WO2018023365A1 - 纳米sapo-34分子筛的合成方法、sapo-34分子筛催化剂及其应用 - Google Patents

纳米sapo-34分子筛的合成方法、sapo-34分子筛催化剂及其应用 Download PDF

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WO2018023365A1
WO2018023365A1 PCT/CN2016/092827 CN2016092827W WO2018023365A1 WO 2018023365 A1 WO2018023365 A1 WO 2018023365A1 CN 2016092827 W CN2016092827 W CN 2016092827W WO 2018023365 A1 WO2018023365 A1 WO 2018023365A1
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sapo
molecular sieve
nano
group
source
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PCT/CN2016/092827
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French (fr)
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吴鹏飞
杨淼
田鹏
刘中民
王林英
刘琳
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中国科学院大连化学物理研究所
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Priority to EA201990146A priority Critical patent/EA038042B1/ru
Priority to AU2016417175A priority patent/AU2016417175B2/en
Priority to EP16910963.4A priority patent/EP3495320B1/en
Priority to US16/321,118 priority patent/US10822244B2/en
Priority to PCT/CN2016/092827 priority patent/WO2018023365A1/zh
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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
    • C01B37/00—Compounds having molecular sieve properties but not having base-exchange properties
    • C01B37/06—Aluminophosphates containing other elements, e.g. metals, boron
    • C01B37/08—Silicoaluminophosphates [SAPO compounds], e.g. CoSAPO
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/82—Phosphates
    • B01J29/84—Aluminophosphates containing other elements, e.g. metals, boron
    • B01J29/85—Silicoaluminophosphates [SAPO compounds]
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
    • B01J37/0018—Addition of a binding agent or of material, later completely removed among others as result of heat treatment, leaching or washing,(e.g. forming of pores; protective layer, desintegrating by heat)
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/08—Heat treatment
    • 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
    • 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
    • C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer

Definitions

  • This invention relates to the field of molecular sieves, and more particularly to the synthesis of SAPO-34 molecular sieves, SAPO-34 molecular sieve catalysts and their use.
  • the silicoaluminophosphate molecular sieve (SAPO-n) has various skeleton structures, and its three-dimensional skeleton structure is composed of PO 2 + , AlO 2 - and SiO 2 tetrahedra.
  • the Si atom is isomorphously substituted for a part of the P atom in the neutral aluminum phosphate skeleton structure or simultaneously substituted with the P and Al atoms, so that the skeleton generates a net negative charge, causing the proton to be acidic, thereby imparting acidity to the SAPO molecular sieve.
  • SAPO-34 molecular sieve with CHA topology has been successfully applied to the MTO commercialization process due to its excellent catalytic performance in methanol to olefins reaction (MTO).
  • MTO methanol to olefins reaction
  • the intrinsic microporous structure of SAPO-34 limits the mass transfer efficiency, resulting in low utilization of SAPO-34 catalyst active sites, and is prone to pore blockage and carbon deposition inactivation.
  • attempts have been made to synthesize SAPO-34 molecular sieves with a meso-microporous composite structure, by introducing mesoporous or macroporous channels between intrinsic microporous structures, or by preparing small crystallites of nanoscale molecular sieves.
  • the mass transfer resistance in the small reaction enhances the diffusion performance of the molecule during the reaction, and enhances the reaction life of the catalytic reaction and the selectivity of the lower olefin.
  • Triethylamine is a cheap and readily available structure-directing agent or templating agent for the synthesis of SAPO-34 molecular sieves.
  • the synthesized product is often SAPO-34 containing a small amount of SAPO-18. /-18 (CHA/AEI) eutectic.
  • SAPO-18 or AlPO-18 is even obtained when the silicon content in the synthetic gel is extremely low or silicon-free.
  • the present invention provides a method for synthesizing a nano-SAPO-34 molecular sieve, characterized in that the nano-SAPO-34 molecular sieve is hydrothermally synthesized in the presence of a functionalized organosilane,
  • the functional organosilane has the structure shown in formula I:
  • R & lt one is C1 ⁇ 10 alkyl;
  • R 2 is a C1 ⁇ 6 alkyl group;
  • R 3 is diethylamino, triethylamino, piperazinyl, pyridyl, or it Lolinyl;
  • x is an integer from 0 to 2
  • y is an integer from 1 to 3
  • x + y 3.
  • n is an integer from 3 to 8; R 1 and R 2 are each independently C 1-4 alkyl; R 3 is piperazinyl, pyridyl or morpholinyl .
  • the method comprises the steps of:
  • SiO 2 : P 2 O 5 : Al 2 O 3 : organic amine: H 2 O 0.2 to 1.2: 0.5 to 1.5: 0.6 to 1.4: 1.5 to 5.5: 50 to 200;
  • step b) crystallization of the mixture obtained in step a) at 150 to 220 ° C for 0.4 to 10 days;
  • step b) After the crystallization of step b) is completed, the solid product is separated and washed and dried to obtain the nano-SAPO-34 molecular sieve.
