary ammonium salts Chemical class 0.000 claims description 3
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 claims description 2
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 2
- 239000003463 adsorbent Substances 0.000 claims description 2
- 229910052783 alkali metal Inorganic materials 0.000 claims description 2
- 150000001340 alkali metals Chemical class 0.000 claims description 2
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 2
- 150000001342 alkaline earth metals Chemical class 0.000 claims description 2
- 239000011230 binding agent Substances 0.000 claims description 2
- 229910021538 borax Inorganic materials 0.000 claims description 2
- 239000003054 catalyst Substances 0.000 claims description 2
- 150000001768 cations Chemical class 0.000 claims description 2
- YOYLLRBMGQRFTN-SMCOLXIQSA-N norbuprenorphine Chemical compound C([C@@H](NCC1)[C@]23CC[C@]4([C@H](C3)C(C)(O)C(C)(C)C)OC)C3=CC=C(O)C5=C3[C@@]21[C@H]4O5 YOYLLRBMGQRFTN-SMCOLXIQSA-N 0.000 claims description 2
- 150000002894 organic compounds Chemical class 0.000 claims description 2
- 235000019353 potassium silicate Nutrition 0.000 claims description 2
- 239000000741 silica gel Substances 0.000 claims description 2
- 229910002027 silica gel Inorganic materials 0.000 claims description 2
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 2
- 239000004328 sodium tetraborate Substances 0.000 claims description 2
- 235000010339 sodium tetraborate Nutrition 0.000 claims description 2
- 239000004408 titanium dioxide Substances 0.000 claims description 2
- 229910004298 SiO 2 Inorganic materials 0.000 abstract description 52
- 229910010413 TiO 2 Inorganic materials 0.000 abstract description 5
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 108
- 238000002441 X-ray diffraction Methods 0.000 description 30
- 239000007864 aqueous solution Substances 0.000 description 23
- 238000001035 drying Methods 0.000 description 15
- 239000000463 material Substances 0.000 description 14
- 238000001914 filtration Methods 0.000 description 13
- 238000009616 inductively coupled plasma Methods 0.000 description 13
- 238000005259 measurement Methods 0.000 description 13
- 238000005406 washing Methods 0.000 description 13
- 238000001228 spectrum Methods 0.000 description 12
- 229910001220 stainless steel Inorganic materials 0.000 description 12
- 239000010935 stainless steel Substances 0.000 description 12
- 239000008367 deionised water Substances 0.000 description 11
- 229910021641 deionized water Inorganic materials 0.000 description 11
- 238000002354 inductively-coupled plasma atomic emission spectroscopy Methods 0.000 description 11
- 239000000376 reactant Substances 0.000 description 11
- 238000002360 preparation method Methods 0.000 description 7
- 238000007873 sieving Methods 0.000 description 7
- 238000010438 heat treatment Methods 0.000 description 5
- 239000011148 porous material Substances 0.000 description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- 229910021536 Zeolite Inorganic materials 0.000 description 3
- 239000002131 composite material Substances 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
- 239000011541 reaction mixture Substances 0.000 description 3
- 239000010457 zeolite Substances 0.000 description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- 238000004438 BET method Methods 0.000 description 1
- 229910017488 Cu K Inorganic materials 0.000 description 1
- 229910017541 Cu-K Inorganic materials 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 230000005260 alpha ray Effects 0.000 description 1
- CSDREXVUYHZDNP-UHFFFAOYSA-N alumanylidynesilicon Chemical compound [Al].[Si] CSDREXVUYHZDNP-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- VFGVNLNBQPXBKA-UHFFFAOYSA-N diazanium;dibromide Chemical class [NH4+].[NH4+].[Br-].[Br-] VFGVNLNBQPXBKA-UHFFFAOYSA-N 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000006317 isomerization reaction Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- AUOKSPBBOCQYIX-UHFFFAOYSA-N n,n-dimethyl-1,1-diphenylmethanamine Chemical class C=1C=CC=CC=1C(N(C)C)C1=CC=CC=C1 AUOKSPBBOCQYIX-UHFFFAOYSA-N 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000011164 primary particle Substances 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
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- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B39/00—Compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites; Their preparation; After-treatment, e.g. ion-exchange or dealumination
- C01B39/02—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof
- C01B39/06—Preparation of isomorphous zeolites characterised by measures to replace the aluminium or silicon atoms in the lattice framework by atoms of other elements, i.e. by direct or secondary synthesis
- C01B39/12—Preparation of isomorphous zeolites characterised by measures to replace the aluminium or silicon atoms in the lattice framework by atoms of other elements, i.e. by direct or secondary synthesis the replacing atoms being at least boron atoms
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- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
- B01J20/16—Alumino-silicates
- B01J20/18—Synthetic zeolitic molecular sieves
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- C01B39/06—Preparation of isomorphous zeolites characterised by measures to replace the aluminium or silicon atoms in the lattice framework by atoms of other elements, i.e. by direct or secondary synthesis
- C01B39/08—Preparation of isomorphous zeolites characterised by measures to replace the aluminium or silicon atoms in the lattice framework by atoms of other elements, i.e. by direct or secondary synthesis the aluminium atoms being wholly replaced
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Abstract
The invention discloses a new EUO molecular sieve, wherein the skeleton element comprises silicon element and boron and/or titanium element, wherein silicon (SiO 2 Calculated) with boron and/or titanium (in B 2 O 3 ,TiO 2 Calculated as a mole ratio) of 3 to 100. The molecular sieve crystal has coffin shape, and the average length is 300-1000 nm. The invention also provides a synthesis method of the EUO molecular sieve, which is simple, convenient and economic.
