CN114014335A - Silicon-germanium UTL type large pore molecular sieve and preparation method thereof - Google Patents
Silicon-germanium UTL type large pore molecular sieve and preparation method 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 109
- 239000002808 molecular sieve Substances 0.000 title claims abstract description 104
- 229910000577 Silicon-germanium Inorganic materials 0.000 title claims abstract description 34
- LEVVHYCKPQWKOP-UHFFFAOYSA-N [Si].[Ge] Chemical compound [Si].[Ge] LEVVHYCKPQWKOP-UHFFFAOYSA-N 0.000 title claims abstract description 34
- 239000011148 porous material Substances 0.000 title claims abstract description 31
- 238000002360 preparation method Methods 0.000 title abstract description 14
- 238000002425 crystallisation Methods 0.000 claims abstract description 29
- 230000008025 crystallization Effects 0.000 claims abstract description 29
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 28
- 238000000034 method Methods 0.000 claims abstract description 17
- 230000008569 process Effects 0.000 claims abstract description 11
- 239000013078 crystal Substances 0.000 claims abstract description 7
- 239000000203 mixture Substances 0.000 claims description 56
- 239000000499 gel Substances 0.000 claims description 42
- YBMRDBCBODYGJE-UHFFFAOYSA-N germanium oxide Inorganic materials O=[Ge]=O YBMRDBCBODYGJE-UHFFFAOYSA-N 0.000 claims description 40
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 34
- 238000006243 chemical reaction Methods 0.000 claims description 25
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical group O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 24
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 claims description 22
- IIYFAKIEWZDVMP-UHFFFAOYSA-N tridecane Chemical compound CCCCCCCCCCCCC IIYFAKIEWZDVMP-UHFFFAOYSA-N 0.000 claims description 22
- 229910052732 germanium Inorganic materials 0.000 claims description 21
- 239000008367 deionised water Substances 0.000 claims description 19
- 229910021641 deionized water Inorganic materials 0.000 claims description 19
- 239000000706 filtrate Substances 0.000 claims description 17
- 238000005406 washing Methods 0.000 claims description 17
- 229910001868 water Inorganic materials 0.000 claims description 15
- 229910052710 silicon Inorganic materials 0.000 claims description 14
- 239000010703 silicon Substances 0.000 claims description 14
- 238000001035 drying Methods 0.000 claims description 13
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 12
- 229910052681 coesite Inorganic materials 0.000 claims description 11
- 229910052906 cristobalite Inorganic materials 0.000 claims description 11
- 239000000377 silicon dioxide Substances 0.000 claims description 11
- 229910052682 stishovite Inorganic materials 0.000 claims description 11
- 238000000967 suction filtration Methods 0.000 claims description 11
- 229910052905 tridymite Inorganic materials 0.000 claims description 11
- 238000003756 stirring Methods 0.000 claims description 10
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 9
- 239000000376 reactant Substances 0.000 claims description 9
- 238000001354 calcination Methods 0.000 claims description 8
- 229940119177 germanium dioxide Drugs 0.000 claims description 8
- 239000012265 solid product Substances 0.000 claims description 8
- -1 polytetrafluoroethylene Polymers 0.000 claims description 6
- 239000000047 product Substances 0.000 claims description 5
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims description 4
- IEXRMSFAVATTJX-UHFFFAOYSA-N tetrachlorogermane Chemical compound Cl[Ge](Cl)(Cl)Cl IEXRMSFAVATTJX-UHFFFAOYSA-N 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 3
- 235000019353 potassium silicate Nutrition 0.000 claims description 3
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 3
- ZRLCXMPFXYVHGS-UHFFFAOYSA-N tetramethylgermane Chemical compound C[Ge](C)(C)C ZRLCXMPFXYVHGS-UHFFFAOYSA-N 0.000 claims description 3
- WNPMJIKMURUYFG-UHFFFAOYSA-N [N+](=O)([O-])[O-].[Ge+2].[N+](=O)([O-])[O-] Chemical compound [N+](=O)([O-])[O-].[Ge+2].[N+](=O)([O-])[O-] WNPMJIKMURUYFG-UHFFFAOYSA-N 0.000 claims description 2
- 238000001816 cooling Methods 0.000 claims description 2
- 229910021485 fumed silica Inorganic materials 0.000 claims description 2
- SCCCLDWUZODEKG-UHFFFAOYSA-N germanide Chemical compound [GeH3-] SCCCLDWUZODEKG-UHFFFAOYSA-N 0.000 claims description 2
- XCLKKWIIZMHQIV-UHFFFAOYSA-N isobutylgermane Chemical compound CC(C)C[Ge] XCLKKWIIZMHQIV-UHFFFAOYSA-N 0.000 claims description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 2
- 239000000741 silica gel Substances 0.000 claims description 2
- 235000012239 silicon dioxide Nutrition 0.000 claims description 2
- 230000003068 static effect Effects 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims 1
- 238000003786 synthesis reaction Methods 0.000 abstract description 26
- 230000015572 biosynthetic process Effects 0.000 abstract description 25
- 238000000746 purification Methods 0.000 abstract description 5
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 abstract description 4
- 230000002860 competitive effect Effects 0.000 abstract 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 19
- 238000002441 X-ray diffraction Methods 0.000 description 9
- 239000007864 aqueous solution Substances 0.000 description 9
- 230000002194 synthesizing effect Effects 0.000 description 9
- 238000012360 testing method Methods 0.000 description 9
- 229910021536 Zeolite Inorganic materials 0.000 description 8
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 8
