CN101774607B - Method for preparing oriented molecular sieve membrane by using diauxic growth method - Google Patents

Method for preparing oriented molecular sieve membrane by using diauxic growth method Download PDF

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CN101774607B
CN101774607B CN 200910263978 CN200910263978A CN101774607B CN 101774607 B CN101774607 B CN 101774607B CN 200910263978 CN200910263978 CN 200910263978 CN 200910263978 A CN200910263978 A CN 200910263978A CN 101774607 B CN101774607 B CN 101774607B
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seed
carrier
molecular sieve
method
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CN101774607A (en
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延静
王晓东
黄伟
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太原理工大学
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Abstract

The invention relates to a method for preparing an oriented molecular sieve membrane by using a diauxic growth method, which comprises that molecular sieve seed crystals are carried on a carrier by using an electrostatic absorption-ultrasound method to form a seed crystal layer; the pH value of seed crystal liquid is adjusted to form a surface electrostatic layer, and the seed crystals are made to contact with the carrier with the maximum a-c surface through the assistance of ultrasound to form an even and successive b-axis oriented molecular sieve seed crystal layer; the molecular sieve seedcrystal layer is prepared into a dense and successive b-axis oriented molecular sieve seed crystal membrane through diauxic growth. The method has the advantages of easy control of the thickness and orientation of molecular sieve membranes, repeatability and suitability for scale production.

Description

一种利用二次生长法制备取向分子筛膜的方法 Preparation of secondary growth method using zeolite membrane oriented Method

技术领域 FIELD

[0001] 本发明涉及一种分子筛膜的制备方法,尤其是一种利用二次生长法在多孔陶瓷载体和硅片上制备b轴取向TS-I分子筛膜的方法。 [0001] The present invention relates to a method for the preparation of secondary growth method b-oriented TS-I zeolite membrane on a porous ceramic support and a method of preparing a film of silicon molecular sieves, in particular a use.

背景技术 Background technique

[0002] 一九八三年,Taramasso等将过渡金属钛引入纯硅沸石(Silicalite-Ι)骨架中, 合成钛硅分子筛TS-I (Titanium silicalite-1),它属于ZSM-5系列沸石分子筛,具有MFI 的拓扑结构。 [0002] 1983, a transition metal like titanium Taramasso introduction of pure silicalite (Silicalite-Ι) backbone, the synthesis of titanium silicalite TS-I (Titanium silicalite-1), which belongs to ZSM-5 series zeolite molecular sieve, with the MFI topology. 钛硅分子筛(TS-I)膜不但具有钛硅分子筛优异的催化氧化性能,而且具有沸石膜材料的特性,可实现反应过程与分离过程的有效集成,提高反应转化率和强化反应过程,已引起研究者们的广泛关注。 Titanium silicalite (TS-I) films not only molecular sieves having excellent catalytic oxidation of titanium silicate, and a zeolite membrane material properties can be achieved effectively integrated reaction and separation process and improve the conversion rate and strengthen the reaction process has attracted the researchers attention.

[0003] TS-I分子筛具有MFI的拓扑结构,MFI型分子筛具有两种交叉孔道,一种是圆形直孔道,另一种是正弦形椭圆孔道。 [0003] TS-I zeolite having the MFI topology, with two cross-MFI zeolite channels, one is a straight circular channel, and the other is a sinusoidal elliptic bore. 如果合成的分子筛膜以(100)晶面平行于支撑体表面生长,即以a轴垂直于表面,渗透将通过MFI分子筛晶体的正弦孔道进行;如以(001)晶面平行于表面生长,即以c轴垂直于表面,渗透将通过反复在两种孔道中交替的方式进行,扩散距离最长;如以(010)晶面平行于表面生长,即以b轴垂直于表面,渗透将通过晶体的直孔道进行,扩散距离最短,是最希望获得的晶体取向方式。 If the molecular sieve membrane synthesis of (100) crystal plane parallel to the surface of the support growth, i.e., the a-axis perpendicular to the surface, penetration will be carried out by the sinusoidal channels MFI molecular sieve crystals; such as (001) crystal plane parallel to the growth surface, i.e., c-axis perpendicular to the surface, the penetration through channels alternately repeated in both the embodiment, the maximum diffusion distance; as in (010) crystal plane parallel to the growth surface, i.e., the b-axis perpendicular to the surface, will penetrate through the crystal for a straight channel, the diffusion distance is the shortest, the crystal orientation is obtained in the most desirable manner.

