WO2017084382A1 - Method for preparaing narrow-distribution small-crystal zsm-5 molecular sieve - Google Patents

Method for preparaing narrow-distribution small-crystal zsm-5 molecular sieve Download PDF

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WO2017084382A1
WO2017084382A1 PCT/CN2016/092180 CN2016092180W WO2017084382A1 WO 2017084382 A1 WO2017084382 A1 WO 2017084382A1 CN 2016092180 W CN2016092180 W CN 2016092180W WO 2017084382 A1 WO2017084382 A1 WO 2017084382A1
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molecular sieve
narrow
zsm
small
distribution
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PCT/CN2016/092180
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Chinese (zh)
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贺久长
张伟
卢永斌
高瑞民
张书勤
刘志玲
张媛
陈刚
张菊
张娟利
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陕西延长石油（集团）有限责任公司
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Publication of WO2017084382A1 publication Critical patent/WO2017084382A1/en

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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
    • C01B39/02—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
    • C01B39/36—Pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11
    • C01B39/38—Type ZSM-5
    • C01B39/40—Type ZSM-5 using at least one organic template directing agent

Definitions

  • the invention belongs to the field of material preparation, and in particular relates to a method for preparing a narrow distribution small-grain ZSM-5 molecular sieve.
  • ZSM-5 is a kind of high silica/aluminum aluminosilicate zeolite molecular sieve. It belongs to medium pore zeolite and has no cage structure.
  • the early synthetic ZSM-5 zeolite molecular sieves are mostly micron molecular sieves and have a wide distribution range. Compared with micron sieves, molecular sieves have larger surface energy and specific surface area, shorter pores, stronger resistance to sulfur poisoning and carbon deposition, and are widely used in refining, petrochemical and organic synthesis. Therefore, As a new type of catalytic material, nano ZSM-5 has attracted extensive attention from researchers at home and abroad.
  • industrial synthetic molecular sieves add rare earth ions, aluminum complexing agents and additives such as glucose starch to the synthetic system, which can significantly reduce the average particle size of the molecular sieve, but have the disadvantage of wide molecular sieve particle size distribution, and lower molecular sieves.
  • the particle size and particle size distribution range is mainly controlled by adding some surfactants and alcohols.
  • He Peng can reduce the particle size and size of the molecular sieve by adding Tween 20 and absolute ethanol in the synthesis of NaY molecular sieve.
  • the small-grain ZSM-5 molecular sieve prepared by the ultrasonic-microwave synthesis method has not only short reaction time, high yield, no addition of auxiliary aid, and a narrow particle size distribution range.
  • the present invention provides a narrow distribution of small-grain ZSM-5 molecular sieve preparation method, the template agent, deionized water, aluminum source is mixed and added to the silicon source, and the obtained mixed solution is placed in an ultrasonic water bath to react 0.5 ⁇ 2h, and then placed in the microwave for 0.5 ⁇ 2h, the obtained product is hydrothermally crystallized, and the obtained product is washed, dried and calcined to obtain a narrow distribution small crystal ZSM-5 molecular sieve.
  • the ultrasonic frequency is 30 to 50 KHZ, and the ultrasonic power is 200 to 500 W.
  • the ultrasonic water bath temperature is 30 to 60 °C.
  • the microwave frequency is 2000 ⁇ 3000MHZ, and the microwave power is 600 ⁇ 1000W.
  • the microwave reaction temperature is 80 to 90 °C.
  • the hydrothermal crystallization is between 1 and 3 h, and the crystallization temperature is 160 to 200 °C.
  • the mixed solution obtained by mixing the deionized water, the aluminum source, the templating agent and the silicon source in the method refers to mixing according to the ratio and the steps of preparing the small-grain ZSM-5 molecular sieve ruthenium raw material according to the prior art.
  • the mixing step is to mix the templating agent, deionized water and aluminum source, and then add a silicon source to obtain a mixed solution, wherein the proportions involved are all the ratios disclosed in the prior literature.
  • the molar ratio of A1 2 0 3 to SiO 2 in the silicon source is 40-100
  • the templating agent is tetrapropylammonium hydroxide
  • the silicon source is tetraethyl orthosilicate.
  • the aluminum source is sodium aluminate.
  • the small-grain ZSM-5 molecular sieve prepared by the method has a narrow particle size distribution range, uniformity, no crystal, regular structure and high crystallinity; the whole preparation process is simple, no auxiliary agent is added, and the synthesis is performed. 3 ⁇ 7 small ⁇ completed, short day, easy to industrialize production.
