WO2022257241A1 - Zinc-doped alpo-36 molecular sieve single crystal and preparation method therefor - Google Patents

Zinc-doped alpo-36 molecular sieve single crystal and preparation method therefor Download PDF

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WO2022257241A1
WO2022257241A1 PCT/CN2021/107961 CN2021107961W WO2022257241A1 WO 2022257241 A1 WO2022257241 A1 WO 2022257241A1 CN 2021107961 W CN2021107961 W CN 2021107961W WO 2022257241 A1 WO2022257241 A1 WO 2022257241A1
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zinc
molecular sieve
single crystal
alpo
doped
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许新统
史文涛
阮双琛
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深圳技术大学
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    • C—CHEMISTRY; METALLURGY
    • 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
    • C01B39/54—Phosphates, e.g. APO or SAPO compounds
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B37/00—Compounds having molecular sieve properties but not having base-exchange properties
    • C01B37/06—Aluminophosphates containing other elements, e.g. metals, boron
    • C01B37/065—Aluminophosphates containing other elements, e.g. metals, boron the other elements being metals only
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
    • C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/01—Particle morphology depicted by an image
    • C01P2004/02—Particle morphology depicted by an image obtained by optical microscopy
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/01—Particle morphology depicted by an image
    • C01P2004/03—Particle morphology depicted by an image obtained by SEM
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size

Definitions

  • the invention relates to the field of molecular sieves, in particular to a zinc-doped AlPO-36 molecular sieve single crystal and a preparation method thereof.
  • Aluminum phosphate molecular sieves (AlPO-n, n refers to different types) are a series of materials with different topological structures. Since the first artificial synthesis of molecular sieves in 1982, due to their diverse pore structures and catalytic sites, they have been used in catalysis, adsorption, and separation. And host-guest material preparation fields play an important role. In the aluminum phosphate molecular sieve family, the AlPO-36 molecular sieve crystal has a unique one-dimensional twelve-membered ring channel structure (along the c-axis), and its channel size is And has good thermal stability, is an ideal host material.
  • the object of the present invention is to provide a zinc-doped AlPO-36 molecular sieve single crystal and a preparation method thereof, aiming at solving the problem that the size of the AlPO-36 molecular sieve crystal prepared by the existing synthesis method is small, and There is a serious problem of twinning.
  • the preparation method of the zinc-doped AlPO-36 molecular sieve single crystal specifically includes the steps of:
  • the colloid E is subjected to a hydrothermal crystallization reaction to prepare the zinc-doped AlPO-36 molecular sieve single crystal.
  • the time for the first stirring is 6h-24h.
  • the adding method is dropwise.
  • the time for the second stirring is 1h-8h.
  • the adding method is dropwise.
  • the time for the third stirring is 1h-8h.
  • the temperature of the hydrothermal crystallization reaction is 150° C., and the time is 50 h.
  • a zinc-doped AlPO-36 molecular sieve single crystal prepared by the above-mentioned preparation method.
  • the size of the zinc-doped AlPO-36 molecular sieve single crystal is 150 ⁇ m ⁇ 30 ⁇ m.
  • the present invention provides a zinc-doped AlPO-36 molecular sieve single crystal and its preparation method.
  • tripropylamine is used as template agent
  • aluminum isopropoxide is used as aluminum source
  • zinc acetate dihydrate is used as zinc source
  • Phosphoric acid is used as the phosphorus source
  • deionized water is used as the solvent.
  • Fig. 1 is the powder X-ray diffraction result diagram of Example 1 of the present invention, wherein (a) is a standard card, and (b) is a zinc-doped AlPO-36 molecular sieve single crystal powder X-ray diffraction pattern.
  • Fig. 2 is a diagram showing the scanning electron microscope characterization results of the zinc-doped AlPO-36 molecular sieve single crystal in Example 2 of the present invention.
  • Fig. 3 is an optical microscope characterization result diagram of the zinc-doped AlPO-36 molecular sieve single crystal in Example 2 of the present invention.
  • Figure 4 is a comparison of the scanning electron microscope characterization results of the zinc-doped AlPO-36 molecular sieve single crystal in Example 2 of the present invention and other published AlPO-36 crystals, where a-e are scanning electron microscopes of other published AlPO-36 crystals Characterization result diagram, Fig. f is the scanning electron microscope characterization result diagram of zinc-doped AlPO-36 crystal.
  • the present invention provides a zinc-doped AlPO-36 molecular sieve single crystal and a preparation method thereof.
  • the present invention will be further described in detail below. It should be understood that the specific embodiments described here are only used to explain the present invention, not to limit the present invention.
  • the inventors found that in the existing methods for preparing AlPO-36 molecular sieve crystals, the synthesized products are basically nanoscale crystals with severe twinning. In particular, the twinning phenomenon exists in all reported AlPO-36 molecular sieves. It is worth noting that any change in conditions in the synthesis of molecular sieves will have a huge impact on the product, including the shape, size and phase of the product.
  • the embodiment of the present invention aims at the problem that in the existing preparation method of AlPO-36 molecular sieve crystals, the synthesized products are basically nanoscale crystals with serious twinning. By optimizing the ratio of reaction materials, zinc-doped large-sized AlPO-36 molecular sieve single crystal.
  • an embodiment of the present invention provides a method for preparing a zinc-doped AlPO-36 molecular sieve single crystal, wherein tripropylamine is used as a template, aluminum isopropoxide is used as an aluminum source, zinc acetate dihydrate is used as a zinc source, Phosphoric acid is used as a phosphorus source, and deionized water is used as a solvent; the tripropylamine, aluminum isopropoxide, zinc acetate dihydrate, phosphoric acid and deionized water are mixed uniformly, and a hydrothermal crystallization reaction is carried out to obtain the zinc-doped AlPO -36 molecular sieve single crystal;
  • tripropylamine is used as a template
  • aluminum isopropoxide is used as an aluminum source
  • zinc acetate dihydrate is used as a zinc source
  • phosphoric acid is used as a phosphorus source
  • deionized water is used as a solvent.