[0004] 现有b轴取向TS-I分子筛膜是利用原位水热合成法制得。 [0004] The conventional TS-I b-axis oriented film is the use of zeolite in situ hydrothermal synthesis. 与原位水热合成法相比,二次生长法因晶种层的引入具有如下优点:由于分子筛膜成核过程与生长过程的分离, 可以通过控制晶种层的取向,调控分子筛膜的取向;晶种层的存在可提高膜层的连续性以及合成过程可控性,更好地控制晶体生长和分子筛膜的微观结构,有效地控制膜的取向性及膜层厚度;在晶化环境以及所使用的原料并未得到充分优化的条件下,同样可以制备出高质量的分子筛膜;由于消除了分子筛膜生长所需要的成核过程,缩短了合成时间,降低了成本,重复性高,适于工业生产。 Compared with the in-situ hydrothermal synthesis method, secondary growth method by the introduction of the seed layer has the following advantages: Due to the molecular sieve membrane to separate nucleation and growth process, by controlling the orientation of the seed layer, the regulation of the molecular sieve alignment film; the presence of the seed layer and the continuity of the film can be improved synthesis process controllability, better control of the microstructure and the crystal growth of the zeolite membrane, and efficiently control the orientation of the film thickness of the film; in the crystallization environment and the raw material has not been fully optimized conditions, can also be prepared in high-quality zeolite membrane; due to the elimination of the nucleation growth of zeolite membranes needed to shorten the synthesis time, reduce costs, high repeatability, adapted industrial production.

[0005] 现已有利用二次生长法合成取向分子筛膜。 [0005] There is now a secondary growth method using synthetic zeolite membrane alignment. Tsapatsis等人利用TPA作为结构导向剂制备晶种层,再以自制的三聚体TPA作为模板剂,经过二次生长,在多孔氧化铝载体上成功地合成出b轴取向、厚度仅为1 μ m的高性能b轴取向Silicalite-I分子筛膜;采用静电吸附法将A型分子筛晶种担载在硅片上,形成a轴取向分子筛晶种层,此时,晶种以最大的bc面与载体接触,二者的作用力最强,体系能量最低,最稳定,再经二次生长后制备出a 轴取向A型分子筛膜。 Et al Tsapatsis prepared using TPA as a seed layer structure directing agent, and then made to trimers TPA as template, after the second growth on a porous alumina support successfully synthesized the b-axis orientation, the thickness of only 1 μ m b-axis oriented high-performance Silicalite-I zeolite membrane; electrostatic adsorption method using zeolite a seed crystals supported on a silicon wafer, forming a sieve-axis orientation of the seed layer, this time, the seed crystal with the greatest surface bc the contact carrier, the two strongest biasing force, the minimum energy of the system, the most stable, and then prepare a zeolite a-type a-axis orientation film after secondary growth. T. Ban等人采用超声法将ZSM-5晶种担载在α -Al2O3载体上,形成b 轴取向晶种层,再经二次生长制备b轴取向ZSM-5分子筛膜,该方法易于操作,设备简单,但是所制得的晶种层取向性较差,非b轴取向的晶种依然大量存在。 T. Ban et al ultrasonic method ZSM-5 seed α -Al2O3 supported on the support to form a b-axis oriented seed layer, and then the b-axis oriented film of zeolite ZSM-5 prepared by the secondary growth, which method is easy to operate , the device is simple, but the resulting alignment is poor seed layer, b-axis oriented seed crystal remains non abound.

发明内容 SUMMARY

[0006] 问题的提出,单纯采用超声法制备晶种层时,所得到的晶种层取向性较差,非b轴取向的晶种所占比例较大,为了解决这个问题,本发明提供一种利用二次生长法制备取向分子筛膜的方法。 Introducing [0006] problem, prepared by simple ultrasonic SYSTEM seed layer seed layer orientation obtained is poor, the proportion of non-seed large b-axis oriented, in order to solve this problem, the present invention provides a Preparation method of alignment secondary growth species using molecular sieve membrane. [0007] —种利用二次生长法制备取向分子筛膜的方法所采取的技术方案包括晶种的担载和二次生长工艺。 [0007] - Preparation of the secondary growth method using the seed zeolite membrane oriented approach adopted solution consists in supporting the seed crystal and the secondary growth process. 首先采用静电吸附-超声法将晶种担载在载体上。 Firstly electrostatic adsorption - ultrasound seed crystals supported on a carrier. 通过调节晶种液的PH值形成表面静电层,使晶种以最大的ac面与载体接触,此时,二者之间的作用力最强, 体系能量最低,最稳定,期间辅以超声振荡使晶种在载体上均勻、连续的分散,使用此方法可得到高质量b轴取向TS-I分子筛晶种层。 Forming a surface layer by adjusting the electrostatic liquid PH value of the seed, the seed crystal at the maximum ac contacted with the support surface, In this case, the force between the two strongest, lowest energy system, the most stable, combined with ultrasonic oscillation period seed crystal on the carrier uniform, continuous dispersion quality can be obtained using this method b-oriented TS-I zeolite seed layer. 而后将担载有晶种的载体与二次生长液一起置于晶化反应釜中进行二次生长,制得b轴取向TS-I分子筛膜。 After the secondary vector carries a growth liquid is placed with the seed crystallization secondary growth reactor, b-axis orientation prepared TS-I molecular sieve membrane.