- 239000010457 zeolite Substances 0.000 description 8
- 238000006555 catalytic reaction Methods 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 5
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 5
- 238000010306 acid treatment Methods 0.000 description 4
- 239000003513 alkali Substances 0.000 description 4
- 230000009286 beneficial effect Effects 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 238000002411 thermogravimetry Methods 0.000 description 3
- 230000009466 transformation Effects 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- 229920002521 macromolecule Polymers 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- NVZWMJWMTWOVNJ-UHFFFAOYSA-N 6-azaspiro[3.4]octane Chemical compound C1CCC21CNCC2 NVZWMJWMTWOVNJ-UHFFFAOYSA-N 0.000 description 1
- 241000288673 Chiroptera Species 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- CSDREXVUYHZDNP-UHFFFAOYSA-N alumanylidynesilicon Chemical compound [Al].[Si] CSDREXVUYHZDNP-UHFFFAOYSA-N 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000002182 crystalline inorganic material Substances 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000006735 epoxidation reaction Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000009616 inductively coupled plasma Methods 0.000 description 1
- 238000002354 inductively-coupled plasma atomic emission spectroscopy Methods 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000003541 multi-stage reaction Methods 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 230000037361 pathway Effects 0.000 description 1
- 238000005504 petroleum refining Methods 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000004540 process dynamic Methods 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- WZOLTEULLCFJTR-UHFFFAOYSA-N tridecane hydrate Chemical compound CCCCCCCCCCCCC.O WZOLTEULLCFJTR-UHFFFAOYSA-N 0.000 description 1
- 230000004580 weight loss Effects 0.000 description 1
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- 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
- C01B39/46—Other types characterised by their X-ray diffraction pattern and their defined composition
- C01B39/48—Other types characterised by their X-ray diffraction pattern and their defined composition using at least one organic template directing agent
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- 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
- C01B39/08—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 belongs to the technical field of molecular sieves, and relates to a silicon-germanium UTL large-pore molecular sieve and a preparation method thereof. In the preparation method, 7-azaspiro- [6,6] is used]-tridecane molecule as organic template. Compared with the existing template, the template used in the patent report has a simple structure, is simple and easy to operate in the synthesis process, and does not need a complex synthesis process and purification steps; the synthesis of UTL molecular sieve adopts hydroxyl to replace F‑As a mineralizer, the silicon-germanium UTL molecular sieve with perfect crystallization and unique appearance can be obtained without adding fluoride. The UTL type molecular sieve synthesized by the template agent has wider synthesis formula range, has no obvious competitive phase and is easier to obtain pure UTL molecular sieve crystals.
Description
Technical Field
The invention belongs to the technical field of molecular sieves, and particularly relates to a silicon-germanium UTL type large pore molecular sieve and a preparation method thereof.
Background
The information in this background section is only for enhancement of understanding of the general background of the invention and is not necessarily to be construed as an admission or any form of suggestion that this information forms the prior art that is already known to a person of ordinary skill in the art.
Molecular sieves are microporous crystalline inorganic materials with pore systems of uniform molecular size and are widely used in the fields of gas adsorption and separation, ion exchange and catalysis, which are associated with environmental protection, chemical conversion and energy conservation, etc. The pore system of the molecular sieve can be divided into small pores, medium pores, large pores and ultra-large pores according to the number of T atoms contained in the pore openings of the molecular sieve. The macroporous and ultra-macroporous molecular sieves are beneficial to the diffusion of macromolecular reactants, intermediate products and final target products and are beneficial to catalyzing reactions in which macromolecules participate.
Germanium-containing molecular sieves are one of the important members of the molecular sieve family, and are synthesized by introducing germanium atoms into the molecular sieve framework. The presence of framework germanium can stabilize smaller secondary structural units in the molecular sieve structure, including double four-membered rings, double three-membered rings, and three-membered rings. In pure silicon molecular sieves, the presence of these smaller secondary building blocks can result in structural distortion, which in turn affects the stability of the molecular sieve. Therefore, the introduction of germanium into the framework of molecular sieves makes it possible to achieve the preparation of novel molecular sieve topologies. There are currently 30 new molecular sieve structures that have been successfully synthesized thanks to the introduction of germanium into the framework.