  • Example 1 is a particle size distribution diagram of a ZSM-5 molecular sieve obtained in Example 1;
  • Example 2 is a particle size distribution diagram of the ZSM-5 molecular sieve obtained in Example 2;
  • Example 3 is a particle size distribution diagram of the ZSM-5 molecular sieve obtained in Example 3;
  • Example 4 is a particle size distribution diagram of the ZSM-5 molecular sieve obtained in Example 4.
  • Example 5 is an SEM image of the small-grain ZSM-5 molecular sieve obtained in Example 4; 6 is an XRD pattern of the small-grain ZSM-5 molecular sieve obtained in Example 4;
  • Example 7 is a particle size distribution diagram of the ZSM-5 molecular sieve obtained in Example 5.
  • the invention finds that only small-grain molecular sieves can be obtained by single ultrasonic treatment or microwave treatment, but the obtained particle size distribution is irregular, and when the two are combined, the obtained small-grain ZSM-5 molecular sieve is obtained. There is a feature that the particle size distribution is narrow.
  • the mixed solution was placed in a stainless steel crystallization vessel, and crystallization was carried out at 200 ° C for 2 hours, and the obtained product was subjected to filtration, washing, drying at 120 ° C, and calcination at 550 ° C for 5 hours.
  • the laser particle size analysis experiment was carried out on the product.
  • the synthesis of Figure 4, Figure 5 and Figure 6 is given.
  • the particle size distribution, SEM image and XRD pattern of the small-grain sample, as shown in Fig. 6, show that the sample shows a typical MFI-type zeolite characteristic peak, and no peak is found, indicating that the sample is pure ZSM-5 molecular sieve.
  • the mixed solution was placed in a stainless steel crystallization vessel, and crystallization was carried out at 160 ° C for 3 hours, and the obtained product was filtered, washed, dried at 120 ° C, and calcined at 550 ° C for 5 hours.
  • the product was subjected to laser particle size analysis.
  • Figure 7 shows the particle size distribution of the synthesized small crystal grain sample.
  • the obtained product was filtered, washed, dried at 120 ° C, and calcined at 550 ° C for 5 hours.
  • the obtained product was filtered, washed, dried at 120 ° C, and calcined at 550 ° C for 5 h.
  • the laser particle size analysis experiment was carried out on the product.
  • the particle size distribution span parameter obtained by the ultrasonic and microwave synergistic treatment is the smallest, and is far less than that without pretreatment and ultrasonic or microwave processing, and the particle size distribution is much smaller than that without treatment.
  • the particle size distribution is narrow by about 30%, so the combination of the two can concentrate the particle size distribution of the prepared small-grain ZSM-5 molecular sieve.

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • General Life Sciences & Earth Sciences (AREA)
  • Geology (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
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  • Inorganic Chemistry (AREA)
  • Silicates, Zeolites, And Molecular Sieves (AREA)

Abstract

The present invention relates to the technical field of material preparation, and a method for preparing a narrow-distribution small-crystal ZSM-5 molecular sieve is disclosed. The goal of the present invention is to provide a method for preparing a narrow-distribution small-crystal ZSM-5 molecular sieve having small crystal, short reaction time, high yield and narrow distribution of crystal size. The preparation method comprises: mixing a template, deionized water and an aluminum source at a certain ratio, then adding a silicon source; placing the resulting mixed solution in a water bath, reacting the mixture for 0.5-2 hours under supersonic waves, then reacting the mixture for 0.5-2 hours under microwaves; subjecting the reaction product to hydrothermal crystallization; washing, drying, and calcining the resulting product so as to obtain a narrow-distribution small-crystal ZSM-5 molecular sieve. The prepared narrow-distribution small-crystal ZSM-5 molecular sieve has the following advantages: distribution range of crystal size is very narrow, molecular sieve is uniform and free from foreign crystals, structure is well-defined, and the degree of crystallinity is high. The entire preparation process is simple, with no added additives and a short synthesis time, and is readily applicable to industrial production.

Description

说明书 发明名称：一种窄分布小晶粒 ZSM-5分子筛制备方法 技术领域  Description: A narrow distribution of small grains ZSM-5 molecular sieve preparation method
[0001] 本发明属于材料制备领域， 尤其涉及一种窄分布小晶粒 ZSM-5分子筛的制备方 法。  [0001] The invention belongs to the field of material preparation, and in particular relates to a method for preparing a narrow distribution small-grain ZSM-5 molecular sieve.
