WO2012010069A1 - 一种在大孔载体上NaA沸石分子筛膜的合成方法 - Google Patents

一种在大孔载体上NaA沸石分子筛膜的合成方法 Download PDF

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WO2012010069A1
WO2012010069A1 PCT/CN2011/077183 CN2011077183W WO2012010069A1 WO 2012010069 A1 WO2012010069 A1 WO 2012010069A1 CN 2011077183 W CN2011077183 W CN 2011077183W WO 2012010069 A1 WO2012010069 A1 WO 2012010069A1
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molecular sieve
membrane
naa
zeolite molecular
naa zeolite
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王金渠
杨建华
盛春光
周志辉
陈赞
鲁金明
殷德宏
张艳
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Dalian University of Technology
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
    • B01D71/02—Inorganic material
    • B01D71/028—Molecular sieves
    • B01D71/0281—Zeolites
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
    • B01D67/0039—Inorganic membrane manufacture
    • B01D67/0051—Inorganic membrane manufacture by controlled crystallisation, e,.g. hydrothermal growth
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/74—Separation; Purification; Use of additives, e.g. for stabilisation
    • C07C29/76—Separation; Purification; Use of additives, e.g. for stabilisation by physical treatment
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2323/00—Details relating to membrane preparation
    • B01D2323/12—Specific ratios of components used
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2323/00—Details relating to membrane preparation
    • B01D2323/42—Details of membrane preparation apparatus