Description
Technical Field
The invention relates to a molecular sieve and a synthesis method and application thereof, in particular to an EUO molecular sieve and a synthesis method and application thereof.
Background
The EUO molecular sieve is a molecular sieve with one-dimensional ten-membered ring linear pore canal, the pore diameter is 0.41nm multiplied by 0.54nm, and a twelve-membered ring (the size is 0.68 multiplied by 0.58 multiplied by 0.81 nm) side pocket structure which is vertically communicated with the through hole is also arranged. Because of the unique pore channel structure, the molecular sieve has excellent catalytic performance in reactions such as xylene isomerization, wax-containing oil product pour point reduction and the like, has good commercial value and application prospect, and is widely interested by a plurality of researchers, and molecular sieves with EUO structures including EU-1, TPZ-3, ZSM-50 and the like are synthesized at present.
Patent US 4537754 in 1981 discloses for the first time a molecular sieve having the structure EUO. Patent EP 0042226 and EP 0051318 disclose the synthesis of EUO-1 and TPZ-3 molecular sieves having the EUO structure using N, N, N ', N ', N ' -hexamethyl-1, 6-hexamethylenediammonium compound as structure directing agent. Patent US 4640829 discloses the synthesis of ZSM-50 zeolite molecular sieves using dibenzyldimethylammonium ions as structure directing agents.
Patent CN 100363258C discloses a preparation method of a silicon-aluminum molecular sieve with an EUO structure, and the molecular sieve prepared by adopting fluoride as a mineralizer has good acidic characteristics. Patent CN 102040230B discloses a preparation method of an EUO type molecular sieve, which synthesizes the EUO type molecular sieve by adding one or more of ethanol, propylene glycol, methanol and acetone as an organic solvent and using a hexamethyl diammonium bromide derivative or a benzhydryl dimethyl ammonium derivative as a structure directing agent. Patent CN 102107143B discloses a preparation method of EUO/mesoporous composite molecular sieve, and the composite molecular sieve prepared by the method has loose nanoparticle aggregation state.
Patent CN 1260239a discloses a process for preparing zeolite with structure type EUO, using at least one of LTA, FAU, MOR, MFI or type EUO molecular sieve material as seed crystal, R 1 R 2 R 3 N + (CH 2 ) n N + R 4 R 5 R 6 The EUO type zeolite molecular sieve is synthesized by taking the alkylated polymethylene alpha-omega diammonium compound as a structure directing agent, but the structure directing agent has a complex structure and high price, and is not beneficial to the industrial application of the EUO molecular sieve.
Disclosure of Invention
A first object of the present invention is to provide an EUO molecular sieve to further optimize the crystal morphology of the molecular sieve and adjust the crystal size. The invention further aims to provide a synthesis method of the EUO molecular sieve, so that the preparation process is simplified, and the preparation cost is reduced.
The inventor has found a new molecular sieve with EUO structure based on the prior art, which has the characteristics of special crystal morphology and uniform size.
The first aspect of the present invention is to provide a novel EUO molecular sieve, the framework elements of which comprise silicon element and boron and/or titanium element, wherein silicon (in SiO 2 Calculated) with boron and/or titanium (in B 2 O 3 ,TiO 2 Calculated as such) is 3 to 100, preferably 15 to 60. The molecular sieve crystals (primary particles) have a coffin morphology (thin hexagonal prisms) with an average length of 300 to 1000nm, preferably an average length of 500 to 800nm.
The aspect ratio of the molecular sieve crystals is 1.5-5, and the average thickness is less than or equal to 100nm; preferably the aspect ratio is 2 to 4, preferably the average thickness is 50 to 100nm.
The specific surface area of the molecular sieve is 250-750 m 2 Per gram, preferably 300 to 700 meters 2 Per gram, more preferably 350 to 650 meters 2 /g; the micropore volume is 0.05-0.40 cm 3 Per gram, preferably 0.08 to 0.35 cm 3 Per gram, more preferably 0.10 to 0.30 cm 3 /g.
In another aspect, the present invention provides a method for synthesizing an EUO molecular sieve, including: and crystallizing the mixture of the silicon dioxide source, the boron oxide source and/or the titanium oxide source, the alkali source, the structure directing agent (R), the water and the seed crystal to obtain the molecular sieve.
In the synthesis method of the EUO molecular sieve, the structure directing agent is selected from at least one of n-octyl trimethyl quaternary ammonium salt or quaternary ammonium base thereof, and is preferably any one or more of n-octyl trimethyl ammonium chloride, n-octyl trimethyl ammonium bromide or n-octyl trimethyl ammonium hydroxide.