背景技术  Background technique
[0002] ZSM-5是一类高硅 /铝比的硅铝酸盐沸石分子筛， 属于中孔沸石， 没有笼结构， 早期合成的 ZSM-5沸石分子筛大都是微米分子筛并且分布范围较宽， 纳米分子筛 与微米分子筛相比， 表面能和比表面积较大， 孔道较短， 抗硫中毒及抗积炭失 活能力较强， 在炼油、 石油化工和有机合成等领域都有着广泛的应用， 因此， 纳米 ZSM-5作为一种新型催化材料受到了国内外研究人员的广泛关注。  [0002] ZSM-5 is a kind of high silica/aluminum aluminosilicate zeolite molecular sieve. It belongs to medium pore zeolite and has no cage structure. The early synthetic ZSM-5 zeolite molecular sieves are mostly micron molecular sieves and have a wide distribution range. Compared with micron sieves, molecular sieves have larger surface energy and specific surface area, shorter pores, stronger resistance to sulfur poisoning and carbon deposition, and are widely used in refining, petrochemical and organic synthesis. Therefore, As a new type of catalytic material, nano ZSM-5 has attracted extensive attention from researchers at home and abroad.
[0003] 目前工业合成分子筛在合成体体系中添加稀土离子、 铝络合剂及葡萄糖淀粉等 添加剂， 可以显著降低分子筛的平均粒径， 但是存在分子筛粒径分布较宽的缺 点， 而要降低分子筛粒径大小和粒径分布范围主要是通过添加一些表面活性剂 和醇类等辅助剂来控制， 如贺鹏在合成 NaY分子筛吋加入吐温 20和无水乙醇可以 降低分子筛的粒径大小和缩小粒径分布范围 （贺鹏， 谭涓， 刘靖， 微细 NaY分子 筛的合成及粒度分布的控制， 工业催化， 2008,16 (11) ： 21-25) 。 中国科学院 山西煤炭化学研究所王建国等人采用低温成核 -高温晶化两步法也能得到形貌规 整的小粒径 ZSM-5分子筛， 但耗吋较长， 结晶度不高， 粒径分布较广 （梁庭钰 ， 牛宪军， 陈佳玲等， 小粒径 ZSM-5分子筛的几种合成条件探讨； 第十七届全国 分子筛学术大会论文集； 2014年） 。 基于此， 我们采用超声 -微波合成方法制备 出来的小晶粒 ZSM-5分子筛不仅具有反应吋间短、 产率高、 不添加任何添加辅助 齐 1J， 并且粒径分布范围非常窄。 [0003] At present, industrial synthetic molecular sieves add rare earth ions, aluminum complexing agents and additives such as glucose starch to the synthetic system, which can significantly reduce the average particle size of the molecular sieve, but have the disadvantage of wide molecular sieve particle size distribution, and lower molecular sieves. The particle size and particle size distribution range is mainly controlled by adding some surfactants and alcohols. For example, He Peng can reduce the particle size and size of the molecular sieve by adding Tween 20 and absolute ethanol in the synthesis of NaY molecular sieve. Particle size distribution range (He Peng, Tan Wei, Liu Jing, Synthesis of Fine NaY Molecular Sieves and Control of Particle Size Distribution, Industrial Catalysis, 2008, 16 (11): 21-25). Wang Jianguo, from the Shanxi Institute of Coal Chemistry, Chinese Academy of Sciences, etc., can also obtain small-size ZSM-5 molecular sieves with regular morphology by low-temperature nucleation-high-temperature crystallization two-step method, but the consumption is longer, the crystallinity is not high, and the particle size distribution More extensive (Liang Tingjun, Niu Xianjun, Chen Jialing et al. Discussion on several synthetic conditions of small particle size ZSM-5 molecular sieve; Proceedings of the 17th National Molecular Sieve Academic Conference; 2014 ). Based on this, the small-grain ZSM-5 molecular sieve prepared by the ultrasonic-microwave synthesis method has not only short reaction time, high yield, no addition of auxiliary aid, and a narrow particle size distribution range.
技术问题  technical problem
[0004] 本发明的目的在于提供一种不但晶粒小而且反应吋间短、 产率高、 晶粒粒径分 布范围窄的窄分布小晶粒 ZSM-5分子筛制备方法。  [0004] It is an object of the present invention to provide a method for preparing a narrow-distributed small-grain ZSM-5 molecular sieve which is not only small in crystal grains but also short in reaction time, high in yield, and narrow in particle size distribution.