The ultra-large pore molecular sieve is beneficial to the diffusion of macromolecules and has important advantages in catalytic reactions in the fields related to petroleum refining and fine chemicals. The germanium-containing molecular sieve generally has larger pore size and has good application prospect in the field of catalysis. For example, Ge-TS-1 molecular sieves have higher catalytic activity in the epoxidation of propylene than TS-1 (M.K. Faraj, U.S. patent 5977009 (1999)). For example, germanium-containing ZSM-5 has improved catalytic activity over conventional ZSM-5 in a range of catalytic reactions (L.G.A.van de Water, J.C.van der Water, J.C.Jansen, T.Maschmeyer, J.Catal.223(2004) 170-. The synthesis of silicon germanium molecular sieves has important value in the preparation of novel molecular sieve structures and in catalytic applications.
UTL-type molecular sieves with two-dimensionally intercommunicated 14X 12-membered ring channel systems were first synthesized by Paillaud and Corma simultaneously in 2004 and were named IM-12 and ITQ-15, respectively (J.L.Paillaud; B.Harbuzaru; J.Patarin; N.bats, Science 2004,304, 990-. The synthesis of ITQ-15 and IM-12 both adopt organic quaternary ammonium salt as a template agent, and the process of synthesizing the template agent is complicated. The subsequent reported template agent for synthesizing the UTL type molecular sieve needs to carefully regulate and control reaction conditions to avoid generating other crystal phases.
The UTL type molecular sieve can generate selective separation of partial skeleton structure units through secondary synthesis, and further generate a topological structure conversion, so as to form a novel high-silicon molecular sieve. The high-silicon molecular sieves obtained by the secondary synthesis are similar to the parent molecular sieve UTL in structure, and are different from the parent molecular sieve UTL in connection mode between layers. After the second synthesis, the interlayer connection mode can be changed from a double-four-membered ring to a single-four-membered ring, an oxygen bridge and a mixed connection mode of the double-four-membered ring and the single-four-membered ring. Relative displacement between the layers may also occur. The secondary synthesis method mainly comprises two methods, namely acid treatment and alkali treatment. The concentration, type, use of organic solvent, time and temperature of acid treatment, among others, have an effect on the newly formed molecular sieve structure, and the acid treatment process is mainly Inverse Sigma Transformation and Assembly-Disassassable-Organization-reaction (ADOR) two reaction pathways (E.Verheyen, L.Joos, K.Van Havenberger, E.Breynaert, N.Kasian, E.Gobechya, K.Houthoofd, C.Martineau, M.Hinterstein, F.Taulelle, V.Van Speybroock, M.Waroquier, S.Bals, G.Van Teleloo, C.E.A.Kichhock and J.A.Martens, Nat.Mather, Wh.10511, S.Bals, G.Van Telodeo, C.E.A.Kichhock and J.A.Martens, Nat.Mather, W.11, W.9.K.Valkyo, G.V.Val.R.R.R.106R.R.R.K.Gray, S.R.R.R.R.R.K.
A.Zukal,O.Shvets and J.
Nat. chem.,2013,5, 628-633). Acid siteThe principle is that the dual-quaternary ring structure unit containing germanium is mainly separated, and the transformation of the topological structure can be successfully realized only by certain requirements on the chemical composition of the dual-quaternary ring structure unit and the distribution of germanium in the dual-quaternary ring structure unit. Partial framework silicon is dissolved in the alkali treatment process, silicon and germanium in the dual-quaternary ring are removed, and the influence of the element composition of the structural unit on the alkali treatment result is small.
The inventors found that the organic templating agent used in the current methods of preparing UTL-type molecular sieves is complex in structure and involves multiple reactions and purification steps, which increases the difficulty of UTL molecular sieve synthesis and limits further research on this material. Because of the above-mentioned properties of UTL, this molecular sieve is the most interesting member of the silicon germanium family of molecular sieves, and is one of the most promising silicon germanium molecular sieves. It is therefore necessary to devise a route to the synthesis of new UTL-type molecular sieves.