[0008] 本发明一种制备取向分子筛膜方法的具体制备步骤依次如下: [0008] DETAILED preparing step of preparing a zeolite membrane oriented method of the present invention sequentially as follows:

[0009] 首先,将TS-I分子筛晶种分散在四丙基氢氧化铵TPAOH水溶液中制成晶种液,调节其PH值为3. 5〜8. 5,将内置滤纸的培养皿放入超声波清洗器,再将载体放入培养皿内的滤纸上,用四丙基氢氧化铵TPAOH水溶液将载体和滤纸浸透,在超声条件下将前述晶种液滴加在载体上,超声直到载体表面干燥后取出,制得b轴取向TS-I分子筛晶种层。 [0009] First, the TS-I zeolite seed crystal dispersion in TPAOH tetrapropylammonium hydroxide aqueous solution to prepare a seed crystal, adjusting the PH value of 3. 5 ~ 8. 5, the filter paper into the built-in dish ultrasonic cleaning, and then the carrier placed on the filter paper in the petri dish, using TPAOH tetrapropylammonium hydroxide aqueous solution and filter paper impregnated carrier, under ultrasonic conditions, the seed crystal added dropwise to the carrier until the carrier surface ultrasonic after drying removed to obtain TS-I b-axis oriented seed layer of molecular sieve.

[0010] 其次,将硅源滴加到四丙基氢氧化铵的水溶液中,于室温下搅拌,再将钛源溶于异丙醇后,将其在0°c、氮气保护作用下,滴加到前述溶胶中,升温至80〜85°C,在此温度下搅拌,蒸发除去溶胶中的醇,加水至原有液面高度,冷却至室温,搅拌1小时,得到二次生长液,二次生长液的组成为:aSi:bTi:cTPA0H:dH20,其中a = l,b = 0. 004 〜0· 013,c = 0· 1 〜 0. 15,d = 60 〜90。 [0010] Next, the silicon source added dropwise tetrapropyl ammonium hydroxide aqueous solution, stirred at room temperature, the titanium source and then dissolved in isopropanol, which was at 0 ° c, the protective effect of nitrogen, a dropping was added to the sol, warmed to 80~85 ° C, stirred at this temperature and evaporated to remove alcohol sol, add water to the original liquid level was cooled to room temperature, stirred for 1 hour, to obtain secondary growth solution, bis composition of the growth liquid views: aSi: bTi: cTPA0H: dH20, wherein a = l, b = 0. 004 ~0 · 013, c = 0 · 1 ~ 0. 15, d = 60 ~90.

[0011] 最后,将所得到的担载有晶种的载体与二次生长液一起置于晶化反应釜中,载体水平放置,担载晶种的载体晶种层向下与二次生长液接触,在170〜185°C二次生长20〜 50小时,取出冷却至室温,用去离子水洗至中性,干燥,550°C焙烧8小时除去模板剂,制得b 轴取向TS-I分子筛膜。 [0011] Finally, the obtained secondary vector carries a growth liquid is placed with the seed crystallization autoclave, a carrier horizontally, the support carrying the seed and the seed layer downward liquid secondary growth contacting, at 170~185 ° C by the secondary growth 20~ 50 hours, then cool to room temperature, washed with deionized water until neutral, dried, 550 ° C was calcined for 8 hours to remove the template agent, b-axis orientation prepared zeolite TS-I membrane.

[0012] 本发明上述方法中所述的载体是片状α -Al2O3多孔陶瓷载体或是硅片;所述的晶种液的浓度为0. 1〜0. 5%,滴加量为0. 5〜Iml ;所述的超声波清洗器的频率为40ΚΗζ,超声功率为100〜200W ;所述的超声波清洗器内的环境温度是40〜65°C;所述的硅源是硅溶胶、正硅酸乙酯或是白炭黑;所述的钛源是钛酸四乙酯或是钛酸四丁酯。 In the above-described method of the invention is a vector [0012] This sheet-like α -Al2O3 porous ceramic support or silicon; the concentration of the seed liquid 1~0 0. 5% was added dropwise in an amount of 0. 5~Iml; frequency of the ultrasonic cleaner for 40ΚΗζ, ultrasonic power 100~200W; ambient temperature in the ultrasonic cleaning is 40~65 ° C; the source of silicon is silica, silicate ethyl or silica; the titanium source is tetraethyl titanate or tetrabutyl titanate.