In the above synthesis method of the EUO molecular sieve, the seed crystal is a IWV molecular sieve with a heterogeneous (non-EUO type molecular sieve) structure. The seed crystal and the silica source (in SiO 2 By weight) of 0.01 to the upper part0.25, preferably 0.03 to 0.18.
In the above method for synthesizing EUO molecular sieve, the silica source (SiO 2 Calculated as B), a boron oxide source and/or a titanium oxide source (calculated as B 2 O 3 ,TiO 2 Based on OH), alkali source (based on OH - The mol ratio of the structural guiding agent (R) to the water is 1 (0.005-0.3): 0.05-0.6): 0.05-1.0): 5-200, preferably 1 (0.01-0.25): 0.1-0.5): 0.1-0.9): 8-100, more preferably 1 (0.02-0.2): 0.15-0.4): 0.15-0.8): 10-50.
In the synthesis method of the EUO molecular sieve, the silicon dioxide source is at least one selected from silicic acid, silica gel, silica sol, tetraethyl silicate and water glass; the boron oxide source is selected from at least one of boric acid, diboron trioxide, borate and borax; the titanium oxide source is selected from tetraethyl titanate and TiCl 4 Hexafluorotitanic acid, ti (SO) 4 ) 2 And at least one of titanium dioxide.
In the above synthesis method of the EUO molecular sieve, the alkali source is selected from one or more of alkali taking alkali metal or alkaline earth metal as cations.
In the above synthesis method of the EUO molecular sieve, the crystallization conditions of the reaction mixture include: crystallizing at 105-210 deg.c for 1-10 days, preferably at 120-195 deg.c for 2-9 days, and more preferably at 135-180 deg.c for 3-8 days.
In the above-mentioned synthetic method of the EUO molecular sieve, the mixture before crystallization treatment is preferably uniformly mixed.
In the above synthesis method of the EUO molecular sieve, after the crystallization treatment, a conventional post-treatment step may be included, such as a step of filtering, washing, and drying to obtain the molecular sieve; and optionally, a step of calcining the obtained molecular sieve may be included.
In the synthesis method of the EUO molecular sieve, the drying temperature of the reaction mixture is 30-150 ℃, preferably 45-120 ℃; the drying time is 1 to 24 hours, preferably 3 to 12 hours.
In the synthesis method of the EUO molecular sieve, the roasting temperature of the reaction mixture is 300-800 ℃, preferably 400-650 ℃; the calcination time is 1 to 10 hours, preferably 3 to 6 hours. In the synthesis method of the EUO molecular sieve, the heating mode adopts a direct heating mode, or adopts a microwave heating mode, or adopts a composite mode of direct heating and microwave heating.
In the above-described synthesis method of the EUO molecular sieve, the seed crystal may be introduced at any time during the preparation process.
Another aspect of the present invention is to provide an EUO molecular sieve composition comprising the aforementioned EUO molecular sieve or an EUO molecular sieve synthesized according to the aforementioned method, and a binder.
In a further aspect, the present invention provides the use of the EUO molecular sieve described above, or the EUO molecular sieve synthesized by the method described above, or a combination thereof, as an adsorbent or a catalyst for the conversion of organic compounds.
The EUO molecular sieve contains silicon element, boron and/or titanium element, has special crystal morphology, coffin morphology (thin hexagonal prism shape) and uniform size. According to the preparation method, n-octyl trimethyl quaternary ammonium salt and/or quaternary ammonium base thereof are adopted as a structure directing agent, and a certain amount of IWV type molecular sieve is added as seed crystals, so that the molecular sieve with the EUO structure is successfully synthesized. The synthesis method is simple, convenient and economic.
Drawings
FIG. 1 is an X-ray diffraction pattern (XRD) of the molecular sieve obtained in example 1;
FIG. 2 is a Scanning Electron Microscope (SEM) photograph of the molecular sieve obtained in example 1;
FIG. 3 is an X-ray diffraction pattern (XRD) of the molecular sieve obtained in example 2;
FIG. 4 is a Scanning Electron Microscope (SEM) photograph of the molecular sieve obtained in example 2;
FIG. 5 is an X-ray diffraction pattern (XRD) of the molecular sieve obtained in example 3;
FIG. 6 is an X-ray diffraction pattern (XRD) of the molecular sieve obtained in example 4;
FIG. 7 is an X-ray diffraction pattern (XRD) of the molecular sieve obtained in example 5;
FIG. 8 is an X-ray diffraction pattern (XRD) of the molecular sieve obtained in example 6;
FIG. 9 is an X-ray diffraction pattern (XRD) of the molecular sieve obtained in example 8;
FIG. 10 is an X-ray diffraction pattern (XRD) of the molecular sieve obtained in example 9;
fig. 11 is an X-ray diffraction pattern (XRD) of the sample obtained in comparative example 1.
Detailed Description
The following detailed description of embodiments of the invention is provided, but it should be noted that the scope of the invention is not limited by these embodiments.