  • the molar ratio of the functionalized organosilane to the additional silicon source in moles of SiO 2 in the mixture obtained in step a) is from 1 to 55:10.
  • the phosphorus source is one or more selected from the group consisting of orthophosphoric acid, metaphosphoric acid, phosphate, and phosphite
  • the aluminum source is selected from the group consisting of aluminum salts, One or more of activated alumina, alkoxyaluminum, and metakaolin
  • the additional source of silicon being selected from one or more of the group consisting of silica sol, active silica, orthosilicate, and metakaolin.
  • the organic amine is one or more of triethylamine, tetraethylammonium hydroxide, morpholine, diethylamine, di-n-propylamine and diisopropylamine. .
  • the organic amine is triethylamine.
  • the crystallization time is from 1 to 7 days.
  • the present invention provides a SAPO-34 molecular sieve catalyst characterized in that the SAPO-34 molecular sieve catalyst is obtained by calcining a nano SAPO-34 molecular sieve synthesized according to the above method by firing in air at 400 to 700 °C.
  • the present invention provides the use of the above SAPO-34 molecular sieve catalyst for the conversion of an oxygenate to a lower olefin, wherein the oxygenate is a C1-4 alcohol and the lower olefin is a C2-6 olefin.
  • the beneficial effects produced by the present invention include, but are not limited to, the following:
  • the nano-SAPO-34 molecular sieve obtained by the method of the present invention has a small primary particle size (about 50 nm to 200 nm), a large external specific surface area (about 80-100 m 2 /g), and a large mesopore volume (about 0.10-0.25m 3 /g);
  • the nano-SAPO-34 molecular sieve obtained by the method of the invention has a pure CHA crystal phase
  • the SAPO-34 molecular sieve catalyst obtained by the method of the present invention exhibits excellent catalytic performance in the MTO reaction, the catalyst life is remarkably prolonged, and the selectivity of the low carbon olefin is improved.
  • Example 1 is a scanning electron micrograph of a sample of a nano-SAPO-34 molecular sieve obtained according to Example 1 of the present application.
  • a process for the synthesis of nano-SAPO-34 molecular sieves by hydrothermal synthesis with the aid of a functional organosilane has a role in the synthesis in at least three aspects: 1) as a crystal growth inhibitor, reducing the crystal grain size; 2) as a silicone source; 3) the functionalized organosilane functional group has a partial structure Directing, inhibiting the use of SAPO-18 eutectic, such as triethylamine as a microporous templating agent, thereby successfully combining A nano-SAPO-34 molecular sieve with a pure CHA crystal phase was formed.
  • SAPO-18 eutectic such as triethylamine as a microporous templating agent
  • the obtained nano SAPO-34 molecular sieve is usually an aggregate of nanoparticles.
  • the functional organosilane is at least one selected from the group consisting of alkoxyorganosilane compounds containing a diethylamino group, a triethylamine group, a piperazinyl group, a pyridyl group or a morpholinyl group.
  • the alkoxyorganosilane is generally regarded as an organosilicon compound in which a silicon atom is directly bonded to 1 to 4 alkoxy groups;
  • the diethylamine group is a molecule in which diethylamine has a hydrogen atom in a molecule of diethylamine.
  • the triethylamine group is a group obtained by losing a hydrogen atom on a nitrogen atom in a triethylamine molecule
  • the piperazinyl group is a hydrogen atom on a nitrogen atom in a six-membered cyclic piperazine molecule a group obtained by an atom
  • the pyridyl group is a group obtained by removing a hydrogen atom from a nitrogen atom or an arbitrary carbon atom in a six-membered cyclic piperazine molecule
  • the morpholinyl group is a six-membered cyclic morpholine molecule A group obtained by losing a hydrogen atom on a nitrogen atom or an arbitrary carbon atom.
  • the functional organosilane has the structure of formula I:
  • n-represents an integer of 1 to 16; R & lt one is C1 ⁇ 10 alkyl; R 2 is a C1 ⁇ 6 alkyl group; R 3 is diethylamino, triethylamino, piperazinyl, pyridyl, or it Lolinyl; x is an integer from 0 to 2, y is an integer from 1 to 3, and x + y 3. Further preferably, n is an integer of from 3 to 8; R 1 and R 2 are each independently a C 1-4 alkyl group; and R 3 is a piperazinyl group, a pyridyl group or a morpholinyl group.
  • the alkyl group is a group formed by the loss of any one of the hydrogen atoms of any linear or branched saturated alkane molecule.