问题的解决方案 技术解决方案 Problem solution Technical solution
[0005] 本发明提供一种窄分布小晶粒 ZSM-5分子筛制备方法， 按比例将模板剂、 去离 子水、 铝源混合后加入硅源， 将得到的混合溶液置于超声水浴中反应 0.5〜2h， 再置于微波中反应 0.5〜2h， 得到的产物进行水热晶化， 获得的产物经洗涤、 干 燥、 焙烧， 得到窄分布小晶粒 ZSM-5分子筛。  [0005] The present invention provides a narrow distribution of small-grain ZSM-5 molecular sieve preparation method, the template agent, deionized water, aluminum source is mixed and added to the silicon source, and the obtained mixed solution is placed in an ultrasonic water bath to react 0.5 ~2h, and then placed in the microwave for 0.5~2h, the obtained product is hydrothermally crystallized, and the obtained product is washed, dried and calcined to obtain a narrow distribution small crystal ZSM-5 molecular sieve.
[0006] 所述超声波频率为 30〜50KHZ， 超声波功率为 200〜500W。  [0006] The ultrasonic frequency is 30 to 50 KHZ, and the ultrasonic power is 200 to 500 W.
[0007] 所述超声水浴温度为 30〜60°C。  [0007] The ultrasonic water bath temperature is 30 to 60 °C.
[0008] 所述微波频率为 2000〜3000MHZ， 微波功率为 600〜1000W。  [0008] The microwave frequency is 2000~3000MHZ, and the microwave power is 600~1000W.
[0009] 所述微波反应温度为 80〜90°C。  [0009] The microwave reaction temperature is 80 to 90 °C.
[0010] 所述水热晶化吋间为 l〜3h， 晶化温度为 160〜200°C。  [0010] The hydrothermal crystallization is between 1 and 3 h, and the crystallization temperature is 160 to 200 °C.
[0011] 该方法中去离子水、 铝源、 模板剂和硅源按比例混合得到的混合溶液指的是按 照现有公幵的制备小晶粒 ZSM-5分子筛吋原料比例及步骤进行混合， 其混合步骤 都为将模板剂、 去离子水和铝源混合， 再向其中加入硅源， 得到混合溶液， 其 中涉及的加入比例都为现有文献公幵的比例。  [0011] The mixed solution obtained by mixing the deionized water, the aluminum source, the templating agent and the silicon source in the method refers to mixing according to the ratio and the steps of preparing the small-grain ZSM-5 molecular sieve ruthenium raw material according to the prior art. The mixing step is to mix the templating agent, deionized water and aluminum source, and then add a silicon source to obtain a mixed solution, wherein the proportions involved are all the ratios disclosed in the prior literature.
[0012] 优选地， 所述铝源中 A1 20 3与硅源中 SiO 2的摩尔比为 40-100， 所述模板剂为四 丙基氢氧化铵、 硅源为正硅酸乙酯， 铝源为铝酸钠。 [0012] Preferably, the molar ratio of A1 2 0 3 to SiO 2 in the silicon source is 40-100, the templating agent is tetrapropylammonium hydroxide, and the silicon source is tetraethyl orthosilicate. The aluminum source is sodium aluminate.
发明的有益效果  Advantageous effects of the invention
有益效果  Beneficial effect
[0013] 该方法制备得到的小晶粒 ZSM-5分子筛具有粒径分布范围非常窄、 均匀、 无杂 晶、 结构规整且结晶度高； 整个制备过程操作简单， 不添加任何辅助剂， 合成 在 3〜7小吋内完成， 吋间短， 易于工业化生产。  [0013] The small-grain ZSM-5 molecular sieve prepared by the method has a narrow particle size distribution range, uniformity, no crystal, regular structure and high crystallinity; the whole preparation process is simple, no auxiliary agent is added, and the synthesis is performed. 3~7 small 完成 completed, short day, easy to industrialize production.
对附图的简要说明  Brief description of the drawing
附图说明  DRAWINGS
[0014] 图 1是实施例 1中所得到 ZSM-5分子筛粒径分布图；  1 is a particle size distribution diagram of a ZSM-5 molecular sieve obtained in Example 1;
[0015] 图 2是实施例 2中所得到 ZSM-5分子筛粒径分布图； 2 is a particle size distribution diagram of the ZSM-5 molecular sieve obtained in Example 2;
[0016] 图 3是实施例 3中所得到 ZSM-5分子筛粒径分布图； 3 is a particle size distribution diagram of the ZSM-5 molecular sieve obtained in Example 3;
[0017] 图 4是实施例 4中所得到 ZSM-5分子筛粒径分布图； 4 is a particle size distribution diagram of the ZSM-5 molecular sieve obtained in Example 4;
[0018] 图 5是实施例 4中所得到小晶粒 ZSM-5分子筛的 SEM图； [0019] 图 6是实施例 4中所得到小晶粒 ZSM-5分子筛的 XRD图； 5 is an SEM image of the small-grain ZSM-5 molecular sieve obtained in Example 4; 6 is an XRD pattern of the small-grain ZSM-5 molecular sieve obtained in Example 4;
[0020] 图 7是实施例 5中所得到 ZSM-5分子筛粒径分布图。 7 is a particle size distribution diagram of the ZSM-5 molecular sieve obtained in Example 5.