All publications, patent applications, patents, and other references mentioned in this specification are herein incorporated by reference in their entirety. Unless defined otherwise, all technical and scientific terms used herein have the meaning commonly understood by one of ordinary skill in the art. In case of conflict, the present specification, definitions, will control.
When the specification derives materials, substances, methods, steps, devices, or elements and the like in the word "known to those skilled in the art", "prior art", or the like, such derived objects encompass those conventionally used in the art at the time of the application, but also include those which are not currently commonly used but which would become known in the art to be suitable for similar purposes.
In the context of this specification, any matters or matters not mentioned are directly applicable to the technology known in the art without modification except for those explicitly stated. Moreover, any embodiment described herein can be freely combined with one or more other embodiments described herein, and the technical solutions or ideas thus formed are all deemed to be part of the original disclosure or original description of the present invention, and should not be deemed to be a new matter which has not been disclosed or contemplated herein, unless such combination is clearly unreasonable by those skilled in the art. The present invention will be described in further detail with reference to examples, but the present invention is not limited to these examples. The X-ray powder diffractometer used in the examples was a model Panalytical X PERPRO X-ray powder diffractometer, using a Cu-K alpha ray source, and the monochromator used the (111) plane of the Ge single crystal as the counterRadiation surface, nickel filter, K alpha 1 wavelengthThe working voltage is 40kV, the current is 40mA, and the scanning range is 3-50 degrees. The crystal size measurement adopts a Scanning Electron Microscope (SEM) model S-4800II type field emission scanning electron microscope, molecular sieve crystals are observed under the magnification of more than 1 ten thousand times, an observation view field is randomly selected, and the average value of the sizes of all the crystals in the observation view field, namely the length, the width and the height (thickness) is calculated. Inductively coupled plasma atomic emission spectrometer (ICP) model number Varian 725-ES. The physical adsorption instrument model is Micromeretic ASAP2020M, and the test conditions are as follows: measuring the temperature to 169 ℃ below zero, carrying out vacuum pretreatment on the molecular sieve for 10 hours at 300 ℃ before measurement, and calculating by adopting a BET method and a t-plot method to obtain parameters such as pore volume, specific surface area and the like.
Example 1
4.826 g of deionized water, 5.237 g of an aqueous solution of the structure directing agent n-octyl trimethyl ammonium chloride (30% by weight of n-octyl trimethyl ammonium chloride), 3.785 g of a silica sol (SiO-containing) 2 40 wt.%), 0.840 g of sodium hydroxide aqueous solution (containing 30 mass% of NaOH), 0.312 g of boric acid, 0.2271 g of seed crystal IWV g of molecular sieve are mixed uniformly to prepare a mixture, and the material ratio (molar ratio) of reactants is:
B 2 O 3 /SiO 2 =0.1;
n-octyl trimethyl ammonium chloride/SiO 2 =0.3;
NaOH/SiO 2 =0.25;
H 2 O/SiO 2 =25。
After being mixed evenly, the mixture is put into a stainless steel reaction kettle and crystallized for 7 days at 170 ℃. Filtering and washing after crystallization, drying in an oven at 110 ℃ for 6 hours, and sieving with a molecular sieve, wherein an XRD spectrum of the sample is shown in figure 1, a scanning electron microscope SEM (scanning electron microscope) image of the sample is shown in figure 2, the crystal is in a coffin shape, the average length is 800nm, the length-width ratio is 3.0, and the average thickness is 100nm.
The dried sample is roasted at 550 ℃ for 6 hours, and the specific surface area of the obtained product is 368 m 2 Per gram, micropore volume 0.15 cm 3 Gram/gram. Measurement of SiO of a sample by inductively coupled plasma atomic emission spectrometry (ICP) 2 /B 2 O 3 =20.9 (molar ratio).
Example 2
6.960 g of deionized water, 15.282 g of the structure directing agent n-octyl trimethyl ammonium chloride aqueous solution (containing 30 wt% n-octyl trimethyl ammonium chloride), 9.469 g of silica sol (containing SiO) 2 40 wt%), 2.354 g of sodium hydroxide aqueous solution (containing 30 mass% of NaOH), 0.935 g of boric acid, 0.3788 g of seed crystal and IWV g of molecular sieve are uniformly mixed to prepare a mixture, and the material ratio (molar ratio) of reactants is as follows:
B 2 O 3 /SiO 2 =0.12;
n-octyl trimethyl ammonium chloride/SiO 2 =0.35;
NaOH/SiO 2 =0.28;
H 2 O/SiO 2 =22。
After being mixed evenly, the mixture is put into a stainless steel reaction kettle and crystallized for 5 days at 165 ℃. Filtering and washing after crystallization, drying in a 110 ℃ oven for 6 hours, and sieving with a molecular sieve, wherein an XRD spectrum of the sample is shown in figure 3, a scanning electron microscope SEM (scanning electron microscope) image of the sample is shown in figure 4, the crystal is in a coffin shape, the average length is 500nm, the length-width ratio is 2.8, and the average thickness is 60nm.