  • the method for synthesizing the nano-SAPO-34 molecular sieve comprises the following synthesis steps:
  • SiO 2 : P 2 O 5 : Al 2 O 3 : organic amine: H 2 O 0.2 to 1.2: 0.5 to 1.5: 0.6 to 1.4: 1.5 to 5.5: 50 to 200;
  • step b) crystallization of the mixture obtained in step a) at 150 to 220 ° C for 0.4 to 10 days;
  • step b) After the step b) is completed, the solid product is separated, washed and dried to obtain the nano-SAPO-34 molecular sieve.
  • the above process can be carried out in a reactor of a conventional hydrothermal synthesis molecular sieve such as a crystallization vessel.
  • the molar ratio of functionalized organosilane to additional silicon source in moles of SiO 2 is from 1 to 55:10. Further preferably, the functional organosilane: additional silicon source is from 1 to 15:3.
  • the inorganic phosphorus compound is selected from at least one of orthophosphoric acid, metaphosphoric acid, phosphate and phosphite.
  • the source of aluminum is selected from at least one of aluminum isopropoxide, pseudoboehmite and aluminum hydroxide.
  • the additional silicon source is selected from at least one of silica sol, active silica, orthosilicate and metakaolin.
  • the organic amine is one or more of triethylamine, tetraethylammonium hydroxide, morpholine, diethylamine, di-n-propylamine and diisopropylamine.
  • the organic amine is selected from the group consisting of triethylamine (abbreviated as TEA).
  • the crystallization time is from 1 to 7 days.
  • the method for synthesizing a nano-SAPO-34 molecular sieve comprises the following steps:
  • step 2) sequentially adding an aluminum source, a phosphorus source, an organic amine and an additional silicon source to the solution of step 1), stirring at room temperature for 1 to 24 hours, and the molar ratio of each component in the mixed solution is as follows: (0.2-1.2) SiO 2 :(0.5-1.5)P 2 O 5 :(0.6-1.4)Al 2 O 3 :(1.5-5.5)organic amine:(50-200)H 2 O; wherein the functionalized organosilane and additional silicon The molar ratio of the source is from 1 to 15:3;
  • step 2) crystallization of the mixed solution of step 2) at 150 to 220 ° C for 0.4 to 10 days;
  • step 4) After the crystallization of step 3) is completed, the solid product is centrifuged, washed with deionized water to neutrality, and dried in air at 120 ° C to obtain a nano SAPO-34 molecular sieve raw powder.
  • SAPO-34 molecular sieve catalyst (or acid catalyst) which comprises nano SAPO-34 synthesized according to any of the above methods by air at 400 to 700 ° C in air. Molecular sieve roasting is obtained.
  • test conditions of the present application are as follows: The elemental composition was measured using a Magix-601 type ray fluorescence analyzer (XRF) manufactured by Philips.
  • XRF ray fluorescence analyzer
  • the SEM morphology analysis was performed using a SU8020 scanning electron microscope from the Scientific Instrument Factory of the Chinese Academy of Sciences.
  • the N 2 physical adsorption analysis was measured using a Micromeritics ASAP Model 2020 physical adsorption analyzer from Micron, USA.
  • the functionalized organosilane and n-octyltrimethoxysilane used in the examples were purchased from Shanghai Dibo Chemical Technology Co., Ltd.
  • Octadecyldimethyltrimethoxysilylpropylammonium chloride was purchased from Sigma Aldrich (Shanghai) Trading Co., Ltd.
  • the functionalized organosilane of the morphyl group is abbreviated as MoSi-n, where n is the value of the corresponding n.
  • the molar ratio of each component of the synthesis system was 0.8S1O 2 : 1.5P 2 O 5 : 0.8Al 2 O 3 : 2TEA: 80H 2 O, and the molar ratio of PiSi-3 to tetraethyl orthosilicate was 1:1.
  • the temperature was programmed to 200 ° C and static crystallization was carried out for 48 h.
  • the solid product was centrifuged, washed repeatedly with deionized water, and dried in air at 120 ° C to obtain a sample of the nano SAPO-34 molecular sieve.
  • the morphology of the obtained samples was characterized by scanning electron microscopy. The electron micrographs are shown in Fig. 1.
  • the obtained samples were strip-shaped nanocrystals aggregated into spherical microparticles.
  • the particle size distribution of the strip-shaped nanocrystal grains is between 50 nm and 200 nm.
  • the obtained sample was subjected to XRD analysis, and the results are shown in Fig. 3 and Table 2. The results show that the synthesized product has a pure SAPO-34 crystal phase.
  • the morphology of the sample obtained by the comparative example was characterized by scanning electron microscopy.
  • the electron micrograph of the sample is shown in Fig. 2.
  • the surface of the sample is a large cube with a smooth surface of about 5 ⁇ m.
  • the XRD diffraction pattern of the sample powder of Comparative Example 1 is also shown in FIG.