  • AlPO-36 molecular sieve single crystal when the added amount of zinc acetate dihydrate was 0, an AlPO-36 molecular sieve single crystal was prepared.
  • AlPO-36 molecular sieve single crystal has a unique one-dimensional twelve-membered ring channel structure (along the c-axis), and its channel size is With good thermal stability, it is an ideal host material.
  • a zinc-doped AlPO-36 molecular sieve single crystal is prepared.
  • the AlPO-36 crystal itself is electrically neutral, and its pore adsorption capacity is weak, and the doping of zinc element into the aluminum phosphate molecular sieve framework can bring about some new changes in physical and chemical properties. Therefore, in this example, the divalent Zn 2 + doped into the AlPO-36 crystal framework to replace Al 3+ to obtain a negatively charged framework, thereby enhancing its pore adsorption.
  • the preparation method of the zinc-doped AlPO-36 molecular sieve single crystal specifically includes the steps of:
  • step S1 in one embodiment, the time for the first stirring is 6h-24h.
  • step S3 in one embodiment, in the step of adding the solution B to the gel A, the adding method is dropwise, so that the solution B is better dispersed in the gel In A.
  • the time for the second stirring is 1h-8h.
  • step S5 in one embodiment, in the step of adding the solution D to the colloid C, the adding method is dropwise.
  • the time for the third stirring is 1h-8h.
  • step S6 in one embodiment, the temperature of the hydrothermal crystallization reaction is 150° C., and the time is 50 h.
  • the crystallization reaction conditions by further optimizing the crystallization reaction conditions, a zinc-doped AlPO-36 molecular sieve single crystal was prepared.
  • step S6 specifically includes:
  • the colloid E was subjected to a hydrothermal crystallization reaction, the reaction temperature was 150°C, and the reaction time was 50h;
  • the hydrothermal crystallization product is washed, filtered and dried in sequence under ultrasonic conditions to obtain a pure zinc-doped AlPO-36 molecular sieve single crystal.
  • the embodiment of the present invention carefully discusses the specific influence of the change of the reaction material ratio on the zinc-doped AlPO-36 molecular sieve crystal, and realizes the zinc-doped AlPO-36 molecular sieve by summarizing the rules, optimizing the reaction material ratio, and further optimizing the crystallization reaction conditions.
  • a 100-micron-scale twin-free zinc-doped AlPO-36 molecular sieve single crystal was synthesized for the first time.
  • the following findings were made:
  • AlPO-5 code name: AFI
  • miscellaneous crystal phase is easy to be produced in a system without Zn doping, and the AlPO-36 pure phase is obtained with the gradual increase of the zinc ratio, but if the ratio is too high, no crystal will be produced;
  • the crystal size increases with the extension of the crystallization time, but when the crystallization time reaches a certain critical point, the crystal size will not continue to grow.
  • the embodiment of the present invention also provides a zinc-doped AlPO-36 molecular sieve single crystal prepared by the above-mentioned preparation method.
  • the size of the zinc-doped AlPO-36 molecular sieve single crystal is 150 ⁇ m ⁇ 30 ⁇ m.
  • the largest twin-free zinc-doped AlPO-36 molecular sieve single crystal has been prepared so far, and the crystal surface is smooth.
  • Aluminum isopropoxide ( ⁇ 98%, Shanghai Aladdin Biochemical Technology Co., Ltd.), zinc acetate dihydrate (99%, Shanghai Aladdin Biochemical Technology Co., Ltd.), phosphoric acid ( ⁇ 85%, Shanghai Lingfeng Chemical Reagent Co., Ltd. company), tripropylamine (99%, Shanghai Aladdin Biochemical Technology Co., Ltd.), deionized water (prepared by Hetai Master-S15UV low-organic ultrapure water machine).
  • the prepared zinc-doped AlPO-36 molecular sieve single crystal was characterized by powder XRD.
  • (a) in the figure is a standard card
  • the AlPO-36 molecular sieve prepared in this example The diffraction peaks of the -36 molecular sieve single crystal are in good agreement with the standard card, and there are no other miscellaneous peaks, indicating that the zinc-doped AlPO-36 molecular sieve single crystal prepared in this example has high crystallinity and no other impurities.
  • the optimized zinc-doped AlPO-36 molecular sieve single crystal was characterized by scanning electron microscopy and optical microscopy, as shown in Figure 2 and Figure 3, respectively. It can be seen from Fig. 2 and Fig. 3 that the zinc-doped AlPO-36 molecular sieve single crystal prepared in this example is a large single crystal with a level of 100 microns, the crystal quality is high, and the twinning phenomenon is eliminated.
  • Fig. 4 is a scanning electron microscope comparison of the zinc-doped AlPO-36 molecular sieve single crystal (Fig. f) prepared in this example and other published AlPO-36 crystals (Fig. a-e). It can be clearly observed from this figure that compared with other published AlPO-36 crystals, the size and quality of the zinc-doped AlPO-36 molecular sieve single crystal prepared in this example have been greatly improved.
  • the present invention provides a zinc-doped AlPO-36 molecular sieve single crystal and its preparation method.
  • the present invention obtains a stable formula by optimizing the ratio of reaction materials. On the basis of obtaining a stable formula, further optimizes the crystal
  • the reaction conditions are optimized, thereby eliminating the twinning phenomenon of AlPO-36 molecular sieve crystals, and for the first time under fluorine-free conditions, the largest single crystal of AlPO-36 molecular sieve has been prepared so far.