The dried sample is roasted at 550 ℃ for 6 hours, and the specific surface area of the obtained product is 411 meters 2 Per gram, micropore volume 0.16 cm 3 /g. Measurement of SiO of a sample by inductively coupled plasma atomic emission spectrometry (ICP) 2 /B 2 O 3 =18.1 (molar ratio).
Example 3
16.782 g of deionized water, 31.993 g of the structure directing agent n-octyl trimethyl ammonium chloride aqueous solution (containing 30 wt% n-octyl trimethyl ammonium chloride), 15.418 g of silica sol (containing SiO) 2 40 wt%), 4.792 g of sodium hydroxide aqueous solution (containing 30 mass% of NaOH), 1.016 g of boric acid and 0.4934 g of seed crystal IWV g of molecular sieve are uniformly mixed to prepare a mixture, and the material ratio (molar ratio) of reactants is as follows:
B 2 O 3 /SiO 2 =0.08;
n-octyl trimethyl ammonium chloride/SiO 2 =0.45;
NaOH/SiO 2 =0.35;
H 2 O/SiO 2 =28。
After being mixed evenly, the mixture is put into a stainless steel reaction kettle and crystallized for 3 days at 180 ℃. Filtering and washing after crystallization, drying in a 110 ℃ oven to obtain a 6-hour molecular sieve, wherein an XRD spectrum of the sample is shown in figure 5, a scanning electron microscope SEM (scanning electron microscope) image of the sample is similar to that of figure 2, the crystal is in a coffin shape, the average length is 650nm, the length-width ratio is 2.6, and the average thickness is 70nm.
The dried sample is roasted at 550 ℃ for 6 hours, and the specific surface area of the obtained product is 396 meters 2 Per gram, micropore volume 0.15 cm 3 /g. Measurement of SiO of a sample by inductively coupled plasma atomic emission spectrometry (ICP) 2 /B 2 O 3 =23.4 (molar ratio).
Example 4
20.921 g of deionized water, 25.583 g of the structure directing agent n-octyl trimethyl ammonium chloride aqueous solution (containing 30 wt% n-octyl trimethyl ammonium chloride), 13.870 g of silica sol (containing SiO) 2 40 wt%), 3.941 g of sodium hydroxide aqueous solution (containing 30 mass% of NaOH), 0.685 g of boric acid, 0.6658 g of seed crystal and IWV g of molecular sieve are uniformly mixed to prepare a mixture, and the material ratio (molar ratio) of reactants is as follows:
B 2 O 3 /SiO 2 =0.06;
n-octyl trimethyl ammonium chloride/SiO 2 =0.40;
NaOH/SiO 2 =0.32;
H 2 O/SiO 2 =30。
After being mixed evenly, the mixture is put into a stainless steel reaction kettle and crystallized for 4 days at 175 ℃. Filtering and washing after crystallization, drying in a 110 ℃ oven for 6 hours, and sieving with a molecular sieve, wherein an XRD spectrum of a sample is shown in figure 6, a scanning electron microscope SEM (scanning electron microscope) image of the sample is similar to that of figure 2, the crystal is in a coffin shape, the average length is 600nm, the length-width ratio is 3.2, and the average thickness is 80nm.
After dryingThe specific surface area of the product obtained after the sample is roasted at 550 ℃ for 6 hours is 401 meters 2 Per gram, micropore volume 0.13 cm 3 /g. Measurement of SiO of a sample by inductively coupled plasma atomic emission spectrometry (ICP) 2 /B 2 O 3 =30.2 (molar ratio).
Example 5
21.977 g of deionized water, 21.463 g of the structure directing agent n-octyl trimethyl ammonium chloride aqueous solution (containing 30 wt% n-octyl trimethyl ammonium chloride), 12.249 g of silica sol (containing SiO) 2 40 wt%), 3.807 g of sodium hydroxide aqueous solution (containing 30 mass% of NaOH), 0.504 g of boric acid and 0.2450 g of seed crystal IWV g of molecular sieve are uniformly mixed to prepare a mixture, and the material ratio (molar ratio) of reactants is as follows:
B 2 O 3 /SiO 2 =0.05;
n-octyl trimethyl ammonium chloride/SiO 2 =0.38;
NaOH/SiO 2 =0.35;
H 2 O/SiO 2 =32。
After being mixed evenly, the mixture is put into a stainless steel reaction kettle and crystallized for 6 days at 160 ℃. Filtering and washing after crystallization, drying in an oven at 110 ℃ for 6 hours, and sieving with a molecular sieve, wherein an XRD spectrum of a sample is shown in figure 7, a scanning electron microscope SEM (scanning electron microscope) image of the sample is similar to that of figure 2, and the crystal has a coffin shape, an average length of 500nm, an aspect ratio of 2.6 and an average thickness of 80nm.
The dried sample is roasted at 550 ℃ for 6 hours, and the specific surface area of the obtained product is 372 meters 2 Per gram, micropore volume 0.15 cm 3 /g. Measurement of SiO of a sample by inductively coupled plasma atomic emission spectrometry (ICP) 2 /B 2 O 3 =34.7 (molar ratio).