The 7-azaspiro- [6,6] -tridecane molecule is a nitrogen spiro heterocyclic quaternary ammonium salt, and documents report that the quaternary ammonium salt can be used for synthesizing molecular sieves to prepare MTW-type silicon-aluminum molecular sieves, but the structural selectivity to the molecular sieves is not high, and MTW crystalline phases tend to be generated under the conditions of different silicon sources, aluminum sources, synthesis conditions and the like. The subject group adopts the quaternary ammonium salt and combines the guiding effect of the dual-quaternary ring structure of the germanium element to prepare various molecular sieves with different topological structures, thereby greatly improving the selectivity of the quaternary ammonium salt molecules to the molecular sieve structure. For example, the preliminary experiments of the subject group show that 5-azaspiro- [4,4] -nonane can be used for synthesizing IWW type silicon germanium molecular sieve, and 6-azaspiro- [5,6] -dodecane can be used for synthesizing ISV type molecular sieve, which means that the quaternary ammonium salt has certain selectivity to the structure of the final silicon germanium molecular sieve and shows certain advantages in the synthesis of the silicon germanium molecular sieve. The topological structure of the final molecular sieve can be changed by changing the size of the ring of the azaspiro, and the method is an innovation in the field of molecular sieve research. There is no information in the reports that molecular sieves of the IWW, ISV and UTL types are competing crystalline phases or occur simultaneously during the synthesis. The synthesis of the molecular sieves needs the participation of different organic templates, the synthesis conditions are not obviously overlapped, and the mutual transformation among the structures is not reported. Therefore, the technical barriers are their structures themselves, and the development and synthesis of molecular sieves with different structures is a hot spot and a difficult problem in the field of molecular sieve synthesis, and is undoubtedly very important if the purpose of synthesizing different molecular sieves is achieved by simply changing the structures of template molecules. Although the templates for synthesizing the ISV and UTL type molecular sieves are very similar, the structures of the compounds are different and the synthesis conditions used are completely different, the UTL type molecular sieve reported in the patent can be synthesized by standing conditions, but the synthesis of the ISV type molecular sieve needs to be carried out under the rotary crystallization condition. In addition, the shortest time required by the two crystallization is different, the UTL type molecular sieve can be completely crystallized within three days at the fastest speed, the ISV type silicon germanium molecular sieve needs the crystallization time of 7 days, otherwise, the ISV type silicon germanium molecular sieve is incompletely crystallized and contains certain amorphous components. UTL-type molecular sieves can be synthesized at 160 ℃ but ISV is preferably synthesized at 175 ℃. In addition, UTL and ISV are two molecular sieves with completely different structures and morphologies, and have different application advantages in the aspect of subsequent catalytic reaction research.
Disclosure of Invention
The invention provides a silicon-germanium UTL type large-pore molecular sieve and a preparation method thereof, aiming at solving the problem that the synthesis of an organic template used for synthesizing a UTL molecular sieve in the prior art is too complex. In the preparation process, 7-azaspiro- [6,6] -tridecane molecules are used as organic template agents, the structure is simple, a complex reaction process is not needed, hydroxide radicals are used as alkaline media in the synthesis, fluoride is not needed to be added, and the UTL silicon germanium UTL type molecular sieve which is well crystallized and has a nano-layered staggered accumulation morphology can be obtained. The prepared UTL molecular sieve sample can realize the conversion of topological structure after acid treatment and alkali treatment.
In order to achieve the above objects, the present invention provides a method for preparing a silicon-germanium UTL zeolite molecular sieve, which comprises using 7-azaspiro- [6,6] -tridecane molecule as an organic template.
The preparation method specifically comprises the following steps:
(1) organic template agent 7-azaspiro- [6,6]Mixing the tridecane hydroxide solution, the germanide and deionized water, stirring until the mixture is clear to obtain a clear solution, and dropwise adding ethyl orthosilicate and SiO into the clear solution2Or water glass and the like, and stirring for 30min at room temperature to obtain a reactant;
(2) transferring the gel reactant to a high-pressure reaction kettle with a polytetrafluoroethylene lining, then putting the high-pressure reaction kettle into a rotary oven, and cooling the high-pressure reaction kettle to room temperature after rotary crystallization to obtain a solid product;
(3) and (3) washing the solid product obtained in the step (2) with deionized water until the pH value of the filtrate is less than 8, and putting the filtrate into an oven to dry overnight to obtain the silicon-germanium UTL type large-pore molecular sieve.
Further, the invention also comprises (4) putting the UTL type large-pore molecular sieve into a muffle furnace, and roasting to obtain the UTL molecular sieve with high crystallinity and without the template agent.
Further, in the step (1), the mass concentration of the solution formed by the 7-azaspiro- [6,6] -tridecane molecule and the deionized water is 10-50 wt%.
Further, in the step (1), 7-azaspiro- [6,6]-the molar ratio of tridecane molecules to germanium source is 3: 4; the molar ratio of the deionized water to the germanium source is H2O:GeO237.5: 1; preferably, the germanium source is at least one of germanium dioxide, tetramethyl germanium, isobutyl germane, germanium tetrachloride and germanium nitrate; more preferably, GeO2After the solution is added into the organic template agent solution, the solution is stirred for 5 to 30 minutes at room temperature, so that the germanium source is fully dissolved, and a precursor structure with a guiding function can be formed in the solution.
Further, in the step (1), the molar ratio of the silicon source to the germanium source is SiO2:GeO2Adding a silicon source into the clear solution, and stirring for 30 minutes at room temperature to obtain a reactant, wherein the reactant is a gel mixture or a clear solution, and the reaction time depends on the type of the silicon source and the stirring time; preferably, the silicon source is at least one of tetraethyl silicate, silicic acid, fumed silica gel, water glass, and silica sol.