[0013] 本发明制备一种取向分子筛膜方法的优点与积极效果在于:本方法分两步进行, 首先是采用静电吸附-超声法将晶种担载在载体上。 [0013] The present invention is the preparation of a zeolite membrane oriented advantages and positive effects of the method comprising: the process in two steps, first using the electrostatic adsorption - ultrasound seed crystals supported on a carrier. 通过预先调节晶种液的PH值使晶种和载体带异性电荷,由于晶种和载体间的静电相互作用,晶种被牢固的吸附在载体表面,且以最大的ac面与载体接触,此时二者之间的静电作用力最强,体系能量最低,最稳定,在静电吸附过程中伴随有超声振荡,可促进晶种更加均勻、连续的担载在载体上。 By pre-adjusting the PH value of the seed liquid carrier and a seed crystal with opposite charges, between the electrostatic interaction between the carrier and the seed, the seed crystal is firmly adsorbed on the surface of the carrier, with a maximum ac-surface contact with a carrier, this when the electrostatic force between the two strongest, lowest energy system, the most stable, with the electrostatic adsorption process with an ultrasonic oscillation, can facilitate more uniform seed crystals, a continuous supported on a carrier. 相比于单纯的超声法,静电吸附-超声法可制得高质量b轴取向TS-I分子筛晶种层。 Compared to a simple ultrasound, electrostatic adsorption - a high quality can be prepared by sonication b-oriented TS-I zeolite seed layer. 其次制备二次生长液,将担载有晶种的载体与二次生长液一起置于晶化反应釜中进行二次生长,即可合成b 轴取向TS-I分子筛膜。 Preparation of secondary growth was followed, with the second carrier carries a growth liquid is placed with the seed crystallization autoclave secondary growth, b-axis orientation can be synthesized TS-I molecular sieve membrane. 该方法因成核过程与生长过程分离,可以通过控制所生成晶种的取向与形貌,进而控制所生成的分子筛膜的取向。 The method of separating nucleation and growth process due to the orientation and morphology of the seed crystal may be generated by the control, thereby controlling the alignment of the molecular sieve film generated. 由于晶种层的存在,在晶化环境以及所使用的原料并未得到充分优化的条件下,同样可以制备出高质量的分子筛膜,使合成范围更宽, 提高合成过程可控性以及重现性。 Due to the presence of the seed layer, in the environment and the crystallization raw materials used have not been fully optimized conditions, can also be prepared in high quality zeolite membrane, so that a wider range of synthesis, improved reproducibility and controllability synthesis process sex. 而在原位水热合成法工艺过程中,是将多孔支撑体在适宜的水热条件下与合成液相接触,分子筛晶体在支撑体表面以交联的方式成核、生长,最终成膜,通常支撑体表面是不均勻的,很难以平铺的方式在其表面上均勻成核,从而导致缺陷的产生和晶体尺寸的不均一,最直接的结果就是低重复性。 In the process of in-situ hydrothermal synthesis method, the porous support is contacted with a liquid phase synthesis under suitable hydrothermal conditions, molecular sieve crystals on the support surface so as to crosslink the nucleation, growth, eventually forming, typically the support surface is uneven, it is difficult to uniformly tiled nucleation on the surface, resulting in non-uniform crystal size and generation of defects, the most direct result is a low reproducibility. 再次,经X射线衍射分析XRD及扫描电镜SEM检测证明,本发明方法所得晶种层及二次生长后所得TS-I分子筛膜b轴取向性均很高。 Again, XRD X-ray diffraction analysis and scanning electron microscopy SEM examination proved that the method of the present invention is obtained after the second seed layer and the resulting growth of zeolite TS-I b-axis orientation film are high. b轴取向分子筛膜,其晶体的直线型孔道垂直于载体,这一结构特点使渗透物通过的路径最短,所受的阻力最小,有利于传质过程,可提高催化反应的选择性,增加一级反应产物的产量。 b-axis orientation molecular sieve membrane, linear tunnel which is perpendicular to the carrier crystals, this factor makes permeate through the shortest path, minimum drag on, favor the mass transfer process can be improved selective catalytic reaction, an increase in yield stage reaction product. 另外,本方法提高了原材料的利用率,降低了成本,适于工业化放大。 Further, the present method improves the utilization of raw materials, reducing the cost, and suitable for industrial amplification.

附图说明 BRIEF DESCRIPTION

[0014] 图1是MFI型分子筛晶体的孔道结构图; [0014] FIG. 1 is a configuration diagram of pore molecular sieve crystals of the MFI type;

[0015] 图2是本发明所得分子筛晶种层的典型X射线衍射分析XRD谱图; [0015] FIG. 2 is a crystalline molecular sieve of this invention was typical X-ray diffraction analysis of the XRD pattern of seed layer;

[0016] 图3是本发明所得分子筛晶种层的典型扫描电镜SEM正面图; [0016] FIG. 3 is a crystalline molecular sieve of this invention was typically a front view of a scanning electron microscope SEM seed layer;

[0017] 图4是本发明所得分子筛膜的典型X射线衍射分析XRD谱图; [0017] FIG. 4 is a zeolite membrane of the present invention obtained X-ray diffraction analysis of a typical XRD spectrum;

[0018] 图5是本发明所得分子筛膜的典型扫描电镜SEM正面图; [0018] FIG. 5 is a typical front view of a scanning electron microscope SEM obtained zeolite membrane of the present invention;

[0019] 图6是本发明所得分子筛膜的典型扫描电镜SEM侧面图。 [0019] FIG. 6 is a side view of a typical SEM scanning electron microscope of the present invention, the resulting zeolite membrane.

具体实施方式 Detailed ways

[0020] 下面用具体实施方式对本发明方法作出进一步的详细说明,以本领域的技术人员能够实现为准,同时,其优点与效果也能够得到体现。 [0020] DETAILED DESCRIPTION below with reference to further detailed description of the method of the present invention to those skilled in the art to carry it out, at the same time, its advantages and effects can be reflected.