Abstract

Disclosed are a zinc-doped AlPO-36 molecular sieve single crystal and a preparation method therefor. The method comprises: uniformly mixing tripropylamine, aluminum isopropoxide, zinc acetate dihydrate, phosphoric acid, and deionized water, and performing a hydrothermal crystallization reaction to obtain the zinc-doped AlPO-36 molecular sieve single crystal. The aluminum isopropoxide, zinc acetate dihydrate, phosphoric acid, tripropylamine, and deionized water are calculated on the basis of Al2O3, ZnO, P2 O5, TPA, H2O, respectively. In terms of molar ratio, Al2O3:ZnO:P2O5:TPA:H2O = 1.0:(0-0.6):1.0:(1.0-1.55):(128-296). In the present invention, by selecting the above-mentioned materials and optimizing the ratio of reaction materials to obtain a stable formula, a zinc-doped AlPO-36 molecular sieve single crystal having the largest size so far is prepared.

Description

一种锌掺杂AlPO-36分子筛单晶及其制备方法A kind of zinc-doped AlPO-36 molecular sieve single crystal and preparation method thereof 技术领域technical field
本发明涉及分子筛领域，尤其涉及一种锌掺杂AlPO-36分子筛单晶及其制备方法。The invention relates to the field of molecular sieves, in particular to a zinc-doped AlPO-36 molecular sieve single crystal and a preparation method thereof.
背景技术Background technique
磷酸铝分子筛(AlPO-n，n指代不同种类)是一系列具有不同拓扑结构的材料，自1982年首次人工合成分子筛以来，因其多样的孔道结构和催化位点，在催化、吸附、分离和主客体材料制备领域发挥着重要作用。在磷酸铝分子筛家族中，AlPO-36分子筛晶体具有独特的一维十二元环孔道结构(沿c轴)，其孔道尺寸为
Figure PCTCN2021107961-appb-000001
并且具有良好的热稳定性，是一种理想的主体材料。迄今为止，已经有许多利用水热法合成MeAlPO-36晶体(Me＝Mg，Fe，Ti)的研究被报道，但产物大多数为纳米级别的小尺寸晶体、并且有着严重的孪晶现象。此外，在AlPO-36晶体的合成中经常出现AlPO-5晶体共生相，这极大地限制了AlPO-36分子筛晶体的应用。 Aluminum phosphate molecular sieves (AlPO-n, n refers to different types) are a series of materials with different topological structures. Since the first artificial synthesis of molecular sieves in 1982, due to their diverse pore structures and catalytic sites, they have been used in catalysis, adsorption, and separation. And host-guest material preparation fields play an important role. In the aluminum phosphate molecular sieve family, the AlPO-36 molecular sieve crystal has a unique one-dimensional twelve-membered ring channel structure (along the c-axis), and its channel size is
Figure PCTCN2021107961-appb-000001
And has good thermal stability, is an ideal host material. So far, there have been many reports on the synthesis of MeAlPO-36 crystals (Me=Mg, Fe, Ti) by hydrothermal method, but most of the products are nano-scale small-sized crystals and have serious twinning phenomenon. In addition, AlPO-5 crystal intergrowth often occurs in the synthesis of AlPO-36 crystals, which greatly limits the application of AlPO-36 molecular sieve crystals.
因此，现有技术还有待于改进和发展。Therefore, the prior art still needs to be improved and developed.
发明内容Contents of the invention
鉴于上述现有技术的不足，本发明的目的在于提供一种锌掺杂AlPO-36分子筛单晶及其制备方法，旨在解决现有合成方法制备得到的AlPO-36分子筛晶体的尺寸小、并且存在严重的孪晶现象的问题。In view of the above-mentioned deficiencies in the prior art, the object of the present invention is to provide a zinc-doped AlPO-36 molecular sieve single crystal and a preparation method thereof, aiming at solving the problem that the size of the AlPO-36 molecular sieve crystal prepared by the existing synthesis method is small, and There is a serious problem of twinning.
本发明的技术方案如下：Technical scheme of the present invention is as follows:
一种锌掺杂AlPO-36分子筛单晶的制备方法，其中，以三丙胺作为模板剂，以异丙醇铝作为铝源、乙酸锌二水合物作为锌源、磷酸作为磷源、去离子水作为溶剂；将所述三丙胺、异丙醇铝、乙酸锌二水合物、磷酸和去离子混合均匀，进行水热晶化反应，得到所述锌掺杂AlPO-36分子筛单晶；所述异丙醇铝、乙酸锌二水合物、磷酸、三丙胺、去离子水分别以Al 2O 3、ZnO、P 2O 5、TPA、H 2O计；按摩尔比计，Al 2O 3：ZnO：P 2O 5： TPA：H 2O＝1.0：(0～0.6)：1.0：(1.0～1.55)：(128～296)。 A method for preparing a zinc-doped AlPO-36 molecular sieve single crystal, wherein, using tripropylamine as a template, aluminum isopropoxide as an aluminum source, zinc acetate dihydrate as a zinc source, phosphoric acid as a phosphorus source, deionized water As a solvent; the tripropylamine, aluminum isopropoxide, zinc acetate dihydrate, phosphoric acid and deionized are mixed evenly, and the hydrothermal crystallization reaction is carried out to obtain the zinc-doped AlPO-36 molecular sieve single crystal; the isopropanol Aluminum propoxide, zinc acetate dihydrate, phosphoric acid, tripropylamine, and deionized water are calculated in terms of Al 2 O 3 , ZnO, P 2 O 5 , TPA, and H 2 O, respectively; in terms of molar ratio, Al 2 O 3 : ZnO : P 2 O 5 : TPA: H 2 O = 1.0: (0-0.6): 1.0: (1.0-1.55): (128-296).