Example 6
18.301 g of deionized water, 23.471 g of the structure directing agent n-octyl trimethyl ammonium chloride aqueous solution (containing 30 wt% n-octyl trimethyl ammonium chloride), 10.180 g of silica sol (containing SiO) 2 40 wt%), 2.712 g of aqueous sodium hydroxide solution (containing 30 wt% NaOH), 0.335 g of boric acid, 0.1222 g of seed crystal IWV g of molecular sieve,the mixture is prepared, and the material ratio (molar ratio) of reactants is as follows:
B 2 O 3 /SiO 2 =0.04;
n-octyl trimethyl ammonium chloride/SiO 2 =0.50;
NaOH/SiO 2 =0.30;
H 2 O/SiO 2 =35。
After being mixed evenly, the mixture is put into a stainless steel reaction kettle and crystallized for 8 days at 155 ℃. Filtering and washing after crystallization, drying in a 110 ℃ oven for 6 hours, and sieving with a molecular sieve, wherein an XRD spectrum of the sample is shown in figure 8, a scanning electron microscope SEM (scanning electron microscope) image of the sample is similar to that of figure 2, the crystal is in a coffin shape, the average length is 600nm, the length-width ratio is 3.2, and the average thickness is 80nm.
The dried sample is roasted at 550 ℃ for 6 hours, and the specific surface area of the obtained product is 391 meters 2 Per gram, micropore volume 0.15 cm 3 /g. Measurement of SiO of a sample by inductively coupled plasma atomic emission spectrometry (ICP) 2 /B 2 O 3 =37.6 (molar ratio).
Example 7
24.327 g of deionized water, 13.350 g of the structure directing agent n-octyl trimethyl ammonium chloride aqueous solution (containing 30 wt% n-octyl trimethyl ammonium chloride), 9.047 g of silica sol (containing SiO) 2 40 wt.%), 3.053 g of sodium hydroxide aqueous solution (containing 30 wt.% of NaOH), 0.223 g of boric acid, 0.2171 g of seed crystal and IWV g of molecular sieve are mixed uniformly to prepare a mixture, and the material ratio (molar ratio) of the reactants is:
B 2 O 3 /SiO 2 =0.03;
n-octyl trimethyl ammonium chloride/SiO 2 =0.32;
NaOH/SiO 2 =0.38;
H 2 O/SiO 2 =38。
After being mixed evenly, the mixture is put into a stainless steel reaction kettle and crystallized for 7 days at 150 ℃. Filtering and washing after crystallization, drying in a 110 ℃ oven for 6 hours to obtain a molecular sieve, wherein the XRD spectrum of the sample is similar to that of fig. 1, the scanning electron microscope SEM (scanning electron microscope) image of the sample is similar to that of fig. 2, the crystal is in a coffin shape, the average length is 800nm, the length-to-width ratio is 2.8, and the average thickness is 60nm.
The dried sample is roasted at 550 ℃ for 6 hours, and the specific surface area of the obtained product is 388 meters 2 Per gram, micropore volume 0.12 cm 3 /g. Measurement of SiO of a sample by inductively coupled plasma atomic emission spectrometry (ICP) 2 /B 2 O 3 =43.3 (molar ratio).
Example 8
22.312 g of deionized water, 9.124 g of the structure directing agent n-octyl trimethyl ammonium chloride aqueous solution (containing 30 wt% n-octyl trimethyl ammonium chloride), 7.067 g of silica sol (containing SiO) 2 40 wt.%), 1.380 g of sodium hydroxide aqueous solution (containing 30 mass% of NaOH), 0.116 g of boric acid, 0.5088 g of seed crystal and IWV g of molecular sieve are uniformly mixed to prepare a mixture, and the material ratio (molar ratio) of reactants is as follows:
B 2 O 3 /SiO 2 =0.02;
n-octyl trimethyl ammonium chloride/SiO 2 =0.28;
NaOH/SiO 2 =0.22;
H 2 O/SiO 2 =40。
After being mixed evenly, the mixture is put into a stainless steel reaction kettle and crystallized for 9 days at 145 ℃. Filtering and washing after crystallization, drying in a 110 ℃ oven for 6 hours, and sieving with a molecular sieve, wherein an XRD spectrum of the sample is shown as figure 9, a scanning electron microscope SEM (scanning electron microscope) image of the sample is similar to that of figure 2, the crystal is in a coffin shape, the average length is 600nm, the length-width ratio is 2.5, and the average thickness is 70nm.
The dried sample was calcined at 550℃for 6 hours to give a product having a specific surface area of 359 m 2 Per gram, micropore volume 0.13 cm 3 /g. Measurement of SiO of a sample by inductively coupled plasma atomic emission spectrometry (ICP) 2 /B 2 O 3 =53.6 (molar ratio).