本发明的实施方式 Embodiments of the invention
[0021] 本发明通过实验发现单独的超声处理或微波处理只能得到小晶粒分子筛， 但得 到的粒径尺寸分布没有规律， 而当两者联用吋发现得到的小晶粒 ZSM-5分子筛则 存在粒径分布窄的特点。  [0021] The invention finds that only small-grain molecular sieves can be obtained by single ultrasonic treatment or microwave treatment, but the obtained particle size distribution is irregular, and when the two are combined, the obtained small-grain ZSM-5 molecular sieve is obtained. There is a feature that the particle size distribution is narrow.
[0022] 下面通过给出的具体实施例对本发明做进一步说明， 但不作为对本发明的限定  [0022] The present invention will be further described by way of specific examples given, but not as a limitation of the invention.
[0023] 实施例 1 : [0023] Example 1 :
[0024] 将 30克去离子水、 0.2克铝酸钠、 17.6克四丙基氢氧化铵和 16毫升正硅酸乙酯依 次混合， 常温搅拌反应 5h， 在 180°C晶化反应 48h， 所得的产物经过滤、 洗涤、 12 0°C干燥， 550°C焙烧 5h。 对该产物进行激光粒度分析实验， 晶粒分布跨度参数 S = 1.57， 粒径中值 D50=7.88um， 粒径跨度范围在 l〜13um， 图 1为该样品的粒径分 布图。  [0024] 30 grams of deionized water, 0.2 grams of sodium aluminate, 17.6 grams of tetrapropylammonium hydroxide and 16 milliliters of tetraethyl orthosilicate were sequentially mixed, stirred at room temperature for 5 h, crystallization at 180 ° C for 48 h, resulting The product was filtered, washed, dried at 120 ° C, and calcined at 550 ° C for 5 h. The laser particle size analysis experiment was carried out on the product. The grain distribution span parameter S = 1.57, the median diameter D50=7.88um, and the particle size span ranged from l~13um. Figure 1 shows the particle size distribution of the sample.
[0025] 实施例 2:  [0025] Example 2:
[0026] 将 30克去离子水、 0.2克铝酸钠、 17.6克四丙基氢氧化铵和 16毫升正硅酸乙酯依 次混合， 然后将该混合溶液置于微波反应器中加热到 80°C反应 2h， 微波频率 2000 MHZ和功率 800W， 装入不锈钢晶化釜中， 在 180°C晶化反应 24h， 所得的产物经 过滤、 洗涤、 120°C干燥， 550°C焙烧 5h。 对该产物进行激光粒度分析实验， 晶粒 分布跨度参数 S=4.39， 粒径中值 D50=438nm， 粒径跨度范围在 0.1〜6um， 图 2为 该样品的粒径分布图。  [0026] 30 grams of deionized water, 0.2 grams of sodium aluminate, 17.6 grams of tetrapropylammonium hydroxide and 16 milliliters of ethyl orthosilicate were sequentially mixed, and then the mixed solution was placed in a microwave reactor and heated to 80 ° C reaction 2h, microwave frequency 2000 MHZ and power 800W, charged into a stainless steel crystallizer, crystallization reaction at 180 ° C for 24 h, the resulting product was filtered, washed, dried at 120 ° C, calcined at 550 ° C for 5 h. The product was subjected to laser particle size analysis. The grain distribution span parameter was S=4.39, the median diameter was D50=438nm, and the particle size span was 0.1~6um. Figure 2 shows the particle size distribution of the sample.
[0027] 实施例 3:  [0027] Example 3:
[0028] 将 30克水、 0.2克铝酸钠、 17.6克模板剂四丙基氢氧化铵和 16毫升正硅酸乙酯依 次混合， 然后将该混合溶液置于 40°C超声水浴中反应 lh， 超声频率 50KHZ和功 率 500W。 将该混合溶液装入不锈钢晶化釜中， 在 180°C晶化反应 24h， 所得的产 物经过滤、 洗涤、 120°C干燥， 550°C焙烧 5h。 对该产物进行激光粒度分析实验， 晶粒分布跨度参数 S=1.74， 粒径中值 D50=666nm， 粒径跨度范围在 0.1〜10um。 图 3为该样品的粒径分布图。 [0028] 30 g of water, 0.2 g of sodium aluminate, 17.6 g of templating agent tetrapropylammonium hydroxide and 16 ml of tetraethyl orthosilicate were sequentially mixed, and then the mixed solution was placed in a 40 ° C ultrasonic water bath for 1 h. , Ultrasonic frequency 50KHZ and power 500W. The mixed solution was placed in a stainless steel crystallization vessel, and crystallization was carried out at 180 ° C for 24 hours. The obtained product was filtered, washed, dried at 120 ° C, and calcined at 550 ° C for 5 h. The laser particle size analysis experiment was carried out on the product. The grain distribution span parameter S=1.74, the median diameter D50=666 nm, and the particle size span ranged from 0.1 to 10 um. Figure 3 is a graph showing the particle size distribution of the sample.