可选地，所述锌掺杂AlPO-36分子筛单晶的制备方法，具体包括步骤：Optionally, the preparation method of the zinc-doped AlPO-36 molecular sieve single crystal specifically includes the steps of:
将异丙醇铝、乙酸锌二水合物、去离子水混合，进行第一次搅拌，得到凝胶A；Mix aluminum isopropoxide, zinc acetate dihydrate, and deionized water, and stir for the first time to obtain gel A;
将磷酸加入到去离子水中进行稀释，得到溶液B；adding phosphoric acid to deionized water for dilution to obtain solution B;
将所述溶液B加入到所述凝胶A中，进行第二次搅拌，得到胶体C；Adding the solution B to the gel A and stirring for the second time to obtain the colloid C;
将三丙胺加入到去离子水中进行稀释，得到溶液D；adding tripropylamine to deionized water for dilution to obtain solution D;
将所述溶液D加入到所述胶体C中，进行第三次搅拌，得到胶体E；Adding the solution D to the colloid C and stirring for the third time to obtain the colloid E;
将所述胶体E进行水热晶化反应，制备得到所述锌掺杂AlPO-36分子筛单晶。The colloid E is subjected to a hydrothermal crystallization reaction to prepare the zinc-doped AlPO-36 molecular sieve single crystal.
可选地，所述第一次搅拌的时间为6h-24h。Optionally, the time for the first stirring is 6h-24h.
可选地，所述将所述溶液B加入到所述凝胶A中的步骤中，所述加入的方式为逐滴加入。Optionally, in the step of adding the solution B to the gel A, the adding method is dropwise.
可选地，所述第二次搅拌的时间为1h-8h。Optionally, the time for the second stirring is 1h-8h.
可选地，所述将所述溶液D加入到所述胶体C中的步骤中，所述加入的方式为逐滴加入。Optionally, in the step of adding the solution D to the colloid C, the adding method is dropwise.
可选地，所述第三次搅拌的时间为1h-8h。Optionally, the time for the third stirring is 1h-8h.
可选地，所述水热晶化反应的温度为150℃，时间为50h。Optionally, the temperature of the hydrothermal crystallization reaction is 150° C., and the time is 50 h.
一种利用如上所述的制备方法制备得到的锌掺杂AlPO-36分子筛单晶。A zinc-doped AlPO-36 molecular sieve single crystal prepared by the above-mentioned preparation method.
可选地，所述锌掺杂AlPO-36分子筛单晶的尺寸为150μm×30μm。Optionally, the size of the zinc-doped AlPO-36 molecular sieve single crystal is 150 μm×30 μm.
有益效果：本发明提供了一种锌掺杂AlPO-36分子筛单晶及其制备方法，本发明以三丙胺作为模板剂，以异丙醇铝作为铝源、乙酸锌二水合物作为锌源、磷酸作为磷源、去离子水作为溶剂，通过优化反应物料比例，消除了AlPO-36分子筛晶体的孪晶现象，且首次在无氟条件下，制备出迄今为止尺寸最大的AlPO-36分子筛单晶。Beneficial effects: the present invention provides a zinc-doped AlPO-36 molecular sieve single crystal and its preparation method. In the present invention, tripropylamine is used as template agent, aluminum isopropoxide is used as aluminum source, zinc acetate dihydrate is used as zinc source, Phosphoric acid is used as the phosphorus source and deionized water is used as the solvent. By optimizing the ratio of reaction materials, the twinning phenomenon of AlPO-36 molecular sieve crystals is eliminated, and the largest single crystal of AlPO-36 molecular sieve is prepared for the first time under fluorine-free conditions. .
附图说明Description of drawings
图1为本发明实施例1的粉末X射线衍射结果图，其中(a)为标准卡片，(b)为锌掺杂AlPO-36分子筛单晶粉末X射线衍射图谱。Fig. 1 is the powder X-ray diffraction result diagram of Example 1 of the present invention, wherein (a) is a standard card, and (b) is a zinc-doped AlPO-36 molecular sieve single crystal powder X-ray diffraction pattern.
图2为本发明实施例2的锌掺杂AlPO-36分子筛单晶的扫描电子显微镜表征结果图。Fig. 2 is a diagram showing the scanning electron microscope characterization results of the zinc-doped AlPO-36 molecular sieve single crystal in Example 2 of the present invention.
图3为本发明实施例2的锌掺杂AlPO-36分子筛单晶的光学显微镜表征结果图。Fig. 3 is an optical microscope characterization result diagram of the zinc-doped AlPO-36 molecular sieve single crystal in Example 2 of the present invention.
图4为本发明实施例2的锌掺杂AlPO-36分子筛单晶与其他已发表的AlPO-36晶体扫描电子显微镜表征结果对比图，其中a-e为其他已发表的AlPO-36晶体的扫描电子显微镜表征结果图，图f为锌掺杂AlPO-36晶体的扫描电子显微镜表征结果图。Figure 4 is a comparison of the scanning electron microscope characterization results of the zinc-doped AlPO-36 molecular sieve single crystal in Example 2 of the present invention and other published AlPO-36 crystals, where a-e are scanning electron microscopes of other published AlPO-36 crystals Characterization result diagram, Fig. f is the scanning electron microscope characterization result diagram of zinc-doped AlPO-36 crystal.
具体实施方式Detailed ways
本发明提供一种锌掺杂AlPO-36分子筛单晶及其制备方法，为使本发明的目的、技术方案及效果更加清楚、明确，以下对本发明进一步详细说明。应当理解，此处所描述的具体实施例仅仅用以解释本发明，并不用于限定本发明。The present invention provides a zinc-doped AlPO-36 molecular sieve single crystal and a preparation method thereof. In order to make the purpose, technical scheme and effect of the present invention clearer and clearer, the present invention will be further described in detail below. It should be understood that the specific embodiments described here are only used to explain the present invention, not to limit the present invention.