[0021] 实施方式1 [0021] Embodiment 1

[0022] (1)将0. 25gTS-l晶种分散在49. 75g的四丙基氢氧化铵TPAOH水溶液中制成晶种液,其PH = 3.5。 [0022] (1) 0. 25gTS-l seed crystals dispersed in tetrapropylammonium hydroxide aqueous solution of TPAOH 49. 75g of seed was prepared, which PH = 3.5. 在超声波清洗器内放一内置滤纸的培养皿,将载体放入培养皿内的滤纸上,用pH = 3. 5的四丙基氢氧化铵TPAOH水溶液将载体与滤纸浸湿,在200W、40KHz、40°C的超声条件下将前述晶种液0. 5ml滴加在载体上,超声直到载体表面干燥后取出,制得b轴取向TS-I分子筛晶种层。 Put in an ultrasonic cleaner filter built in a Petri dish, place the vector into the filter paper in the petri dish, with pH = tetrapropyl ammonium hydroxide aqueous solution of TPAOH 3.5 will support filter paper soaked in 200W, 40KHz under ultrasonic condition of 40 ° C to the seed crystal was added dropwise at 0. 5ml carrier, ultrasonic removed until the surface of the support and dried to prepare a b-axis oriented TS-I zeolite seed layer.

[0023] (2)按照(1)的方法将0. 05gTS-l晶种分散在49. 95g的四丙基氢氧化铵TPAOH水溶液中制成晶种液,其PH = 6。 [0023] (2) The method (1) will be 0. 05gTS-l seed crystals dispersed in tetrapropylammonium hydroxide aqueous solution of TPAOH 49. 95g of seed was prepared, which PH = 6. 在100W、40KHz、65°C的超声条件下将前述晶种液Iml滴加在载体上,超声直到载体表面干燥后取出,制得b轴取向TS-I分子筛晶种层。 At 100W, ultrasonic condition 40KHz, 65 ° C seed crystals of the aforementioned solution was added dropwise Iml on a support, the support surface of the ultrasonic taken until drying, to obtain TS-I b-axis oriented seed layer of molecular sieve.

[0024] (3)按照(1)的方法将0. 15gTS-l晶种分散在49. 85g的四丙基氢氧化铵TPAOH水溶液中制成晶种液,其PH = 8. 5。 [0024] (3) according to (1) the method of 0. 15gTS-l seed crystals dispersed in tetrapropylammonium hydroxide aqueous solution of TPAOH 49. 85g of seed was prepared, which PH = 8. 5. 在160W、40KHZ、50°C的超声条件下将前述晶种液0. 65ml 滴加在载体上,超声直到载体表面干燥后取出,制得b轴取向TS-I分子筛晶种层。 At 160W, ultrasonic condition 40KHZ, 50 ° C seed crystals of the aforementioned solution was added dropwise to the carrier 0. 65ml, ultrasonic removed until the surface of the support and dried to prepare a b-axis oriented TS-I zeolite seed layer.

[0025] 实施方式2 [0025] Embodiment 2

[0026] 按照实施例1中(1)的方法制备晶种层。 [0026] Following the procedure in Example 1 (1) Preparation of seed crystal layer. 在10.8:3ml四丙基氢氧化铵QO % ) TPAOH的水溶液中加入96. 77ml的水,搅拌15分钟,再向其中滴加16克的硅溶胶(40% ),将0. 145克的钛酸四丁酯溶于3. 5ml的异丙醇后,在0°C、氮气保护作用下滴加到前述溶胶中, 搅拌20分钟,升温至80°C,在此温度下搅拌,蒸发除去溶胶中的醇,加水至原有液面高度, 冷却至室温,搅拌1小时,得到二次生长液,其组成为=ISiO2:0. 004ΤΒ0Τ:0· 1ΤΡΑ0Η:60Η20。 3ml was added tetrapropylammonium hydroxide of QO%) aqueous solution of TPAOH 96. 77ml of water, stirred for 15 minutes, again silica sol (40%) which was added dropwise 16 g of the titanium 0.145 g: 10.8 after tetrabutyl 3. 5ml of acid in isopropanol, at 0 ° C, was added dropwise to a nitrogen protective effect of the sol, stirred for 20 minutes, warmed to 80 ° C, stirred at this temperature, the sol is removed by evaporation in an alcohol, adding water to the original liquid level was cooled to room temperature, stirred for 1 hour, to obtain secondary growth solution consisting of = ISiO2:. 0 004ΤΒ0Τ: 0 · 1ΤΡΑ0Η: 60Η20.

[0027] 将担载有晶种的载体与二次生长液一并置于晶化反应釜中,载体水平放置,担载晶种的载体晶种层向下与二次生长液接触,在180°C二次生长M小时,取出冷却至室温,用去离子水洗至中性,干燥,550°C焙烧8小时除去模板剂,制得b轴取向TS-I分子筛膜。 [0027] A seed crystal supporting carrier liquid together with secondary growth crystallization reactor was placed in a horizontal position the carrier, the carrier carrying seed seed layer downward into contact with the liquid secondary growth, 180 ° C M secondary growth hours, then cool to room temperature, washed with deionized water until neutral, dried, 550 ° C was calcined for 8 hours to remove the template agent, b-axis orientation prepared TS-I molecular sieve membrane.