Further, in the step (2), the crystallization conditions are as follows: rotating and crystallizing at the temperature of 150-180 ℃ for 24-168 hours, preferably at the temperature of 175 ℃ for 96 hours, so as to achieve the balance of reducing energy consumption and ensuring the crystallization degree of the sample; preferably, the rotation speed is 15 to 40rpm, preferably 40rpm if a smaller crystal grain is prepared, preferably 15rpm if a larger crystal grain is prepared or crystallized under a standing condition; more preferably, the crystallization process is whole-process dynamic or static crystallization in a closed high-pressure kettle in a constant temperature state; and after the crystallization treatment, the steps of washing, separating, drying and roasting the obtained crystallization product are also included.
Further, in the step (3), the washing process is that deionized water is used for washing while suction filtration is carried out until the pH value of the obtained filtrate is less than 8; the drying temperature is 60-90 ℃.
Further, in the step (4), the calcination temperature is 500-700 ℃, the calcination time is 3-4 hours, and the calcination time is more preferably 3 hours at 600 ℃.
Compared with the prior art, the invention has the following advantages:
(1) the invention takes 7-azaspiro- [6,6] -tridecane molecule as an organic template agent for preparing the silicon-germanium UTL type zeolite molecular sieve, the substance has the advantages of easy synthesis and simple structure, compared with the previously reported template agent for synthesizing the UTL type molecular sieve, the substance has low cost, simple and easy synthesis process and good selectivity to the UTL type molecular sieve, can synthesize a target product in a wider gel system, and fluorine ions are not added in the crystallization process of the molecular sieve, so the whole synthesis system is relatively safe, has little pollution and is environment-friendly.
(2) The UTL-type molecular sieve obtained by the preparation method of the silicon-germanium UTL-type zeolite molecular sieve provided by the invention has an intercommunicated two-dimensional 14x12 ultra-large pore canal system, is a catalytic material with great potential, has good crystallinity of a sample, no impurities, stable structure after high-temperature roasting, good thermal stability and higher germanium content, and creates a very powerful condition for subsequent structural recombination.
Drawings
The accompanying drawings, which are incorporated in and constitute a part of this specification, are included to provide a further understanding of the invention, and are incorporated in and constitute a part of this specification, illustrate exemplary embodiments of the invention and together with the description serve to explain the invention and not to limit the invention.
FIG. 1 is an X-ray diffraction (XRD) pattern of a sample obtained in example 1 before and after calcination;
FIG. 2 is a Scanning Electron Microscope (SEM) photograph of a calcined sample obtained in example 1;
FIG. 3 is a thermogravimetric analysis (TGA) plot of the unfired sample obtained in example 1;
FIG. 4 is a nitrogen adsorption isotherm graph of the calcined sample obtained in example 1;
FIG. 5 is an X-ray diffraction (XRD) pattern of a calcined sample obtained in example 2;
FIG. 6 is an X-ray diffraction (XRD) pattern of a calcined sample obtained in example 3.
Detailed Description
The invention will be further described with reference to specific embodiments, and the advantages and features of the invention will become apparent as the description proceeds. The examples are illustrative only and do not limit the scope of the present invention in any way. It will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the spirit and scope of the invention, and that such changes and modifications may be made without departing from the spirit and scope of the invention.
It is noted that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of exemplary embodiments according to the invention. As used herein, the singular forms "a", "an" and "the" are intended to include the plural forms as well, and it should be understood that when the terms "comprises" and/or "comprising" are used in this specification, they specify the presence of stated features, steps, operations, devices, components, and/or combinations thereof, unless the context clearly indicates otherwise.
As described in the background, the prior art organic templating agents are complex in structure and involve multiple reactions and purification steps. In order to solve the technical problems, the invention provides a preparation method of a silicon-germanium UTL type zeolite molecular sieve, which uses 7-azaspiro- [6,6] -tridecane molecules as an organic template agent to prepare the molecular sieve.
The 7-azaspiro- [6,6] -tridecane molecule has the advantages of simple structure, no need of multi-step reaction, difficulty in mixing impurities and no need of multiple purification steps; the invention takes the simple and easily synthesized 7-azaspiro- [6,6] -tridecane molecule as the template agent in the preparation process of the zeolite molecular sieve, is very beneficial to large-scale industrialized preparation of the zeolite molecular sieve, saves the cost to a certain extent and reduces the energy consumption.
The invention takes 7-azaspiro- [6,6] -tridecane molecule as an organic template agent, and does not need to add fluoride for assistance in the crystallization process, thereby avoiding the problem of environmental pollution caused by the fluoride. In addition, due to the action of electric charges, the existence of fluoride ions prevents aluminum and other trivalent metal elements from being doped in the zeolite framework, and the invention takes 7-azaspiro- [6,6] -tridecane molecules as an organic template agent and can be suitable for preparing zeolite molecular sieves doped with trivalent metals.