[0029] 实施例 4: Example 4:
[0030] 将 30克去离子水、 0.2克铝酸钠、 17.6克四丙基氢氧化铵和 16毫升正硅酸乙酯依 次混合， 然后将该混合溶液置于 50°C超声水浴中反应 2h， 超声频率 30KHZ和功 率 500W， 再转入微波反应器中加热到 90°C反应 lh， 微波频率 2450MHZ和功率 90 0W。 将该混合溶液装入不锈钢晶化釜中， 在 200°C晶化反应 2h， 所得的产物经过 滤、 洗涤、 120°C干燥， 550°C焙烧 5h。 对该产物进行激光粒度分析实验， 晶粒分 布跨度参数 S=0.16， 粒径中值 D50=283nm， 粒径跨度范围在 0.2〜0.4um， 附图 4 、 图 5和图 6给出了合成的小晶粒样品的粒径分布图、 SEM图和 XRD图， 由图 6可 知， 样品表现出典型的 MFI型沸石特征峰， 且未发现杂峰， 说明试样为纯 ZSM-5 分子筛。  [0030] 30 g of deionized water, 0.2 g of sodium aluminate, 17.6 g of tetrapropylammonium hydroxide and 16 ml of ethyl orthosilicate were sequentially mixed, and then the mixed solution was placed in a 50 ° C ultrasonic water bath for 2 h. Ultrasonic frequency 30KHZ and power 500W, then transferred to microwave reactor for heating to 90 °C for 1h, microwave frequency 2450MHZ and power 90 0W. The mixed solution was placed in a stainless steel crystallization vessel, and crystallization was carried out at 200 ° C for 2 hours, and the obtained product was subjected to filtration, washing, drying at 120 ° C, and calcination at 550 ° C for 5 hours. The laser particle size analysis experiment was carried out on the product. The grain distribution span parameter S=0.16, the median diameter D50=283 nm, and the particle size span ranged from 0.2 to 0.4 um. The synthesis of Figure 4, Figure 5 and Figure 6 is given. The particle size distribution, SEM image and XRD pattern of the small-grain sample, as shown in Fig. 6, show that the sample shows a typical MFI-type zeolite characteristic peak, and no peak is found, indicating that the sample is pure ZSM-5 molecular sieve.
[0031] 实施例 5:  Example 5:
[0032] 将 30克去离子水、 0.2克铝酸钠、 17.6克四丙基氢氧化铵和 16毫升正硅酸乙酯依 次混合， 然后将该混合溶液置于 60°C超声水浴中反应 lh， 超声频率 40KHZ和功 率 300W， 再转入微波反应器中加热到 85°C反应 2h， 微波频率 3000MHZ和功率 10 00W。 将该混合溶液装入不锈钢晶化釜中， 在 160°C晶化反应 3h， 所得的产物经 过滤、 洗涤、 120°C干燥， 550°C焙烧 5h。 对该产物进行激光粒度分析实验， 晶粒 分布跨度参数 S=0.43， 粒径中值 D50=307nm， 粒径跨度范围在 0.1〜6um， 图 7为 合成的小晶粒样品的粒径分布图。  [0032] 30 g of deionized water, 0.2 g of sodium aluminate, 17.6 g of tetrapropylammonium hydroxide and 16 ml of tetraethyl orthosilicate were sequentially mixed, and then the mixed solution was placed in a 60 ° C ultrasonic water bath for 1 h. Ultrasonic frequency 40KHZ and power 300W, then transferred to microwave reactor for heating to 85 °C for 2h, microwave frequency 3000MHZ and power 10 00W. The mixed solution was placed in a stainless steel crystallization vessel, and crystallization was carried out at 160 ° C for 3 hours, and the obtained product was filtered, washed, dried at 120 ° C, and calcined at 550 ° C for 5 hours. The product was subjected to laser particle size analysis. The grain distribution span parameter S=0.43, the median diameter D50=307 nm, and the particle size span ranged from 0.1 to 6 μm. Figure 7 shows the particle size distribution of the synthesized small crystal grain sample.