[0028] 实施方式3 [0028] Embodiment 3

[0029] 按照实施例1中⑵的方法制备晶种层,在实施例2的基础上,按照实施例2的方法,向7. 04ml的四丙基氢氧化铵(20% ) TPAOH的水溶液中加入56. 68ml的水,搅拌15分钟,再向其中滴加11. 09克的正硅酸乙酯,将0. 145g的钛酸四丁酯溶于3. 5ml的异丙醇后, 在0°C、氮气保护作用下滴加到前述溶胶中,搅拌20分钟,升温至82°C,在此温度下搅拌,蒸发除去溶胶中的醇,加水至原有液面高度,冷却至室温,搅拌1小时,得到二次生长液,其组成为=ITEOS:0. 008ΤΒ0Τ:0· 13ΤΡΑ0Η:65Η20,在175°C二次生长36 小时,制得b 轴取向TS-I 分子筛膜。 Preparation of the seed layer according to the method of Example ⑵ 1 embodiment, on the basis of Example 2, the procedure of Example 2 aqueous solution [0029] to tetrapropylammonium hydroxide (20%) 7. 04ml of the TPAOH after adding 56. 68ml water, stirred for 15 minutes, the dropwise addition of 11.09 g tetraethyl orthosilicate, tetrabutyl titanate 0. 145g 3. 5ml of isopropyl alcohol was dissolved in 0 ° C, under nitrogen, was added dropwise to the protective effect of the sol, stirred for 20 minutes, warmed to 82 ° C, stirred at this temperature, sol alcohol was removed by evaporation, water was added to the original liquid level was cooled to room temperature, stirred for 1 hour to obtain secondary growth solution consisting of = ITEOS:. 0 008ΤΒ0Τ: 0 · 13ΤΡΑ0Η: 65Η20, secondary growth for 36 hours at 175 ° C, b-axis orientation prepared TS-I molecular sieve membrane.

[0030] 实施方式4 [0030] Embodiment 4

[0031] 按照实施例1中(1)的方法制备晶种层,在实施例2的基础上,按照实施例2的方法,向6. 5ml的四丙基氢氧化铵(20% )TPAOH的水溶液中加入48. 48ml的水,搅拌15分钟,再向其中加入2. 56g的白炭黑,将0. 145g的钛酸四丁酯溶于3. 5ml的异丙醇后,在0°C、 氮气保护作用下滴加到前述溶胶中,搅拌20分钟,升温至82°C,在此温度下搅拌,蒸发除去溶胶中的醇,加水至原有液面高度,冷却至室温,搅拌1小时,得到二次生长液,其组成为: ISiO2:0. 01TB0T:0. 15TPA0H: 70H20,在180°C二次生长20 小时,制得b 轴取向TS-I 分子筛膜。 [0031] Preparation of the seed layer according to the method described in Example 1 (1), on the basis of Example 2, the procedure of Example 2, tetrapropyl ammonium hydroxide to 6. 5ml of (20%) TPAOH of 48. 48ml of water after the water was added, stirred for 15 minutes, to which was added 2. 56g of silica, of the tetrabutyl titanate was dissolved in 0. 145g 3. 5ml of isopropanol, from 0 ° C under nitrogen was added dropwise to the protective effect of the sol, stirred for 20 minutes, warmed to 82 ° C, stirred at this temperature, sol alcohol was removed by evaporation, water was added to the original liquid level was cooled to room temperature, stirred for 1 hour , secondary growth was obtained, consisting of: ISiO2: 0 01TB0T:. 0 15TPA0H:. 70H20, secondary growth for 20 hours at 180 ° C, b-axis orientation prepared TS-I molecular sieve membrane.

[0032] 实施方式5 [0032] Embodiment 5

[0033] 按照实施例1中(3)的方法制备晶种层,在实施例2的基础上,按照实施例2的方法,向8. 4ml的四丙基氢氧化铵(20% )TPAOH的水溶液中加入90. 53ml的水,搅拌15分钟,再向其中滴加13. 24g的正硅酸乙酯,将0. 145g的钛酸四乙酯溶于3. 5ml的异丙醇后, 在0°C、氮气保护作用下滴加到前述溶胶中,搅拌20分钟,升温至83°C,在此温度下搅拌,蒸发除去溶胶中的醇,加水至原有液面高度,冷却至室温,搅拌1小时,得到二次生长液,其组成为:1TE0S:0. 01TE0T:0. 13TPA0H: 85H20,在185°C二次生长36 小时,制得b 轴取向TS-I 分子筛膜。 [0033] Preparation of the seed layer according to the method described in Example 1 (3), on the basis of Example 2, the procedure of Example 2, tetrapropyl ammonium hydroxide to 8. 4ml of (20%) TPAOH of 90. 53ml of water after water was added, stirred for 15 minutes, the dropwise addition of TEOS 13. 24g, 0. 145g of the tetraethyl titanate 3. 5ml of isopropyl alcohol was dissolved in 0 ° C, under nitrogen, was added dropwise to the protective effect of the sol, stirred for 20 minutes, warmed to 83 ° C, stirred at this temperature, to remove alcohol sol evaporation, adding water to the original liquid level was cooled to room temperature, stirred for 1 hour, to obtain secondary growth solution consisting of: 1TE0S: 0 01TE0T:. 0 13TPA0H:. 85H20, secondary growth for 36 hours at 185 ° C, b-axis orientation prepared TS-I molecular sieve membrane.