Wherein the 7-azaspiro- [6,6] -tridecane is synthesized by a single synthesis reaction and simple purification steps, including evaporation of excess water and recrystallization of the solid in anhydrous diethyl ether.
Example 1
8.21g of organic template agent 7-azaspiro- [6,6]Tridecane (19.16% aqueous solution) and 10.32g of deionized water were mixed homogeneously, then 1.10g of germanium dioxide was added and stirred at room temperature for 10 minutes to give a clear solution. Thereafter, 4.48g of tetraethyl silicate was added, the mixture was kept in a sealed state, and the mixture was stirred at room temperature for 45 minutes to obtain a gel mixture. The molar ratio of the gel mixture is SiO2:GeO2:SDAOH:H2O ═ 0.8:0.4:0.3: 30. Transferring the obtained gel mixture into a high-pressure inner liner of a reaction kettle, dynamically crystallizing in an oven at 175 ℃ for 168 hours (40rpm), taking out a sample, carrying out suction filtration, washing for multiple times until the pH of the obtained filtrate is less than 8, drying at 80 ℃, roasting at 600 ℃ for 3 hours, and then carrying out conventional test. The obtained solid product is characterized by an X-ray diffractometer to obtain XRD data as shown in figure 1, the crystallinity of the sample is intact, and the UTL type topological structure can be confirmed by comparing with a standard spectrogram. The molecular sieve is in the form of thin sheet with crystal size as shown in FIG. 2Relatively uniform, about 5x5 μm in length and width, and about 0.1 μm in thickness. The XRD pattern of the UTL-type molecular sieve after 600 c calcination showed that the structure remained intact, indicating that the molecular sieve was stable at least at 600 c. As shown in FIG. 3, TGA analysis reveals a total weight loss after calcination of about 20.0 wt%.
In this example, the molecular sieve obtained was subjected to nitrogen desorption at 77k (as shown in FIG. 4), giving a total specific surface area of 577m2In terms of a volume of micropores, 0.20cm3In terms of/g, the mean pore diameter is 1.7 nm. An inductively coupled plasma emission spectrometer (ICP-OES) test is carried out, and the silicon-germanium ratio is about 3.3.
Example 2
8.21g of organic template agent 7-azaspiro- [6,6]Tridecane (19.16% aqueous solution) and 10.32g of deionized water were mixed homogeneously, then 2.3g of germanium tetrachloride were added and stirred at room temperature for 10 minutes to give a clear solution. Thereafter, 4.48g of tetraethyl silicate was added, the mixture was kept in a sealed state, and the mixture was stirred at room temperature for 45 minutes to obtain a gel mixture. The molar ratio of the gel mixture is SiO2:GeO2:SDAOH:H2O ═ 0.8:0.4:0.3: 30. Transferring the obtained gel mixture into a high-temperature resistant reaction kettle lining, placing the gel mixture into an oven at 170 ℃ for dynamic crystallization for 168 hours (40rpm), taking out a sample, carrying out suction filtration, washing for multiple times until the pH of the obtained filtrate is less than 8, drying at 80 ℃, roasting at 600 ℃ for 3 hours, and then carrying out conventional test. The obtained solid product was characterized by an X-ray diffractometer to obtain XRD data as shown in FIG. 5. The molecular sieve is well crystallized and no amorphous product is seen. It can be seen that the same molar ratio of the gel mixture has resulted in a silicon germanium molecular sieve with UTL-type topology with good crystallinity after 96 hours of dynamic crystallization.
Example 3
5.59g of organic template agent 7-azaspiro- [6,6]Tridecane (19.16% aqueous solution) and 15.37g of deionized water were mixed homogeneously, then 0.70g of germanium dioxide was added and stirred at room temperature for 10 minutes to give a clear solution. Then 0.82g SiO was added2The mixture was stirred at room temperature for 45 minutes while maintaining the sealed state, to obtain a gel mixture. The molar ratio of the gel mixture is SiO2:GeO2:SDAOH:H2O＝0.8:0.4:0.3:60. Transferring the obtained gel mixture into a high-temperature resistant reaction kettle lining, placing the gel mixture into an oven at 170 ℃ for dynamic crystallization for 150 hours (40rpm), taking out a sample, carrying out suction filtration, washing for multiple times until the pH of the obtained filtrate is less than 8, drying at 80 ℃, roasting at 600 ℃ for 3 hours, and then carrying out conventional test. The obtained solid product is characterized by an X-ray diffractometer to obtain XRD data as shown in figure 6.