[0033] 实施例 6:  Example 6:
[0034] 将 30克去离子水、 0.2克铝酸钠、 17.6克四丙基氢氧化铵和 16毫升正硅酸乙酯依 次混合， 然后将该混合溶液置于 60°C超声水浴中反应 0.5h， 超声频率 30KHZ和功 率 400W再转入微波反应器中加热到 80°C反应 0.5h， 微波频率 3000MHZ和功率 600 W。 将该混合溶液装入不锈钢晶化釜中， 在 170°C晶化反应 3h， 所得的产物经过 滤、 洗涤、 120°C干燥， 550°C焙烧 5h。 对该产物进行激光粒度分析实验， 晶粒分 布跨度参数 S=1.55， 粒径中值 D50=538nm， 粒径跨度范围在 0.1〜7um。  [0034] 30 grams of deionized water, 0.2 grams of sodium aluminate, 17.6 grams of tetrapropylammonium hydroxide and 16 milliliters of tetraethyl orthosilicate were sequentially mixed, and then the mixed solution was placed in a 60 ° C ultrasonic water bath to react 0.5 h, ultrasonic frequency 30KHZ and power 400W are transferred to the microwave reactor and heated to 80 ° C for 0.5 h, microwave frequency 3000 MHZ and power 600 W. The mixed solution was placed in a stainless steel crystallizer and crystallized at 170 ° C for 3 hours. The obtained product was filtered, washed, dried at 120 ° C, and calcined at 550 ° C for 5 hours. The laser particle size analysis experiment was carried out on the product, and the grain distribution span parameter S=1.55, the median diameter D50=538 nm, and the particle size span ranged from 0.1 to 7 um.
[0035] 实施例 7:  [0035] Example 7:
[0036] 将 30克去离子水、 0.2克铝酸钠、 17.6克四丙基氢氧化铵和 16毫升正硅酸乙酯依 次混合， 然后将该混合溶液置于 45°C超声水浴中反应 2h， 超声频率 40KHZ和功 率 400W， 再转入微波反应器中加热到 83°C反应 lh， 微波频率 3000MHZ和功率 70 0W。 将该混合溶液装入不锈钢晶化釜中， 在 190°C晶化反应 2.5h， 所得的产物经 过滤、 洗涤、 120°C干燥， 550°C焙烧 5h。 对该产物进行激光粒度分析实验， 晶粒 分布跨度参数 S=0.82， 粒径中值 D50=348nm， 粒径跨度范围在 0.1〜6um。 [0036] 30 grams of deionized water, 0.2 grams of sodium aluminate, 17.6 grams of tetrapropylammonium hydroxide and 16 milliliters of ethyl orthosilicate After mixing, the mixed solution was placed in a 45 ° C ultrasonic water bath for 2 h, ultrasonic frequency 40 KHZ and power 400 W, and then transferred to a microwave reactor for heating to 83 ° C for 1 h, microwave frequency 3000 MHZ and power 70 0 W. The mixed solution was placed in a stainless steel crystallization vessel, and crystallization was carried out at 190 ° C for 2.5 hours. The obtained product was filtered, washed, dried at 120 ° C, and calcined at 550 ° C for 5 h. The laser particle size analysis experiment was carried out on the product. The grain distribution span parameter S=0.82, the median diameter D50=348 nm, and the particle size span ranged from 0.1 to 6 um.
[0037] 由上述实施例对比可以看出经过超声和微波协同处理， 得到的粒径分布跨度参 数最小， 且远小于没有前处理和采用超声或微波进行处理， 且粒径分布远小于 没有处理的， 较超声或微波处理的粒径分布窄 30%左右， 因此两者联用可以使制 备得到的小晶粒 ZSM-5分子筛的粒径分布集中。  [0037] It can be seen from the comparison of the above embodiments that the particle size distribution span parameter obtained by the ultrasonic and microwave synergistic treatment is the smallest, and is far less than that without pretreatment and ultrasonic or microwave processing, and the particle size distribution is much smaller than that without treatment. Compared with ultrasonic or microwave treatment, the particle size distribution is narrow by about 30%, so the combination of the two can concentrate the particle size distribution of the prepared small-grain ZSM-5 molecular sieve.