  • the sample of Comparative Example 1 showed a distinct broad peak at 16-17.5°, 21-22.5°, 30-32°, etc., indicating that the sample of Comparative Example 1 was SAPO-34/-18 with a high SAPO-34 content.
  • Crystal for specific crystal phase content analysis, please refer to the International Molecular Sieve Association website http://www.iza-online.org/default.htm).
  • the proportion of the ingredients and the synthesis process were the same as in Example 1, but the piperazinyl organosilane PiSi-3 was not added, and the piperazinyl organosilane PiSi-3 in Example 1 was used as the quaternary ammonium salt surface containing the same SiO 2 mole number.
  • the active agent octadecyldimethyltrimethoxysilylpropylammonium chloride (TPOAC) is substituted.
  • the XRD diffraction spectrum of the sample powder of Comparative Example 2 is shown in Fig. 3.
  • the diffraction spectrum showed that the sample of Comparative Example 2 using TPOAC contained the SAPO-18 cocrystal.
  • the XRD diffraction spectrum of the sample powder of Comparative Example 3 is shown in Fig. 3.
  • the diffraction spectrum showed that the sample of Comparative Example 3 using n-octyltrimethoxy contained a SAPO-18 cocrystal.
  • Table 1 Molecular sieve synthesis ingredients, crystallization conditions and element composition table
  • ⁇ represents the XRD diffraction angle
  • d represents the interplanar spacing
  • I represents the relative diffraction peak intensity
  • I 0 represents the relative maximum diffraction peak intensity
  • Table 3 sample specific surface area and pore volume
  • V micropores represent the pore volume of the material
  • S BET represents the BET surface area of the material
  • S micropores represent the specific pore surface area of the material
  • S mesopores represent the mesoporous specific surface area of the material.
  • Example 1 The samples obtained in Examples 1 to 4 and Comparative Example 1 were subjected to air baking at 600 ° C for 4 hours, and then tableted and crushed to 40 to 60 mesh.
  • a 0.3 g sample was weighed into a fixed bed reactor and evaluated for MTO reaction.