发明人发现，在现有的AlPO-36分子筛晶体的制备方法中，所合成的产物基本都为纳米级别的晶体，且孪晶严重。尤其是孪晶现象，在所有已报道的AlPO-36分子筛中全部存在。值得注意的是，在分子筛合成中任何条件的变化都会对产物有着巨大的影响，包括产物的形貌、尺寸和物相等。The inventors found that in the existing methods for preparing AlPO-36 molecular sieve crystals, the synthesized products are basically nanoscale crystals with severe twinning. In particular, the twinning phenomenon exists in all reported AlPO-36 molecular sieves. It is worth noting that any change in conditions in the synthesis of molecular sieves will have a huge impact on the product, including the shape, size and phase of the product.
本发明实施例针对现有AlPO-36分子筛晶体的制备方法中，所合成的产物基本都为纳米级别的晶体且孪晶严重这一问题，通过优化反应物料比例，制备出锌掺杂的大尺寸AlPO-36分子筛单晶。The embodiment of the present invention aims at the problem that in the existing preparation method of AlPO-36 molecular sieve crystals, the synthesized products are basically nanoscale crystals with serious twinning. By optimizing the ratio of reaction materials, zinc-doped large-sized AlPO-36 molecular sieve single crystal.
基于此，本发明实施例提供一种锌掺杂AlPO-36分子筛单晶的制备方法，其中，以三丙胺作为模板剂，以异丙醇铝作为铝源、乙酸锌二水合物作为锌源、磷酸作为磷源、去离子水作为溶剂；将所述三丙胺、异丙醇铝、乙酸锌二水合物、磷酸和去离子水混合均匀，进行水热晶化反应，得到所述锌掺杂AlPO-36分子筛单晶；Based on this, an embodiment of the present invention provides a method for preparing a zinc-doped AlPO-36 molecular sieve single crystal, wherein tripropylamine is used as a template, aluminum isopropoxide is used as an aluminum source, zinc acetate dihydrate is used as a zinc source, Phosphoric acid is used as a phosphorus source, and deionized water is used as a solvent; the tripropylamine, aluminum isopropoxide, zinc acetate dihydrate, phosphoric acid and deionized water are mixed uniformly, and a hydrothermal crystallization reaction is carried out to obtain the zinc-doped AlPO -36 molecular sieve single crystal;
所述异丙醇铝、乙酸锌二水合物、磷酸、三丙胺、去离子水分别以Al 2O 3、ZnO、P 2O 5、TPA、H 2O计；按摩尔比计，Al 2O 3：ZnO：P 2O 5：TPA：H 2O＝1.0：(0～0.6)：1.0：(1.0～1.55)：(128～296)。 The aluminum isopropoxide, zinc acetate dihydrate, phosphoric acid, tripropylamine, and deionized water are calculated in terms of Al 2 O 3 , ZnO, P 2 O 5 , TPA, and H 2 O respectively; in terms of molar ratio, Al 2 O 3 : ZnO: P 2 O 5 : TPA: H 2 O = 1.0: (0-0.6): 1.0: (1.0-1.55): (128-296).
本实施例中，以三丙胺作为模板剂，以异丙醇铝作为铝源、乙酸锌二水合物作为锌源、磷酸作为磷源、去离子水作为溶剂，通过优化反应物料比例，获得稳定的配方。采 用上述配方，消除了AlPO-36分子筛晶体的孪晶现象，且首次在无氟条件下，制备出迄今为止尺寸最大的AlPO-36分子筛单晶。In this example, tripropylamine is used as a template, aluminum isopropoxide is used as an aluminum source, zinc acetate dihydrate is used as a zinc source, phosphoric acid is used as a phosphorus source, and deionized water is used as a solvent. By optimizing the ratio of reaction materials, a stable formula. Using the above formula, the twinning phenomenon of AlPO-36 molecular sieve crystals is eliminated, and for the first time under fluorine-free conditions, the largest single crystal of AlPO-36 molecular sieve has been prepared so far.
本实施例中，当乙酸锌二水合物的加入量为0时，制备得到AlPO-36分子筛单晶。AlPO-36分子筛单晶具有独特的一维十二元环孔道结构(沿c轴)，其孔道尺寸为
Figure PCTCN2021107961-appb-000002
Figure PCTCN2021107961-appb-000003
具有良好的热稳定性，是一种理想的主体材料。 In this example, when the added amount of zinc acetate dihydrate was 0, an AlPO-36 molecular sieve single crystal was prepared. AlPO-36 molecular sieve single crystal has a unique one-dimensional twelve-membered ring channel structure (along the c-axis), and its channel size is
Figure PCTCN2021107961-appb-000002
Figure PCTCN2021107961-appb-000003
With good thermal stability, it is an ideal host material.
本实施例中，当乙酸锌二水合物的加入量不为0时，制备得到锌掺杂AlPO-36分子筛单晶。AlPO-36晶体本身是电中性的，其孔道吸附能力较弱，而锌元素掺杂进磷酸铝分子筛骨架中可以带来一些新的物理化学性质变化，因此本实施例将二价的Zn 2+掺杂进AlPO-36晶体骨架中取代Al 3+，以获得带负电荷的骨架，从而增强其孔道吸附力。 In this example, when the added amount of zinc acetate dihydrate is not 0, a zinc-doped AlPO-36 molecular sieve single crystal is prepared. The AlPO-36 crystal itself is electrically neutral, and its pore adsorption capacity is weak, and the doping of zinc element into the aluminum phosphate molecular sieve framework can bring about some new changes in physical and chemical properties. Therefore, in this example, the divalent Zn 2 + doped into the AlPO-36 crystal framework to replace Al 3+ to obtain a negatively charged framework, thereby enhancing its pore adsorption.