Example 4
11.97g of organic template agent 7-azaspiro- [6,6]Tridecane (19.16% aqueous solution) and 3.97g of deionized water were mixed homogeneously, then 3.07g of germanium tetrachloride were added and stirred at room temperature for 10 minutes to give a clear solution. Thereafter, 6.07g of tetraethyl silicate was added, and the mixture was kept in a sealed state and stirred at room temperature for 45 minutes to obtain a gel mixture. The molar ratio of the gel mixture is SiO2:GeO2:SDAOH:H2O ═ 0.8:0.4:0.3: 15. Transferring the obtained gel mixture into a high-temperature resistant reaction kettle lining, placing the gel mixture into a 165 ℃ oven for dynamic crystallization for 168 hours (40rpm), taking out a sample, carrying out suction filtration, washing for multiple times until the pH of the obtained filtrate is less than 8, drying at 80 ℃, roasting at 600 ℃ for 3 hours, and then carrying out conventional test. The XRD data of the obtained solid product is represented by an X-ray diffractometer and shown in figure 6, the XRD spectrogram is greatly changed after water is reduced, a small new peak appears between 11-12 degrees and 16-17 degrees, and it can be seen that the reduction of the water content of the synthesized gel can cause the change of the topological structure, so that the synthesized water content cannot be too low.
Example 5
10.40g of organic template agent 7-azaspiro- [6,6]Tridecane (19.16% aqueous solution) and 8.59g of deionized water were mixed homogeneously, then 1.35g of tetramethylgermanium was added and stirred at room temperature for 10 minutes to give a clear solution. Then 1.23g of SiO were added2The mixture was stirred at room temperature for 45 minutes while maintaining the sealed state, to obtain a gel mixture. The molar ratio of the gel mixture is SiO2:GeO2:SDAOH:H2O ═ 0.8:0.4:0.4: 30. Transferring the obtained gel mixture into a high-temperature resistant reaction kettle lining, placing the gel mixture in a 175 ℃ oven for dynamic crystallization for 140 hours (15rpm), taking out a sample, carrying out suction filtration, and washing for multiple times until the pH of the obtained filtrate is less than that of the filtrateDrying at the temperature of 8 and 80 ℃, and roasting at the temperature of 600 ℃ for 3 hours to obtain the UTL type molecular sieve with complete crystallization.
Example 6
13.00g of organic template agent 7-azaspiro- [6,6]Tridecane (19.16% aqueous solution) and 7.38g of deionized water were mixed homogeneously, then 1.05g of germanium dioxide was added and stirred at room temperature for 10 minutes to give a clear solution. Then 1.23g of SiO were added2The mixture was stirred at room temperature for 45 minutes while maintaining the sealed state, to obtain a gel mixture. The molar ratio of the gel mixture is SiO2:GeO2:SDAOH:H2O ═ 0.8:0.4:0.5: 60. Transferring the obtained gel mixture into a high-temperature resistant reaction kettle lining, dynamically crystallizing the gel mixture in an oven at 180 ℃ for 168 hours (40rpm), taking out a sample, carrying out suction filtration, washing for multiple times until the pH of the obtained filtrate is less than 8, drying the filtrate at 80 ℃, roasting the filtrate at 600 ℃ for 3 hours to obtain the well-crystallized UTL type molecular sieve, and then carrying out conventional test.
Example 7
7.80g of organic template agent 7-azaspiro- [6,6]Tridecane (19.16% aqueous solution) and 9.80g of deionized water were mixed homogeneously, followed by addition of 2.09g of germanium dioxide and stirring at room temperature for 10 minutes to give a clear solution. Thereafter, 4.25g of tetraethyl silicate was added, the mixture was kept in a sealed state, and the mixture was stirred at room temperature for 45 minutes to obtain a gel mixture. The molar ratio of the gel mixture is SiO2:GeO2:SDAOH:H2O ═ 0.8:0.8:0.3: 30. Transferring the obtained gel mixture into a high-temperature resistant reaction kettle lining, placing the gel mixture into a 160 ℃ oven for dynamic crystallization for 168 hours (40rpm), taking out a sample, carrying out suction filtration, washing for multiple times until the pH of the obtained filtrate is less than 8, drying at 80 ℃, roasting at 600 ℃ for 3 hours, and then carrying out conventional test.
Example 8
10.40g of organic template agent 7-azaspiro- [6,6]Tridecane (19.16% aqueous solution) and 8.59g of deionized water were mixed homogeneously, followed by addition of 2.09g of germanium dioxide and stirring at room temperature for 10 minutes to give a clear solution. Thereafter, 4.25g of tetraethyl silicate was added, the mixture was kept in a sealed state, and the mixture was stirred at room temperature for 45 minutes to obtain a gel mixture. The molar ratio of the gel mixture is SiO2:GeO2:SDAOH:H2O ═ 0.8:0.8:0.4: 30. Transferring the obtained gel mixture into a high-temperature resistant reaction kettle lining, placing the gel mixture into a drying oven at 150 ℃ for dynamic crystallization for 196 hours (40rpm), taking out a sample, carrying out suction filtration, washing for multiple times until the pH of the obtained filtrate is less than 8, drying at 80 ℃, roasting at 600 ℃ for 3 hours, and then carrying out conventional test.