Example 9
5.412 g of deionized water, 7.191 g of the structure directing agent n-octyl trimethyl ammonium chloride aqueous solution (containing 30 wt% n-octyl trimethyl ammonium chloride), 6.238 g of silica sol (containing SiO) 2 40 weight percentThe materials of the mixture are prepared by uniformly mixing 1.108 g of sodium hydroxide aqueous solution (containing 30 mass percent of NaOH), 0.188 g of tetraethyl titanate and 0.2495 g of IWV type molecular sieve with seed crystal:
TiO 2 /SiO 2 =0.02;
n-octyl trimethyl ammonium chloride/SiO 2 =0.25;
NaOH/SiO 2 =0.20;
H 2 O/SiO 2 =20。
The dried sample is baked at 550 ℃ for 6 hours, then mixed uniformly, and then is put into a stainless steel reaction kettle for crystallization at 170 ℃ for 5 days. Filtering and washing after crystallization, drying in an oven at 110 ℃ for 6 hours, and sieving with a molecular sieve, wherein an XRD spectrum of a sample is shown as figure 10, a scanning electron microscope SEM (scanning electron microscope) image of the sample is similar to that of figure 2, and the crystal has a coffin shape, an average length of 750nm, an aspect ratio of 2.6 and an average thickness of 80nm.
The specific surface area of the obtained product is 376 m 2 Per gram, micropore volume 0.15 cm 3 /g. Measurement of SiO of a sample by inductively coupled plasma atomic emission spectrometry (ICP) 2 /TiO 2 =55.7 (molar ratio).
Example 10
As in example 1. 2.135 g of deionized water, 5.237 g of an aqueous solution of the structure directing agent n-octyl trimethyl ammonium bromide (30% by weight of n-octyl trimethyl ammonium bromide), 3.785 g of a silica sol (SiO-containing) 2 40 wt.%), 0.840 g of sodium hydroxide aqueous solution (containing 30 mass% of NaOH), 0.312 g of boric acid, 0.2271 g of seed crystal IWV g of molecular sieve are mixed uniformly to prepare a mixture, and the material ratio (molar ratio) of reactants is:
B 2 O 3 /SiO 2 =0.1;
n-octyl trimethyl ammonium bromide/SiO 2 =0.3;
NaOH/SiO 2 =0.25;
H 2 O/SiO 2 =25。
After being mixed evenly, the mixture is put into a stainless steel reaction kettle and crystallized for 7 days at 170 ℃. Filtering and washing after crystallization, drying in a 110 ℃ oven for 6 hours, and screening the molecular sieve, wherein the XRD spectrum of the sample is similar to that of fig. 1, the scanning electron microscope SEM (scanning electron microscope) image of the sample is similar to that of fig. 2, the crystal is in a coffin shape, the average length is 820nm, the length-to-width ratio is 3.1, and the average thickness is 90nm.
The dried sample was calcined at 550℃for 6 hours to give a product having a specific surface area of 379 m 2 Per gram, micropore volume 0.12 cm 3 /g. Measurement of SiO of a sample by inductively coupled plasma atomic emission spectrometry (ICP) 2 /B 2 O 3 =19.8 (molar ratio).
Example 11
As in example 1. 5.253 g of deionized water, 4.808 g of the structure directing agent n-octyltrimethylammonium hydroxide aqueous solution (containing 30 wt% of n-octyltrimethylammonium hydroxide), 3.785 g of silica sol (containing SiO) 2 40 wt.%), 0.840 g of sodium hydroxide aqueous solution (containing 30 mass% of NaOH), 0.312 g of boric acid, 0.2271 g of seed crystal IWV g of molecular sieve are mixed uniformly to prepare a mixture, and the material ratio (molar ratio) of reactants is:
B 2 O 3 /SiO 2 =0.1;
n-octyl trimethyl ammonium hydroxide/SiO 2 =0.3;
NaOH/SiO 2 =0.25;
H 2 O/SiO 2 =25。
After being mixed evenly, the mixture is put into a stainless steel reaction kettle and crystallized for 7 days at 170 ℃. Filtering and washing after crystallization, drying in a 110 ℃ oven for 6 hours to obtain a molecular sieve, wherein the XRD spectrum of the sample is similar to that of fig. 1, the scanning electron microscope SEM (scanning electron microscope) image of the sample is similar to that of fig. 2, the crystal is in a coffin shape, the average length is 800nm, the length-to-width ratio is 3.0, and the average thickness is 80nm.
The dried sample is roasted at 550 ℃ for 6 hours, and the specific surface area of the obtained product is 392 m 2 Per gram, micropore volume 0.13 cm 3 /g. Measurement of SiO of a sample by inductively coupled plasma atomic emission spectrometry (ICP) 2 /B 2 O 3 =22.4 (molar ratio).
Comparative example 1
In analogy to example 1, 4.826 gDeionized water, 5.237 g of an aqueous solution of n-octyl trimethyl ammonium chloride (30 wt% n-octyl trimethyl ammonium chloride), 3.785 g of a silica sol (SiO-containing) 2 40 wt.%), 0.840 g of sodium hydroxide aqueous solution (containing 30 mass% of NaOH), 0.312 g of boric acid, 0.2271 g of seed crystal and MWW type molecular sieve are mixed uniformly to prepare a mixture, and the material ratio (molar ratio) of reactants is as follows:
B 2 O 3 /SiO 2 =0.1;
n-octyl trimethyl ammonium chloride/SiO 2 =0.3;
NaOH/SiO 2 =0.25;
H 2 O/SiO 2 =25。
After being mixed evenly, the mixture is put into a stainless steel reaction kettle and crystallized for 7 days at 170 ℃. After crystallization, filtering and washing, drying the mixture in an oven at 110 ℃ for 6 hours to obtain a molecular sieve, wherein the XRD spectrum of the sample is shown in figure 11 and is not EUO type molecular sieve.