在一种实施方式中，所述锌掺杂AlPO-36分子筛单晶的制备方法，具体包括步骤：In one embodiment, the preparation method of the zinc-doped AlPO-36 molecular sieve single crystal specifically includes the steps of:
S1、将异丙醇铝、乙酸锌二水合物、去离子水混合，进行第一次搅拌，得到凝胶A；S1. Mix aluminum isopropoxide, zinc acetate dihydrate, and deionized water, and stir for the first time to obtain gel A;
S2、将磷酸加入到去离子水中进行稀释，得到溶液B；S2, adding phosphoric acid to deionized water for dilution to obtain solution B;
S3、将所述溶液B加入到所述凝胶A中，进行第二次搅拌，得到胶体C；S3, adding the solution B into the gel A, and stirring for the second time to obtain a colloid C;
S4、将三丙胺加入到去离子水中进行稀释，得到溶液D；S4, adding tripropylamine to deionized water for dilution to obtain solution D;
S5、将所述溶液D加入到所述胶体C中，进行第三次搅拌，得到胶体E；S5, adding the solution D into the colloid C, and stirring for the third time to obtain the colloid E;
S6、将所述胶体E进行水热晶化反应，制备得到所述锌掺杂AlPO-36分子筛单晶。S6, subjecting the colloid E to a hydrothermal crystallization reaction to prepare the zinc-doped AlPO-36 molecular sieve single crystal.
步骤S1中，在一种实施方式中，所述第一次搅拌的时间为6h-24h。In step S1, in one embodiment, the time for the first stirring is 6h-24h.
步骤S3中，在一种实施方式中，所述将所述溶液B加入到所述凝胶A中的步骤中，所述加入的方式为逐滴加入，使溶液B更好地分散于凝胶A中。In step S3, in one embodiment, in the step of adding the solution B to the gel A, the adding method is dropwise, so that the solution B is better dispersed in the gel In A.
在一种实施方式中，所述第二次搅拌的时间为1h-8h。In one embodiment, the time for the second stirring is 1h-8h.
步骤S5中，在一种实施方式中，所述将所述溶液D加入到所述胶体C中的步骤中，所述加入的方式为逐滴加入。In step S5, in one embodiment, in the step of adding the solution D to the colloid C, the adding method is dropwise.
在一种实施方式中，所述第三次搅拌的时间为1h-8h。In one embodiment, the time for the third stirring is 1h-8h.
步骤S6中，在一种实施方式中，所述水热晶化反应的温度为150℃，时间为50h。本实施例中，通过进一步优化晶化反应条件，制备得到锌掺杂AlPO-36分子筛单晶。In step S6, in one embodiment, the temperature of the hydrothermal crystallization reaction is 150° C., and the time is 50 h. In this example, by further optimizing the crystallization reaction conditions, a zinc-doped AlPO-36 molecular sieve single crystal was prepared.
在一种实施方式中，步骤S6具体包括：In one embodiment, step S6 specifically includes:
将所述胶体E进行水热晶化反应，反应温度为150℃，反应时间为50h；The colloid E was subjected to a hydrothermal crystallization reaction, the reaction temperature was 150°C, and the reaction time was 50h;
反应结束后，将水热晶化产物在超声条件下依次进行洗涤、过滤、干燥，得到纯净的锌掺杂AlPO-36分子筛单晶。After the reaction, the hydrothermal crystallization product is washed, filtered and dried in sequence under ultrasonic conditions to obtain a pure zinc-doped AlPO-36 molecular sieve single crystal.
本发明实施例仔细探讨了反应物料比例的变化对于锌掺杂AlPO-36分子筛晶体的具体影响，并通过总结规律、优化反应物料比例、进一步优化晶化反应条件实现了锌掺杂AlPO-36分子筛大单晶的制备，首次合成了百微米级别无孪晶的锌掺杂AlPO-36分子筛单晶。在调节初始凝胶比例的过程中，有如下发现：The embodiment of the present invention carefully discusses the specific influence of the change of the reaction material ratio on the zinc-doped AlPO-36 molecular sieve crystal, and realizes the zinc-doped AlPO-36 molecular sieve by summarizing the rules, optimizing the reaction material ratio, and further optimizing the crystallization reaction conditions. For the preparation of large single crystals, a 100-micron-scale twin-free zinc-doped AlPO-36 molecular sieve single crystal was synthesized for the first time. During the adjustment of the initial gel ratio, the following findings were made:
1、在无Zn掺杂的体系中容易产生AlPO-5(代号:AFI)杂晶相，随着锌比例逐渐上升得到AlPO-36纯相，但比例过高会导致无晶体产生；1. AlPO-5 (code name: AFI) miscellaneous crystal phase is easy to be produced in a system without Zn doping, and the AlPO-36 pure phase is obtained with the gradual increase of the zinc ratio, but if the ratio is too high, no crystal will be produced;
2、晶体质量随着三丙胺模板剂含量的增多呈现先上升后下降的趋势，当存在过多的三丙胺时，孪晶现象会加剧；2. As the content of tripropylamine template increases, the crystal quality shows a trend of first increasing and then decreasing. When there is too much tripropylamine, the twinning phenomenon will be intensified;
3、晶体尺寸随着水含量的增加呈现先增大后减小的趋势，当体系中存在过多的水时将无法得到AlPO-36晶体；3. The crystal size increases first and then decreases with the increase of water content. When there is too much water in the system, AlPO-36 crystals cannot be obtained;
4、晶化温度过低时无法得到AlPO-36晶体，但过高的晶化温度将带来AlPO-5(代号:AFI)杂晶相。处于可以成核AlPO-36晶体的临界温度时，产物的孪晶现象将得到有效抑制甚至消失；4. When the crystallization temperature is too low, AlPO-36 crystals cannot be obtained, but if the crystallization temperature is too high, it will bring AlPO-5 (code: AFI) heterocrystalline phase. At the critical temperature that can nucleate AlPO-36 crystals, the twinning phenomenon of the product will be effectively suppressed or even disappear;
5、晶体尺寸随着晶化时间的延长而增大，但当晶化时间到某一临界点时，晶体尺寸将不会继续增长。5. The crystal size increases with the extension of the crystallization time, but when the crystallization time reaches a certain critical point, the crystal size will not continue to grow.