[0034] 实施方式6 [0034] Embodiment 6

[0035] 按照实施例1中(2)的方法制备晶种层,在实施例2的基础上,按照实施例2的方法,向7. 46ml的四丙基氢氧化铵(20% ) TPAOH的水溶液中加入73. 24ml的水,搅拌15分钟,再向其中滴加10. 19g的正硅酸乙酯,将0. 145g的钛酸四乙酯溶于3. 5ml的异丙醇后, 在0°C、氮气保护作用下滴加到前述溶胶中,搅拌20分钟,升温至8rC,在此温度下搅拌,蒸发除去溶胶中的醇,加水至原有液面高度,冷却至室温,搅拌1小时,得到二次生长液,其组成为=ITEOS:0. 013ΤΕ0Τ:0· 15ΤΡΑ0Η:90Η20,在185°C二次生长40 小时,制得b 轴取向TS-I 分子筛膜。 [0035] Preparation of the seed layer according to the method described in Example 1 (2), on the basis of Example 2, the procedure of Example 2, tetrapropyl ammonium hydroxide to 7. 46ml of (20%) TPAOH of 73. 24ml of water after water was added, stirred for 15 minutes, the dropwise addition of TEOS 10. 19g, 0. 145g of the tetraethyl titanate 3. 5ml of isopropyl alcohol was dissolved in 0 ° C, under nitrogen, was added dropwise to the protective effect of the sol, stirred for 20 minutes, warmed to the 8RC, stirred at this temperature, sol alcohol was removed by evaporation, water was added to the original liquid level was cooled to room temperature, stirred for 1 hours, to obtain secondary growth solution consisting of = ITEOS:. 0 013ΤΕ0Τ: 0 · 15ΤΡΑ0Η: 90Η20, secondary growth 40 hours at 185 ° C, b-axis orientation prepared TS-I molecular sieve membrane.

[0036] 实施方式7 [0036] Embodiment 7

[0037] 按照实施例1中(1)的方法制备晶种层,在实施例2的基础上,按照实施例2的方法,向8. 08ml的四丙基氢氧化铵(20% ) TPAOH的水溶液中加入86. 49ml的水,搅拌15分钟, 再向其中滴加11.94g的硅溶胶(40% ),将0. 145g的钛酸四乙酯溶于3. 5ml的异丙醇后, 在0°C、氮气保护作用下滴加到前述溶胶中,搅拌20分钟,升温至85°C,在此温度下搅拌,蒸发除去溶胶中的醇,加水至原有液面高度,冷却至室温,搅拌1小时,得到二次生长液,其组成为=ISiO2:0. 008TE0T:0. 1TPA0H:70H20,在170°C二次生长50 小时,制得b 轴取向TS-I 分子筛膜。 [0037] Preparation of the seed layer according to the method described in Example 1 (1), on the basis of Example 2, the procedure of Example 2, the tetrapropyl ammonium hydroxide (20%) 8. 08ml of the TPAOH 86. 49ml of water after the water was added, stirred for 15 minutes, the dropwise addition of 11.94g of silica sol (40%), and 0. 145g of tetraethyl titanate in isopropanol 3. 5ml in 0 ° C, under nitrogen, was added dropwise to the protective effect of the sol, stirred for 20 minutes, warmed to 85 ° C, stirred at this temperature, to remove alcohol sol evaporation, adding water to the original liquid level was cooled to room temperature, stirred for 1 hour, to obtain secondary growth solution consisting of = ISiO2: 0 008TE0T:.. 0 1TPA0H: 70H20, secondary growth 50 hours at 170 ° C, b-axis orientation prepared TS-I molecular sieve membrane.