  • the reaction was carried out by a nitrogen gas activation at 550 ° C for 1 hour and then cooling to 450 ° C.
  • the methanol was carried by nitrogen, the flow rate of nitrogen was 42 ml/min, and the mass velocity of methanol was 4 h -1 .
  • the reaction product was analyzed by on-line gas chromatography (Varian 3800, FID detector, capillary column PoraPLOT Q-HT). The results are shown in Table 4.
  • the methanol conversion rate is 100% of the reaction time.

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Abstract

一种合成纳米SAPO-34分子筛的方法、SAPO-34分子筛催化剂及其应用。通过在水热法合成中加入微孔模板剂及具有官能化有机硅烷模板剂，合成了纳米SAPO-34分子筛。所述纳米SAPO-34分子筛经焙烧后得到SAPO-34分子筛催化剂，该催化剂可用于含氧化合物制低碳烯烃反应中。通过该方法所得到的纳米SAPO-34分子筛具有纯净的CHA晶相，并且通过该方法所得到的SAPO-34分子筛催化剂在MTO反应中表现出优异的催化性能，催化剂寿命显著延长，低碳烯烃选择性提高。

Description

纳米SAPO-34分子筛的合成方法、SAPO-34分子筛催化剂及其应用 技术领域
本发明涉及分子筛领域，更具体地涉及SAPO-34分子筛的合成方法、SAPO-34分子筛催化剂及其应用。
背景技术
磷酸硅铝分子筛(SAPO-n)的骨架结构种类多样，其三维骨架结构由PO2 +、AlO2 -和SiO2四面体构成。Si原子同晶取代中性磷酸铝骨架结构中的部分P原子或同时取代P和Al原子，使骨架产生净的负电荷，引起质子酸性，从而赋予SAPO分子筛酸催化性能。
这之中，具有CHA拓扑结构的SAPO-34分子筛由于其在甲醇制烯烃反应(MTO)中的优异催化性能已被成功应用于MTO商业化过程。然而，SAPO-34本征的微孔结构限制了传质效率，导致SAPO-34催化剂活性位利用率低，易发生孔道堵塞与积碳失活。为了解决这个问题，人们尝试合成具有介-微孔复合结构的SAPO-34分子筛，通过在本征微孔结构之间引入介孔或大孔通道，或者制备纳米级的分子筛的小晶粒来减小反应中的传质阻力，增强反应过程中分子的扩散性能，提升催化反应的反应寿命与低碳烯烃选择性。
三乙胺是一种廉价易得的合成SAPO-34分子筛的结构导向剂或模板剂，但是使用三乙胺作为单一的模板剂时，合成得到的产品往往是含有少量SAPO-18的SAPO-34/-18(CHA/AEI)共晶。在合成凝胶中硅含量极低或无硅时，甚至会得到SAPO-18或AlPO-18(Micorporous Mesoporous Materials，2008，115，332-337)。另外，使用三乙胺导向的SAPO-34分子筛粒径较大(3～5μm)，会限制MTO反应中的分子传质过程。这些都不利于获得优异的MTO催化反应结果。
发明内容
鉴于上述现有状况，本发明的一个目的是提供一种新的合成纳米SAPO-34分子筛的方法以克服现有技术中的一个或多个缺陷。
为此，在一方面，本发明提供一种用于合成纳米SAPO-34分子筛的方法，其特征在于，在官能化有机硅烷存在下，采用水热法合成所述纳米SAPO-34分子筛，所述官能化有机硅烷具有式I所示的结构：
Figure PCTCN2016092827-appb-000001
其中，n为1～16的整数；R1为C1～10烷基；R2为C1～6的烷基；R3为二乙胺基、三乙胺基、哌嗪基、吡啶基或吗啉基；x为0～2的整数，y为1～3的整数，并且x+y＝3。
在一个优选实施方案中，在所述式I中，n为3～8的整数；R1和R2各自独立地为C1～4烷基；R3为哌嗪基、吡啶基或吗啉基。
在一个优选实施方案中，所述方法包括如下步骤：
a)将所述官能化有机硅烷溶于水中，然后依次加入铝源、磷源、有机胺和额外的硅源，得到具有如下摩尔配比的混合物：
SiO2∶P2O5∶Al2O3∶有机胺∶H2O＝0.2～1.2∶0.5～1.5∶0.6～1.4∶1.5～5.5∶50～200；
b)将步骤a)所得的混合物置于150～220℃下晶化0.4～10天；
c)在步骤b)的晶化完成后，将固体产物分离并洗涤和干燥，即得到所述纳米SAPO-34分子筛。
在一个优选实施方案中，步骤a)所得的混合物中所述官能化有机硅烷与所述额外的硅源以SiO2的摩尔数计的摩尔比为1～55∶10。