本发明实施例还提供一种利用如上所述的制备方法制备得到的锌掺杂AlPO-36分子筛单晶。The embodiment of the present invention also provides a zinc-doped AlPO-36 molecular sieve single crystal prepared by the above-mentioned preparation method.
在一种实施方式中，所述锌掺杂AlPO-36分子筛单晶的尺寸为150μm×30μm。In one embodiment, the size of the zinc-doped AlPO-36 molecular sieve single crystal is 150 μm×30 μm.
本发明实施例制备得到了迄今为止尺寸最大的无孪晶的锌掺杂AlPO-36分子筛单晶，且晶体表面光滑。In the embodiment of the present invention, the largest twin-free zinc-doped AlPO-36 molecular sieve single crystal has been prepared so far, and the crystal surface is smooth.
下面对本发明实施例反应物料的来源作举例说明：The source of the reaction material of the embodiment of the present invention is illustrated below:
异丙醇铝(≥98％，上海阿拉丁生化科技股份有限公司)，乙酸锌二水合物(99％，上海阿拉丁生化科技股份有限公司)，磷酸(≥85％，上海凌峰化学试剂有限公司)，三丙胺 (99％，上海阿拉丁生化科技股份有限公司)，去离子水(由和泰Master-S15UV低有机物型超纯水机制备)。Aluminum isopropoxide (≥98%, Shanghai Aladdin Biochemical Technology Co., Ltd.), zinc acetate dihydrate (99%, Shanghai Aladdin Biochemical Technology Co., Ltd.), phosphoric acid (≥85%, Shanghai Lingfeng Chemical Reagent Co., Ltd. company), tripropylamine (99%, Shanghai Aladdin Biochemical Technology Co., Ltd.), deionized water (prepared by Hetai Master-S15UV low-organic ultrapure water machine).
下面通过具体的实施例对本发明作进一步地说明。The present invention will be further described below by specific examples.
实施例1Example 1
通过优化凝胶组分和晶化条件，对制备出的锌掺杂AlPO-36分子筛单晶进行粉末XRD表征。如图1所示，图中(a)为标准卡片，(b)为本实施例制备出的锌掺杂AlPO-36分子筛单晶，由此图可以看出，本实施例所制备出的AlPO-36分子筛单晶的衍射峰与标准卡片吻合度高，无其他杂峰存在，说明本实施例所制备出的锌掺杂AlPO-36分子筛单晶结晶度高，无其他杂质。By optimizing the gel composition and crystallization conditions, the prepared zinc-doped AlPO-36 molecular sieve single crystal was characterized by powder XRD. As shown in Figure 1, (a) in the figure is a standard card, and (b) is the zinc-doped AlPO-36 molecular sieve single crystal prepared in this example. As can be seen from this figure, the AlPO-36 molecular sieve prepared in this example The diffraction peaks of the -36 molecular sieve single crystal are in good agreement with the standard card, and there are no other miscellaneous peaks, indicating that the zinc-doped AlPO-36 molecular sieve single crystal prepared in this example has high crystallinity and no other impurities.
实施例2Example 2
对优化后制备出的锌掺杂AlPO-36分子筛单晶进行扫描电子显微镜和光学显微镜表征，分别如图2、图3所示。由图2、图3可以看出，本实施例所制备出的锌掺杂AlPO-36分子筛单晶为百微米级别的大单晶，晶体质量高，消除了孪晶现象。The optimized zinc-doped AlPO-36 molecular sieve single crystal was characterized by scanning electron microscopy and optical microscopy, as shown in Figure 2 and Figure 3, respectively. It can be seen from Fig. 2 and Fig. 3 that the zinc-doped AlPO-36 molecular sieve single crystal prepared in this example is a large single crystal with a level of 100 microns, the crystal quality is high, and the twinning phenomenon is eliminated.
图4为本实施例所制备出的锌掺杂AlPO-36分子筛单晶(图f)与其他已发表的AlPO-36晶体(图a-e)扫描电子显微镜对比图。通过此图可以清楚地观察到，相较于其他已发表的AlPO-36晶体，本实施例所制备的锌掺杂AlPO-36分子筛单晶的尺寸和质量都有了巨大提升。Fig. 4 is a scanning electron microscope comparison of the zinc-doped AlPO-36 molecular sieve single crystal (Fig. f) prepared in this example and other published AlPO-36 crystals (Fig. a-e). It can be clearly observed from this figure that compared with other published AlPO-36 crystals, the size and quality of the zinc-doped AlPO-36 molecular sieve single crystal prepared in this example have been greatly improved.
综上所述，本发明提供了一种锌掺杂AlPO-36分子筛单晶及其制备方法，本发明通过优化反应物料比例获得稳定的配方，在获得了稳定配方的基础上，再进一步优化晶化反应条件，从而消除了AlPO-36分子筛晶体的孪晶现象，且首次在无氟条件下，制备出迄今为止尺寸最大的AlPO-36分子筛单晶。In summary, the present invention provides a zinc-doped AlPO-36 molecular sieve single crystal and its preparation method. The present invention obtains a stable formula by optimizing the ratio of reaction materials. On the basis of obtaining a stable formula, further optimizes the crystal The reaction conditions are optimized, thereby eliminating the twinning phenomenon of AlPO-36 molecular sieve crystals, and for the first time under fluorine-free conditions, the largest single crystal of AlPO-36 molecular sieve has been prepared so far.
应当理解的是，本发明的应用不限于上述的举例，对本领域普通技术人员来说，可以根据上述说明加以改进或变换，所有这些改进和变换都应属于本发明所附权利要求的保护范围。It should be understood that the application of the present invention is not limited to the above examples, and those skilled in the art can make improvements or transformations according to the above descriptions, and all these improvements and transformations should belong to the protection scope of the appended claims of the present invention.