Claims (20)
1. An EUO molecular sieve, characterized in that: the framework element of the molecular sieve comprises silicon element and boron and/or titanium element, wherein the molar ratio of silicon to boron and/or titanium is 15-60; the molecular sieve crystal has coffin shape, and the average length is 300-1000 nm.
2. The EUO molecular sieve according to claim 1, characterized in that: the average length of the molecular sieve crystals is 500-800 nm.
3. The EUO molecular sieve according to claim 1, characterized in that: the aspect ratio of the molecular sieve crystals is 1.5-5, and the average thickness is less than or equal to 100nm.
4. The EUO molecular sieve of claim 3, wherein: the aspect ratio of the molecular sieve crystals is 2-4, and the average thickness is 50-100 nm.
5. The EUO molecular sieve according to claim 1, characterized in that: the specific surface area of the molecular sieve is 250-750 m 2 Per gram, the micropore volume is 0.05-0.40 cm 3 /g.
6. The EUO molecular sieve of claim 5, wherein: the specific surface area of the molecular sieve is 300-700 meters 2 Per gram, the micropore volume is 0.08-0.35 cm 3 /g.
7. The EUO molecular sieve of claim 6, wherein: the specific surface area of the molecular sieve is 350-650 m 2 Per gram, the micropore volume is 0.10-0.30 cm 3 /g.
8. A synthesis method of an EUO molecular sieve is characterized by comprising the following steps: the synthesis steps comprise: crystallizing a mixture of a silica source, a boron oxide source and/or a titanium oxide source, an alkali source, a structure directing agent, water and seed crystals to obtain an EUO molecular sieve; the structure directing agent is selected from at least one of n-octyl trimethyl quaternary ammonium salt or quaternary ammonium base thereof, the seed crystal is IWV molecular sieve, and the mole ratio of the silicon dioxide source, the boron oxide source and/or the titanium oxide source, the alkali source, the structure directing agent and water is 1 (0.005-0.3): (0.05-0.6): (0.05-1.0): (5-200).
9. The method of synthesis according to claim 8, wherein: the structure directing agent is any one or more of n-octyl trimethyl ammonium chloride, n-octyl trimethyl ammonium bromide or n-octyl trimethyl ammonium hydroxide.
10. The method of synthesis according to claim 8, wherein: the mass ratio of the seed crystal to the silicon dioxide source is 0.01-0.25.
11. The method of synthesis according to claim 10, wherein: the mass ratio of the seed crystal to the silicon dioxide source is 0.03-0.18.
12. The method of synthesis according to claim 8, wherein: the molar ratio of the silicon dioxide source, the boron oxide source and/or the titanium oxide source, the alkali source, the structure directing agent and the water is 1 (0.01-0.25): 0.1-0.5): 0.1-0.9): 8-100.
13. The method of synthesis according to claim 12, wherein: the molar ratio of the silicon dioxide source, the boron oxide source and/or the titanium oxide source, the alkali source, the structure directing agent and the water is 1 (0.02-0.2): (0.15-0.4): (0.15-0.8): (10-50).
14. The method of synthesis according to claim 8, wherein: the silicon dioxide source is at least one selected from silicic acid, silica gel, silica sol, tetraethyl silicate and water glass; the boron oxide source is selected from at least one of boric acid, diboron trioxide, borate and borax; the titanium oxide source is selected from tetraethyl titanate and TiCl 4 Hexafluorotitanic acid, ti (SO) 4 ) 2 And at least one of titanium dioxide.
15. The method of synthesis according to claim 8, wherein: the alkali source is selected from one or more of alkali taking alkali metal or alkaline earth metal as cation.
16. The method of synthesis according to claim 8, wherein: the crystallization conditions of the mixture include: crystallizing at 105-210 ℃ for 1-10 days.
17. The method of synthesis according to claim 16, wherein: the crystallization condition of the mixture comprises crystallization for 2-9 days at 120-195 ℃.
18. The method of synthesis according to claim 17, wherein: the crystallization conditions of the mixture comprise crystallization for 3-8 days at 135-180 ℃.
19. An EUO molecular sieve composition characterized by: comprising a molecular sieve according to any one of claims 1 to 7 or synthesized according to the synthesis method of any one of claims 8 to 18, and a binder.
20. Use of the EUO molecular sieve according to any one of claims 1 to 7 or a molecular sieve synthesized according to the synthesis method of any one of claims 8 to 18, or the EUO molecular sieve composition according to claim 19 as an adsorbent or a catalyst for the conversion of organic compounds.
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CN109052426A (en) * | 2018-09-28 | 2018-12-21 | 华东师范大学 | A kind of synthetic method of high germanium IWV topological structure molecular sieve |
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