在一个优选实施方案中，在步骤a)中，所述磷源为选自正磷酸、偏磷酸、磷酸盐和亚磷酸盐中的一种或多种；所述铝源为选自铝盐、活性氧化铝、烷氧基铝和偏高岭土中的一种或多种；所述额外的硅源选自硅溶胶、活性二氧化硅、正硅酸酯和偏高岭土中的一种或多种。
在一个优选实施方案中，在步骤a)中，所述有机胺为三乙胺、四乙基氢氧化铵、吗啉、二乙胺、二正丙胺和二异丙胺中的一种或多种。
在一个优选实施方案中，在步骤a)中，所述有机胺为三乙胺。
在一个优选实施方案中，在步骤b)中，所述晶化的时间为1～7天。
在另一方面，本发明提供一种SAPO-34分子筛催化剂，其特征在于，所述SAPO-34分子筛催化剂通过在400～700℃的空气中焙烧根据上述方法合成的纳米SAPO-34分子筛得到。
在另一方面，本发明提供上述SAPO-34分子筛催化剂在含氧化合物转化制低碳烯烃中的应用，其中所述含氧化合物是C1～4醇，所述低碳烯烃是C2～6烯烃。
本发明产生的有益效果包括但不限于以下方面：
(1)通过本发明方法所得到的纳米SAPO-34分子筛具有小的初级颗粒尺寸(约50nm～200nm)、大的外比表面积(约80-100m2/g)，大的中孔容积(约0.10-0.25m3/g)；
(2)通过本发明方法所得到的纳米SAPO-34分子筛具有纯的CHA晶相；
(3)通过本发明方法所得到的SAPO-34分子筛催化剂在MTO反应中表现出优异的催化性能，催化剂寿命显著延长，低碳烯烃选择性提高。
附图说明
图1为根据本申请实施例1得到的纳米SAPO-34分子筛样品的扫描电镜照片。
图2为根据本申请对比例1得到的SAPO-34分子筛样品的扫描电镜照片。
图3为根据本申请实施例1与对比例1～3得到的SAPO-34分子筛样品的XRD衍射谱图。
具体实施方式
根据本发明的一个方面，提供了一种在官能化有机硅烷辅助下通过水热法合成纳米SAPO-34分子筛的方法。所述官能化有机硅烷在合成中的作用至少在于以下三个方面：1)作为晶体生长抑制剂，降低晶体粒度；2)作为有机硅源；3)所述官能化有机硅烷的官能团具有部分结构导向作用，抑制使用诸如三乙胺作为微孔模板剂产生的SAPO-18共晶，由此成功合 成出具有纯净CHA晶相的纳米SAPO-34分子筛。
在本发明中，获得的纳米SAPO-34分子筛通常为纳米颗粒的聚集体。
在本发明中，所述官能化有机硅烷选自含有二乙胺基、三乙胺基、哌嗪基、吡啶基或吗啉基的烷氧基有机硅烷化合物中的至少一种。其中，所述烷氧基有机硅烷一般可以看作硅原子与1～4个烷氧基直接相连构成的有机硅化合物；所述二乙胺基为二乙胺分子中氮原子上失去氢原子所得到的基团；所述三乙胺基为三乙胺分子中氮原子上失去氢原子所得到的基团；所述哌嗪基为六元环状哌嗪分子中某一氮原子上失去氢原子所得到的基团；所述吡啶基为六元环状哌嗪分子中氮原子或任意碳原子上失去氢原子所得到的基团；所述吗啉基为六元环状吗啉分子中氮原子或任意碳原子上失去氢原子所得到的基团。
优选地，所述官能化有机硅烷具有式I所示的结构：
Figure PCTCN2016092827-appb-000002
其中，n为1～16的整数；R1为C1～10烷基；R2为C1～6的烷基；R3为二乙胺基、三乙胺基、哌嗪基、吡啶基或吗啉基；x为0～2的整数，y为1～3的整数，并且x+y＝3。进一步优选地，n为3～8的整数；R1和R2各自独立地为C1～4烷基；R3为哌嗪基、吡啶基或吗啉基。
在本发明中，所述烷基为任意直链或支链饱和烷烃分子失去任意一个氢原子所形成的基团。
在本发明中，优选地，所述纳米SAPO-34分子筛的合成方法包括如下合成步骤：
a)将官能化有机硅烷溶于水中后，依次加入铝源、磷源、有机胺和额外的硅源(即有机硅源或无机硅源)，得到具有如下摩尔配比的混合物 (其中所述官能化有机硅烷与所述额外的硅源的加入量以SiO2的摩尔数计，磷源的加入量以P2O5的摩尔数计，铝源的加入量以Al2O3的摩尔数计)：
SiO2∶P2O5∶Al2O3∶有机胺∶H2O＝0.2～1.2∶0.5～1.5∶0.6～1.4∶1.5～5.5∶50～200；
b)将步骤a)所得的混合物置于150～220℃下晶化0.4～10天；
c)待所述步骤b)晶化完成后，固体产物经分离、洗涤、干燥，即得到所述纳米SAPO-34分子筛。
上述方法可以在常规水热合成分子筛的反应器如晶化釜中进行。
优选地，在步骤a)的混合物中，有官能化有机硅烷与额外的硅源以SiO2的摩尔数计的摩尔比(官能化有机硅烷：额外的硅源)为1～55∶10。进一步优选地，官能化有机硅烷：额外的硅源为1～15∶3。
优选地，在步骤a)中，所述无机磷化合物选自正磷酸、偏磷酸、磷酸盐和亚磷酸盐中的至少一种。
优选地，在步骤a)中，所述铝源选自异丙醇铝、拟薄水铝石和氢氧化铝中的至少一种。
优选地，在步骤a)中，所述额外的硅源选自硅溶胶、活性二氧化硅、正硅酸酯和偏高岭土中的至少一种。
优选地，在步骤a)中，所述有机胺为三乙胺、四乙基氢氧化铵、吗啉、二乙胺、二正丙胺和二异丙胺中的一种或多种。进一步优选地，在步骤a)中，所述有机胺选自三乙胺(简写为TEA)。
优选地，在步骤b)中，晶化的时间为1～7天。