[0038] 以上内容是结合具体的实施方式对本发明所做的进一步详细说明， 不能认定本 发明的具体实施只局限于这些说明。 对于本发明所属技术领域的普通技术人员 来说， 在不脱离本发明构思的前提下， 还可以做出若干简单推演或替换， 都应 当视为属于本发明的保护范围。  The above is a further detailed description of the present invention in connection with the specific embodiments, and the specific embodiments of the present invention are not limited to the description. It will be apparent to those skilled in the art that the present invention may be practiced without departing from the spirit and scope of the invention.

Claims

权利要求书 Claim
[权利要求 1] 一种窄分布小晶粒 ZSM-5分子筛制备方法， 其特征在于： 按比例将模 板剂、 去离子水、 铝源混合后加入硅源， 将得到的混合溶液置于超声 水浴中反应 0.5〜2h， 再置于微波中反应 0.5〜2h， 产物进行水热晶化 ， 获得的产物经洗涤、 干燥、 焙烧， 得到窄分布小晶粒 ZSM-5分子筛  [Claim 1] A method for preparing a narrow-distribution small-grain ZSM-5 molecular sieve, characterized in that: a template agent, a deionized water, and an aluminum source are mixed in proportion, and then added to a silicon source, and the obtained mixed solution is placed in an ultrasonic water bath. The reaction is carried out for 0.5~2h, and then placed in a microwave for 0.5~2h. The product is hydrothermally crystallized, and the obtained product is washed, dried and calcined to obtain a narrow distribution small crystal ZSM-5 molecular sieve.
[权利要求 2] 如权利要求 1所述的窄分布小晶粒 ZSM-5分子筛制备方法， 其特征在 于： 所述超声波频率为 30〜50KHZ， 超声波功率为 200〜500W。 [Claim 2] The method for preparing a narrow-distribution small-grain ZSM-5 molecular sieve according to claim 1, wherein the ultrasonic frequency is 30 to 50 kHz and the ultrasonic power is 200 to 500 watts.
[权利要求 3] 如权利要求 2所述的窄分布小晶粒 ZSM-5分子筛制备方法， 其特征在 于： 所述超声水浴温度为 30〜60°C。 [Claim 3] The method for preparing a narrow-distribution small-grain ZSM-5 molecular sieve according to claim 2, wherein: the ultrasonic water bath temperature is 30 to 60 °C.
[权利要求 4] 如权利要求 1所述的窄分布小晶粒 ZSM-5分子筛制备方法， 其特征在 于： 所述微波频率为 2000〜3000MHZ， 微波功率为 600〜1000W。 [Claim 4] The method for preparing a narrow-distribution small-grain ZSM-5 molecular sieve according to claim 1, wherein: the microwave frequency is 2000 to 3000 MHz, and the microwave power is 600 to 1000 W.
[权利要求 5] 如权利要求 4所述的窄分布小晶粒 ZSM-5分子筛制备方法， 其特征在 于： 所述微波反应温度为 80〜90°C。 [Claim 5] The method for preparing a narrow-distribution small-grain ZSM-5 molecular sieve according to claim 4, wherein the microwave reaction temperature is 80 to 90 °C.
[权利要求 6] 如权利要求 1所述的窄分布小晶粒 ZSM-5分子筛制备方法， 其特征在 于： 所述水热晶化吋间为 l〜3h， 晶化温度为 160〜200°C。 [Claim 6] The method for preparing a narrow-distribution small-grain ZSM-5 molecular sieve according to claim 1, wherein: the hydrothermal crystallization is 1 to 3 hours, and the crystallization temperature is 160 to 200 ° C. .
[权利要求 7] 如权利要求 1所述的窄分布小晶粒 ZSM-5分子筛制备方法， 其特征在 于： 所述铝源中 A1 20 3与硅源中 SiO 2的摩尔比为 40-100。 [Claim 7] The method for preparing a narrow-distribution small-grain ZSM-5 molecular sieve according to claim 1, wherein: the molar ratio of A1 2 0 3 to SiO 2 in the silicon source in the aluminum source is 40-100 .
[权利要求 8] 如权利要求 7所述的窄分布小晶粒 ZSM-5分子筛制备方法， 其特征在 于： 所述模板剂为四丙基氢氧化铵。 [Claim 8] The method for preparing a narrow-distributed small-grain ZSM-5 molecular sieve according to claim 7, wherein the templating agent is tetrapropylammonium hydroxide.
[权利要求 9] 如权利要求 8所述的窄分布小晶粒 ZSM-5分子筛制备方法， 其特征在 于： 所述硅源为正硅酸乙酯， 铝源为铝酸钠。 [Claim 9] The method for preparing a narrow-distribution small-grain ZSM-5 molecular sieve according to claim 8, wherein: the silicon source is tetraethyl orthosilicate, and the aluminum source is sodium aluminate.
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