Claims (7)

1. 一种利用二次生长法制备b轴取向TS-I分子筛膜的方法,其方法是采用静电吸附一超声法将分子筛晶种担载在载体上,调节晶种液的PH值形成表面静电层,在超声辅助下使晶种以最大的ac面与载体接触,制得b轴取向TS-I分子筛晶种层;将担载有晶种的载体与二次生长液一起置于晶化反应釜中进行二次生长,取出,冷却至室温,用去离子水洗至中性,干燥、焙烧后制得b轴取向TS-I分子筛膜;该方法的具体制备步骤依次进行如下:首先,将TS-I分子筛晶种分散在四丙基氢氧化铵TPAOH水溶液中制成晶种液,调节其PH值为3. 5〜8. 5,将内置滤纸的培养皿放入超声波清洗器,再将载体放入培养皿内的滤纸上,用四丙基氢氧化铵TPAOH水溶液将载体和滤纸浸透,在超声条件下将前述晶种液滴加在载体上,超声直到载体表面干燥后取出,制得b轴取向TS-I分子筛晶种层;其次 Preparation 1. A method of utilizing secondary growth method b-oriented TS-I zeolite membrane, which is a electrostatic adsorption ultrasound molecular sieve seed crystals supported on a carrier, adjusting the PH value of the liquid crystal seed forming surface electrostatic layer, the seed crystal at the maximum ac contacted with the support surface, b-axis orientation prepared zeolite TS-I seed layer under ultrasound assisted; and carries a secondary carrier liquid crystal growing seed crystal was placed with reaction autoclave for secondary growth, removed, cooled to room temperature, washed with deionized water until neutral, dried to obtain TS-I b-axis oriented film was calcined zeolite; specific preparation steps of the process sequence as follows: first, the TS -I zeolite seed crystal dispersion in TPAOH tetrapropylammonium hydroxide aqueous solution to prepare a seed crystal, adjusting the PH value of 3. 5 ~ 8. 5, the filter paper into the petri dish built ultrasonic cleaning, and then the carrier placed on the filter paper in the petri dish, using TPAOH tetrapropylammonium hydroxide aqueous solution and filter paper impregnated carrier, under ultrasonic conditions, the seed crystal added dropwise to the carrier, the carrier surface ultrasonic removed until after drying, to obtain b zeolite TS-I-axis orientation of the seed layer; Second 将硅源滴加到四丙基氢氧化铵的水溶液中,于室温下搅拌,得到溶胶,再将钛源溶于异丙醇后,将其在0°C、氮气保护作用下,滴加到前述溶胶中,升温至80〜85°C,在此温度下搅拌,蒸发除去溶胶中的醇,加水至原有液面高度,冷却至室温,搅拌1小时,得到二次生长液,其组成为:aSi:bTi:cTPA0H:dH20,其中a = 1,b = 0. 004 〜0. 013,c = 0. 1 〜 0. 15,d = 60 〜90 ;最后,将所得到的担载有晶种的载体与二次生长液一起置于晶化反应釜中,载体水平放置,担载晶种的载体晶种层向下与二次生长液接触,在170〜185°C二次生长20〜50小时,取出冷却至室温,用去离子水洗至中性,干燥,550°C焙烧8小时除去模板剂,制得b轴取向TS-I分子筛膜。 The silicon source added dropwise tetrapropyl ammonium hydroxide aqueous solution, stirred at room temperature to give a sol, the titanium source and then dissolved in isopropanol, which was at 0 ° C, nitrogen protection, was added dropwise the sol was warmed to 80~85 ° C, stirred at this temperature, the sol is removed by evaporation of the alcohol, add water to the original liquid level was cooled to room temperature, stirred for 1 hour, to obtain secondary growth solution consisting of .: aSi: bTi: cTPA0H: dH20, wherein a = 1, b = 0. 004 ~0 013, c = 0. 1 ~ 0. 15, d = 60 ~90; Finally, the resulting crystal-supporting secondary growth species carriers were placed together with the crystallization reactor, the carrier horizontally, carrying the seed carrier seed layer downward into contact with the liquid secondary growth, secondary growth at 170~185 ° C 20~ 50 hours, then cool to room temperature, washed with deionized water until neutral, dried, 550 ° C was calcined for 8 hours to remove the template agent, b-axis orientation prepared TS-I molecular sieve membrane.
2.如权利要求1所述的方法,其载体是片状α-Al2O3多孔陶瓷载体或是硅片。 2. The method according to claim 1, which is a sheet-like carrier α-Al2O3 porous ceramic support or a silicon wafer.
3.如权利要求1所述的方法,其晶种液的浓度是0. 1〜0. 5%,滴加量为0. 5〜1ml。 The method according to claim 1, which is the concentration of the seed liquid was 0.5 1~0. 5%, was added dropwise in an amount of 0. 5~1ml.
4.如权利要求1所述的方法,其超声波清洗器的频率为40KHz,超声功率为100〜 200W。 4. The method according to claim 1, which frequency is 40KHz ultrasonic cleaning, ultrasonic power 100~ 200W.
5.如权利要求1所述的方法,其超声波清洗器内的环境温度为40〜65°C。 5. The method according to claim 1, the ambient temperature in which the ultrasonic cleaning is 40~65 ° C.
6.如权利要求1所述的方法,其硅源是硅溶胶、正硅酸乙酯或是白炭黑。 6. The method according to claim 1, which is a source of silicon sol, orthosilicate or silica.
7.如权利要求1所述的方法,其钛源是钛酸四乙酯或是钛酸四丁酯。 7. The method according to claim 1, which is the titanium source tetrabutyl titanate or tetraethyl titanate.
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