作为一个优选的实施例方式，所述合成纳米SAPO-34分子筛的方法包括如下步骤：
1)将官能化有机硅烷溶于水中，室温搅拌4～24小时；
2)向步骤1)的溶液中依次加入铝源、磷源、有机胺和额外的硅源，置于室温搅拌1～24小时，混合溶液中各组分的摩尔比例范围如下：(0.2～1.2)SiO2∶(0.5～1.5)P2O5∶(0.6～1.4)Al2O3∶(1.5～5.5)有机胺∶(50～200)H2O；其中官能化有机硅烷与额外的硅源的摩尔比为1～15∶3；
3)将步骤2)的混合溶液在150～220℃下晶化0.4～10天；
4)待步骤3)的晶化完成后，将固体产物经离心分离，用去离子水洗至中性，在120℃空气中干燥，得到纳米SAPO-34分子筛原粉。
根据本申请的另一方面，提供了一种SAPO-34分子筛催化剂(或酸催化剂)，所述SAPO-34分子筛催化剂通过在400～700℃空气中将根据上述任一方法合成的纳米SAPO-34分子筛焙烧得到。
根据本申请的又一方面，提供了一种上述SAPO-34分子筛催化剂在含氧化合物转化制烯烃反应中的应用。
实施例
下面通过实施例详述本申请，但本申请并不局限于这些实施例。
在未做特殊说明的情况下，本申请的测试条件如下：元素组成采用Philips公司的Magix-601型射线荧光分析仪(XRF)测定。
X射线粉末衍射物相分析(XRD)采用荷兰帕纳科(PANalytical)公司的X’Pert PRO X射线衍射仪，Cu靶，Kα辐射源(λ＝0.15418nm)，电压40KV，电流40mA。
SEM形貌分析采用中国科学院科学仪器厂SU8020型扫描电子显微镜。
N2物理吸附分析采用美国麦克公司的Micromeritics ASAP 2020型物理吸附分析仪测定。
实施例中所采用的官能化有机硅烷与正辛基三甲氧基硅烷，购买于上海笛柏化学品技术有限公司。十八烷基二甲基三甲氧硅丙基氯化铵购买于西格玛奥德里奇(上海)贸易有限公司。作为非限制性实例，在所述式I中，R1为甲基；R2为甲基；R3为哌嗪基、吡啶基、吗啉基中的任一一种；x＝1；y＝2；n＝3～8；并且将R3为哌嗪基的官能化有机硅烷简写为PiSi-n，将R3为吡啶基的官能化有机硅烷简写为BiSi-n，将R3为吗啉基的官能化有机硅烷简写为MoSi-n，其中的n即为相应n的取值。例如，“PiSi-3”表示化学结构为当式I中的n＝3、R1为甲基、R2为甲基、R3为哌嗪基、x＝1、y＝2的官能化有机硅烷化合物。
实施例1
各原料摩尔配料比例、晶化条件和样品元素组成见表1。具体配料过程如下：
将9.28g PiSi-3和71.40g去离子水混合搅拌1小时，依次加入135.64g拟薄水铝石(Al2O3质量百分含量72.5％)、34.58g磷酸(H3PO4质量百分含量85％)、20.24g三乙胺和8.33g正硅酸乙酯，然后搅拌陈化24小时，之后将凝胶混合物转移到不锈钢反应釜中。合成体系各组分的摩尔配比为0.8S1O2∶1.5P2O5∶0.8Al2O3∶2TEA∶80H2O，PiSi-3与正硅酸乙酯的摩尔比为1∶1。
将反应釜放入烘箱后，程序升温到200℃，静态晶化48h。反应结束后，将固体产物离心，用去离子水反复洗涤，在120℃空气中烘干得到纳米SAPO-34分子筛样品。
采用扫描电镜对所得样品的形貌进行表征，其电镜照片如图1所示，所得样品为条状纳米晶粒聚集成球状微米颗粒。条状纳米晶粒的粒径分布在50nm～200nm之间。对所得样品进行XRD分析，结果见图3和表2，结果表明合成产物具有纯净的SAPO-34晶相。
采用XRF对所得样品进行元素组成分析，结果见表1。
对比例1
配料比例及合成过程同实施例1，但没有加入哌嗪基有机硅烷PiSi-3，并且将实施例1中的哌嗪基有机硅烷PiSi-3以含有同样SiO2摩尔数的正硅酸乙酯替代。
采用扫描电镜对对比例所得的样品的形貌进行表征，其电镜照片如图2所示，表面该样品为粒径5μm左右的表面光滑的立方体大晶粒。
对比例1样品原粉的XRD衍射谱图也如图3所示。对比例1的样品在16-17.5°、21-22.5°、30-32°等处出现明显的宽包峰，显示对比例1的样品为SAPO-34含量较高的SAPO-34/-18共晶(具体各晶相含量分析可参考国际分子筛协会的网站http：//www.iza-online.org/default.htm)。
对比例2
配料比例及合成过程同实施例1，但没有加入哌嗪基有机硅烷PiSi-3，并且将实施例1中的哌嗪基有机硅烷PiSi-3以含有同样SiO2摩尔数的季铵盐类表面活性剂十八烷基二甲基三甲氧硅丙基氯化铵(TPOAC)替代。
对比例2样品原粉的XRD衍射谱图如图3所示。该衍射谱图表明，使用TPOAC的对比例2的样品中含有SAPO-18共晶。
对比例3
配料比例及合成过程同实施例1，但没有加入哌嗪基有机硅烷PiSi-3，并且将实施例1中的哌嗪基有机硅烷PiSi-3以含有同样P2O5摩尔数的不含有机官能团的正辛基三甲氧基硅烷替代。
对比例3样品原粉的XRD衍射谱图如图3所示。该衍射谱图表明，使用正辛基三甲氧基的对比例3的样品中含有SAPO-18共晶。