Claims (10)

  1. 一种锌掺杂AlPO-36分子筛单晶的制备方法，其特征在于，以三丙胺作为模板剂，以异丙醇铝作为铝源、乙酸锌二水合物作为锌源、磷酸作为磷源、去离子水作为溶剂；将所述三丙胺、异丙醇铝、乙酸锌二水合物、磷酸和去离子混合均匀，进行水热晶化反应，得到所述锌掺杂AlPO-36分子筛单晶；A kind of preparation method of zinc-doped AlPO-36 molecular sieve single crystal, it is characterized in that, with tripropylamine as template agent, with aluminum isopropoxide as aluminum source, zinc acetate dihydrate as zinc source, phosphoric acid as phosphorus source, remove Ionized water is used as a solvent; the tripropylamine, aluminum isopropoxide, zinc acetate dihydrate, phosphoric acid and deionized are mixed evenly, and a hydrothermal crystallization reaction is carried out to obtain the zinc-doped AlPO-36 molecular sieve single crystal;
    所述异丙醇铝、乙酸锌二水合物、磷酸、三丙胺、去离子水分别以Al 2O 3、ZnO、P 2O 5、TPA、H 2O计；按摩尔比计，Al 2O 3：ZnO：P 2O 5：TPA：H 2O＝1.0：(0～0.6)：1.0：(1.0～1.55)：(128～296)。 The aluminum isopropoxide, zinc acetate dihydrate, phosphoric acid, tripropylamine, and deionized water are calculated in terms of Al 2 O 3 , ZnO, P 2 O 5 , TPA, and H 2 O respectively; in terms of molar ratio, Al 2 O 3 : ZnO: P 2 O 5 : TPA: H 2 O = 1.0: (0-0.6): 1.0: (1.0-1.55): (128-296).
  2. 根据权利要求1所述的锌掺杂AlPO-36分子筛单晶的制备方法，其特征在于，所述制备方法具体包括步骤：The preparation method of zinc-doped AlPO-36 molecular sieve single crystal according to claim 1, is characterized in that, described preparation method specifically comprises the step:
    将异丙醇铝、乙酸锌二水合物、去离子水混合，进行第一次搅拌，得到凝胶A；Mix aluminum isopropoxide, zinc acetate dihydrate, and deionized water, and stir for the first time to obtain gel A;
    将磷酸加入到去离子水中进行稀释，得到溶液B；adding phosphoric acid to deionized water for dilution to obtain solution B;
    将所述溶液B加入到所述凝胶A中，进行第二次搅拌，得到胶体C；Adding the solution B to the gel A and stirring for the second time to obtain the colloid C;
    将三丙胺加入到去离子水中进行稀释，得到溶液D；adding tripropylamine to deionized water for dilution to obtain solution D;
    将所述溶液D加入到所述胶体C中，进行第三次搅拌，得到胶体E；Adding the solution D to the colloid C and stirring for the third time to obtain the colloid E;
    将所述胶体E进行水热晶化反应，制备得到所述锌掺杂AlPO-36分子筛单晶。The colloid E is subjected to a hydrothermal crystallization reaction to prepare the zinc-doped AlPO-36 molecular sieve single crystal.
  3. 根据权利要求2所述的锌掺杂AlPO-36分子筛单晶的制备方法，其特征在于，所述第一次搅拌的时间为6h-24h。The method for preparing zinc-doped AlPO-36 molecular sieve single crystal according to claim 2, characterized in that the time for the first stirring is 6h-24h.
  4. 根据权利要求2所述的锌掺杂AlPO-36分子筛单晶的制备方法，其特征在于，所述将所述溶液B加入到所述凝胶A中的步骤中，所述加入的方式为逐滴加入。The preparation method of zinc-doped AlPO-36 molecular sieve single crystal according to claim 2, characterized in that, in the step of adding the solution B to the gel A, the adding method is gradually Add dropwise.
  5. 根据权利要求2所述的锌掺杂AlPO-36分子筛单晶的制备方法，其特征在于，所述第二次搅拌的时间为1h-8h。The method for preparing zinc-doped AlPO-36 molecular sieve single crystal according to claim 2, characterized in that, the time for the second stirring is 1h-8h.
  6. 根据权利要求2所述的锌掺杂AlPO-36分子筛单晶的制备方法，其特征在于，所述将所述溶液D加入到所述胶体C中的步骤中，所述加入的方式为逐滴加入。The preparation method of zinc-doped AlPO-36 molecular sieve single crystal according to claim 2, characterized in that, in the step of adding the solution D to the colloid C, the adding method is dropwise join in.
  7. 根据权利要求2所述的锌掺杂AlPO-36分子筛单晶的制备方法，其特征在于，所述第三次搅拌的时间为1h-8h。The method for preparing zinc-doped AlPO-36 molecular sieve single crystal according to claim 2, characterized in that the time for the third stirring is 1h-8h.
  8. 根据权利要求2所述的锌掺杂AlPO-36分子筛单晶的制备方法，其特征在于， 所述水热晶化反应的温度为150℃，时间为50h。The method for preparing zinc-doped AlPO-36 molecular sieve single crystal according to claim 2, characterized in that, the temperature of the hydrothermal crystallization reaction is 150° C., and the time is 50 h.
  9. 一种利用权利要求1-8任一项所述的制备方法制备得到的锌掺杂AlPO-36分子筛单晶。A zinc-doped AlPO-36 molecular sieve single crystal prepared by the preparation method described in any one of claims 1-8.
  10. 根据权利要求9所述的锌掺杂AlPO-36分子筛单晶，其特征在于，所述锌掺杂AlPO-36分子筛单晶的尺寸为150μm×30μm。The zinc-doped AlPO-36 molecular sieve single crystal according to claim 9, characterized in that the size of the zinc-doped AlPO-36 molecular sieve single crystal is 150 μm×30 μm.
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