Example 9
13.00g of organic template agent 7-azaspiro- [6,6]Tridecane (19.16% aqueous solution) and 7.38g of deionized water were mixed homogeneously, then 2.09g of germanium dioxide was added and stirred at room temperature for 10 minutes to give a clear solution. Thereafter, 4.25g of tetraethyl silicate was added, the mixture was kept in a sealed state, and the mixture was stirred at room temperature for 45 minutes to obtain a gel mixture. The molar ratio of the gel mixture is SiO2:GeO2:SDAOH:H2O ═ 0.8:0.8:0.5: 30. Transferring the obtained gel mixture into a high-temperature resistant reaction kettle lining, placing the gel mixture into a 160 ℃ oven for dynamic crystallization for 96 hours (40rpm), taking out a sample, carrying out suction filtration, washing for multiple times until the pH of the obtained filtrate is less than 8, drying at 80 ℃, roasting at 600 ℃ for 3 hours, and then carrying out conventional test.
Claims (10)
1. A silicon germanium UTL type large pore molecular sieve is characterized in that the silicon germanium UTL type large pore molecular sieve takes 7-azaspiro- [6,6] -tridecane molecules as organic template agent to prepare the molecular sieve.
2. The silicon germanium UTL-type large pore molecular sieve of claim 1, wherein the method of preparing the large pore molecular sieve comprises the steps of:
(1) mixing the solution of the organic template agent 7-azaspiro- [6,6] -tridecane hydroxide, germanide and deionized water, stirring until the mixture is clear, then dropwise adding a silicon source, and stirring for 30min at room temperature after the completion to obtain a reactant;
(2) transferring the gel reactant to a high-pressure reaction kettle with a polytetrafluoroethylene lining, then putting the high-pressure reaction kettle into a rotary oven, and cooling the high-pressure reaction kettle to room temperature after rotary crystallization to obtain a solid product;
(3) and (3) washing the solid product obtained in the step (2) with deionized water until the pH value of the filtrate is less than 8, and putting the filtrate into an oven to dry overnight to obtain the silicon-germanium UTL type large-pore molecular sieve.
3. The silicon germanium, UTL, large pore molecular sieve of claim 2, wherein the method further comprises placing the UTL molecular sieve in a muffle furnace and calcining to obtain the template agent-depleted, high crystallinity UTL molecular sieve.
4. The silicon germanium UTL-type large pore molecular sieve of claim 2, wherein in step (1), the mass concentration of the solution of 7-azaspiro- [6,6] -tridecane molecule and deionized water is 10-50 wt%.
5. The silicon germanium, UTL, large pore molecular sieve of claim 4, wherein in step (1), the 7-azaspiro- [6,6] is present]-the molar ratio of tridecane molecules to germanium source is 3: 4; the molar ratio of the deionized water to the germanium source is H2O:GeO237.5: 1; preferably, the germanium source is at least one of germanium dioxide, tetramethyl germanium, isobutyl germane, germanium tetrachloride and germanium nitrate; more preferably, GeO2After adding into the organic template solution, stirring for 5-30 minutes at room temperature to fully dissolve the germanium source.
6. The silicon-germanium UTL-type large pore molecular sieve of claim 2, wherein in step (1), the molar ratio of the silicon source to the germanium source is SiO2:GeO2Adding a silicon source into the clear solution, and stirring at room temperature for 30 minutes to obtain a reactant, wherein the reactant is a gel mixture or a clear solution; preferably, the silicon source is at least one of tetraethyl silicate, silicic acid, fumed silica gel, water glass, and silica sol.
7. The silicon germanium UTL-type large pore molecular sieve of claim 2, wherein in the step (2), the crystallization process conditions are: rotating and crystallizing at 150-180 deg.c for 96-168 hr, preferably at 175 deg.c for 96 hr to reach the balance of lowering power consumption and ensuring the crystallization degree of the sample; preferably, the rotation speed is 15 to 40rpm, preferably 40rpm if a small crystal grain is prepared, and preferably 15rpm if a large crystal grain is prepared or crystallized under a standing condition.
8. The silicon germanium UTL-type large pore molecular sieve of claim 7, wherein the crystallization process is a full course dynamic or static crystallization inside a closed autoclave at a constant temperature; and after the crystallization treatment, the steps of washing, separating, drying and roasting the obtained crystallization product are also included.
9. The silicon germanium UTL-type large pore molecular sieve of claim 2, wherein in step (3), the washing is performed by washing with deionized water while performing suction filtration until the pH of the filtrate is less than 8; the drying temperature is 60-90 ℃.
10. The silicon germanium UTL-type large pore molecular sieve of claim 2, wherein in step (4), the calcination temperature is 500-.
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