实施例2～12
具体配料比例和晶化条件见表1，具体配料过程同实施例1。
对实施例2～12所得样品进行XRD分析，数据结果与表2接近，即峰位置和形状相同，依合成条件的变化，峰的相对峰强度在±10％范围内波动，表明合成产物具有SAPO-34结构的特征。
对实施例2～12所得样品进行XRF元素组成分析，结果见表1。
采用扫描电镜对实施例2～12所得样品的形貌进行分析，所得电镜照片均与图1相似。
表1：分子筛合成配料、晶化条件及元素组成表
Figure PCTCN2016092827-appb-000003
表2：实施例1获得的样品的XRD结果
Figure PCTCN2016092827-appb-000004
其中θ表示XRD衍射角，d表示晶面间距，I表示相对衍射峰强度，I0表示相对最大衍射峰强度。
实施例13
对实施例1～4和对比例1所得的样品于600℃下通入空气焙烧4小时，然后进行N2物理吸附分析，结果见表3。从表3的结果可以看出，与对比例1的数据相比，实施例1～4所得样品具有明显增加的外比表面积和介孔容积。
表3样品的比表面积及孔容
Figure PCTCN2016092827-appb-000005
其中V微孔表示材料微孔孔容，SBET表示材料BET表面积，S微孔表示材料微孔比表面积，S介孔表示材料介孔比表面积
实施例14
将实施例1～4和对比例1所得的样品于600℃下通入空气焙烧4小时，然后压片、破碎至40～60目。称取0.3g样品装入固定床反应器，进行MTO反应评价。在550℃下通氮气活化1小时，然后降温至450℃进行反应。甲醇由氮气携带，氮气流速为42ml/min，甲醇质量空速4h-1。反应产物由在线气相色谱进行分析(Varian3800，FID检测器，毛细管柱PoraPLOT Q-HT)。结果示于表4。
表4：样品的甲醇转化制烯烃反应结果
Figure PCTCN2016092827-appb-000006
a.甲醇转化率为100％的反应时间。
b.100％甲醇转化率时，最高(乙烯+丙烯)选择性。
本申请虽然以优选实施方式公开如上，但并不用来限定本发明的范围，任何本领域技术人员在不脱离本发明构思的前提下，都可以做出若干可能的变动和修改，因此本申请的保护范围应当以本申请权利要求所界定的范围为准。

Claims (10)

  1. 一种用于合成纳米SAPO-34分子筛的方法，所述方法包括：在官能化有机硅烷存在下，采用水热法合成所述纳米SAPO-34分子筛，所述官能化有机硅烷具有式I所示的结构：
    Figure PCTCN2016092827-appb-100001
    其中，n为1～16的整数；R1为C1～10烷基；R2为C1～6的烷基；R3为二乙胺基、三乙胺基、哌嗪基、吡啶基或吗啉基；x为0～2的整数，y为1～3的整数，并且x+y＝3。
  2. 根据权利要求1所述的方法，其特征在于，在所述式I中，n为3～8的整数；R1和R2各自独立地为C1～4烷基；R3为哌嗪基、吡啶基或吗啉基。
  3. 根据权利要求1或2所述的方法，其特征在于，所述方法包括如下步骤：
    a)将所述官能化有机硅烷溶于水中，然后依次加入铝源、磷源、有机胺和额外的硅源，得到具有如下摩尔配比的混合物：
    SiO2∶P2O5∶Al2O3∶有机胺∶H2O＝0.2～1.2∶0.5～1.5∶0.6～1.4∶1.5～5.5∶50～200；
    b)将步骤a)所得的混合物置于150～220℃下晶化0.4～10天；
    c)在步骤b)的晶化完成后，将固体产物分离并洗涤和干燥，即得到所述纳米SAPO-34分子筛。
  4. 根据权利要求3所述的方法，其特征在于，步骤a)所得的混合物中所述官能化有机硅烷与所述额外的硅源以SiO2的摩尔数计的摩尔比为1～55∶10。
  5. 根据权利要求3所述的方法，其特征在于，在步骤a)中，所述磷源为选自正磷酸、偏磷酸、磷酸盐和亚磷酸盐中的一种或多种；所述铝源为选自铝盐、活性氧化铝、烷氧基铝和偏高岭土中的一种或多种；所述额 外的硅源选自硅溶胶、活性二氧化硅、正硅酸酯和偏高岭土中的一种或多种。
  6. 根据权利要求3所述的方法，其特征在于，在步骤a)中，所述有机胺为三乙胺、四乙基氢氧化铵、吗啉、二乙胺、二正丙胺和二异丙胺中的一种或多种。
  7. 根据权利要求3所述的方法，其特征在于，在步骤a)中，所述有机胺为三乙胺。
  8. 根据权利要求3所述的方法，其特征在于，在步骤b)中，所述晶化的时间为1～7天。
  9. 一种SAPO-34分子筛催化剂，其特征在于，所述SAPO-34分子筛催化剂通过在400～700℃的空气中焙烧根据权利要求1～8中任一项所述的方法合成的纳米SAPO-34分子筛得到。
  10. 根据权利要求9所述的SAPO-34分子筛催化剂在含氧化合物转化制低碳烯烃中的应用，其中所述含氧化合物是C1～4醇，所述低碳烯烃是C2～6烯烃。
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