Definitions

  • the invention relates to a method for synthesizing a zeolite molecular sieve membrane, in particular to preparing a NaA with excellent performance after pre-coating a seed crystal by a hot dipping method on a macroporous carrier.
  • Zeolite molecular sieve membrane Zeolite molecular sieve membrane.
  • Pervaporation is a membrane separation technology that has been rapidly developed in the past two decades. It utilizes the adsorption (or dissolution or sieving) and diffusion properties of the components in a binary or multi-component liquid mixture on the separation membrane to achieve separation of the mixture. It is known from the principle of pervaporation that the pervaporation membrane separation process is not limited by the vapor-liquid equilibrium, and therefore has unique advantages for the separation of near-boiling and azeotrope which are difficult to handle by conventional separation means. In addition, for the removal of some trace components in the mixture, pervaporation shows higher separation efficiency, and compared with traditional separation methods such as distillation, absorption, extraction, etc., pervaporation has incomparable advantages, such as equipment.
  • the pervaporation membranes used today are mostly organic polymer membranes, and such materials have the disadvantages of poor chemical stability, thermal stability and mechanical stability, and it is difficult to obtain high flux and selectivity, thereby making their application fields subject to The limit.
  • the zeolite molecular membrane uses a porous material as a carrier to grow a zeolite molecular sieve on its surface. It has a uniform pore size and a pore size similar to the molecular size, adjustable surface characteristics, high temperature resistance, good chemical stability, solvent resistance and microbial corrosion. High performance, high strength, wear resistance, easy cleaning, etc., making it high temperature , a large pressure gradient, and use in harsh operating environments such as acid-base media or bio-erosion with a certain intensity, Has a unique advantage. Zeolite molecular sieve membrane has become one of the most promising membranes, and its preparation and application research have become the research hotspot and frontier of membrane science and technology.
  • the NaA zeolite molecular sieve membrane has a three-dimensional eight-membered ring channel system with a crystal channel diameter of 4.1 ⁇ ⁇ 4.1 ⁇ , and the composition of Si/Al Ratio (referred to as the molar ratio) is 1:1 It is extremely hydrophilic, and it exhibits excellent ideal molecular sieve selectivity and extremely high permeation flux for dehydration of organic matter over a wide range of concentrations, thus separating the organic solvent mixture.
  • NaA The component that is permeated through the membrane is only water, and the permeate flux is two orders of magnitude larger than the organic membrane 1-2, which makes NaA
  • the zeolite membrane can be efficiently separated in a wide concentration range including an azeotrope, and the application range is wide, so that the purity of the product can reach a higher demand. It is also important that the molecular sieve itself has excellent physical properties such as high temperature resistance, good chemical stability, solvent resistance and microbial corrosion resistance.
  • the NaA zeolite membrane can be used in conditions such as high temperature, strong solvent, and strong biocorrosion. NaA
  • the technical problem to be solved by the present invention is to provide a macroporous carrier for the market.
  • High performance, highly reproducible NaA was prepared on the surface of macroporous supports by providing a novel seed coating method, a two-step seed-assisted secondary growth method.
  • Zeolite molecular sieve membranes are applied to water by pervaporation to remove ethanol.
  • NaOH, NaAlO 2 , silica sol and deionized water are added in order, and the synthetic liquid is obtained by vigorous stirring and aging, and then the treated carrier tube is firstly subjected to a two-step seeding method, that is, firstly, the NaA crystal is thermally dipped. Apply to the surface of the carrier, then apply NaA seed crystals to the macroporous support such as ⁇ -Al 2 O 3 , stainless steel or mullite by lift or spin coating; or apply large crystal The high-performance NaA zeolite molecular sieve membrane is obtained by a secondary repair synthesis method without applying a small seed crystal.
  • the NaA zeolite molecular sieve membrane with excellent separation performance was synthesized by dynamic hydrothermal crystallization in a rotary oven by controlling the growth of the synthetic membrane and the separation performance of the membrane by the difference in the grain size of the seed crystal.
  • the grain size of the large seed crystal is slightly smaller than the average pore size of the carrier.
  • the seed crystal serves to modify the macropore pore size to reduce the pore size of the carrier, so that the NaA zeolite can form a uniform and continuous NaA zeolite membrane on the surface of the carrier, while preventing a large amount of NaA zeolite.
  • Molecular sieves are formed in the pores of the carrier, resulting in a decrease in the flux of the membrane and at the same time inducing the growth of the NaA zeolite molecular sieve.
  • the small seed crystals mainly induce NaA zeolite which induces uniformity and separation performance of the NaA zeolite molecular sieve on the surface of the carrier.
  • Molecular sieve membrane The prepared membrane was characterized by scanning electron microscopy and XRD, and the separation performance of the membrane was evaluated by pervaporation separation of water in ethanol using a NaA membrane.
  • the treated carrier tube is passed through a two-step seeding method, that is, first, a NaA seed crystal is applied to the surface of the carrier by hot dipping, and then the NaA seed crystal is applied to ⁇ -Al 2 by lift or spin coating.
  • a macroporous support such as O 3 , stainless steel or mullite; or by applying a large seed crystal, without applying a small seed crystal, the other synthesis conditions remain the same as the two-step seed method of simultaneously applying the size seed crystal method.
  • the prepared NaA molecular sieve membrane is soaked in neutralized water with deionized water.
  • the synthesized membrane is repeatedly rinsed with deionized water to neutrality and then naturally dried. It can also be dried in an oven at 20-100 °C for 6-24 hours. use.
  • the pore size of the carrier tube may be from 0.1 ⁇ m to 4 ⁇ m and the porosity is from 30 to 50%.
  • NaA The large seed crystal refers to a NaA zeolite molecular sieve crystal grain having a size of 1 - 3 ⁇ m.
  • the NaA small seed crystal refers to a NaA zeolite molecular sieve grain having a size of 50 - 600 nm.
  • the hot dipping method refers to putting a carrier tube preheated at a temperature of 50-200 ° C into a prepared large seed crystal solution, and the immersion time is 10-50s, the concentration of seed crystals in the seed solution is 2-10wt.%,
  • the seed crystal is applied to the surface of the carrier; the method is to form a negative pressure by rapid cooling of the hot air in the carrier tube, so that the seed crystal in the seed liquid is adsorbed into the surface channel of the carrier tube.
  • the synthesized NaA zeolite molecular sieve membrane is pervaporated to carry out ethanol dehydration, and the concentration in ethanol is 50-99 wt.%. In the range of the separation, the separation performance is excellent, the repeatability is high, and it is suitable for large-scale applications.
  • the effect of the present invention is to provide a method for seeding a seed on a macroporous support, and to regulate the growth of the NaA zeolite membrane by the size of the seed crystal, thereby overcoming the difficulty of film formation on the macroporous support.
  • a dense continuous high-performance NaA zeolite membrane is prepared on the surface of a carrier having a macroporous ⁇ -Al 2 O 3 having a length of 5 to 120 cm, which is available on the domestic market, and the membrane is pervaporated to carry out ethanol dehydration in ethanol.
  • the concentration is in the range of 50-99wt.%, the separation performance is excellent, the repeatability is high, and it is suitable for large-scale application, and has important industrial application value and practical significance.
  • Figure 1 is a surface view a and a cross-sectional view b of an SEM image of an ⁇ -Al 2 O 3 carrier tube.
  • Figure 2 is a surface view a and a cross-sectional view b of the SEM image of the synthesized NaA film.
  • Figure 3 is a surface view a and a cross-sectional view b of the SEM image of the synthesized NaA film.
  • Figure 4 is an XRD picture of a synthetic NaA film.
  • * is the characteristic peak of the carrier tube Al 2 O 3 .
  • Figure 5 is a flow chart of pervaporation.
  • the carrier tube used in the embodiment of the present invention is provided by Nanjing University of Technology with a nominal pore size of 2-3 ⁇ m and a porosity of 30-40% ⁇ -Al 2 O 3 tube, or Guangdong Foshan Ceramic Research Institute or Jiexi Smooth Technology Co., Ltd.
  • An ⁇ -Al 2 O 3 tube having a nominal pore size of 2-3 ⁇ m and a porosity of 30-40% is provided, and the tube length is 80 cm.
  • the surface of the carrier tube is sequentially used 600# and 800#
  • the waterproof sandpaper is sanded until the surface of the carrier is smooth, and then ultrasonically shaken with acid and alkali to remove the residue in the carrier pores, washed with deionized water until neutral, and then dried naturally, and finally at 150 °C. Dry at room temperature for use.
  • Step 1 The carrier tube is pretreated in the same manner as in step 1 of Example 1.
  • Step 2 Preparation of carrier seed layer: The large seed crystal is applied to the surface of the carrier only by hot dipping-wiping method, and no small seed crystal is coated. Steps are the same as the embodiment Step 1 in step 2 of the procedure (1).
  • the NaA film obtained is M2, that is, M2 before the repair. Since only a large seed crystal is coated, the separation selectivity of the one-step crystallized NaA zeolite membrane needs to be improved, and in order to further improve the separation performance of the NaA zeolite membrane, a two-step crystallization synthesis is employed. As described above, the first step of the synthesis process is exactly the same as in step 3 of the embodiment 1. In the second step, the conditions and formulation were changed.
  • the two ends of the membrane tube synthesized in the first step were blocked with a Teflon plug and placed vertically in a stainless steel reaction vessel, and then the above synthetic liquid was transferred to a crystallization vessel, and then the kettle was fixed in a rotary oven at 100 °C. After crystallization for a certain period of time, it was taken out, cooled to room temperature, and the film tube was taken out and washed with deionized water until neutral, and dried. The surface morphology of the dried NaA zeolite molecular sieve membrane was confirmed by SEM photograph (Fig. 3), and the obtained NaA membrane was repaired M2. It can be seen from the figure that the second step of the synthesis is only to repair the defects existing in the first unsynthesized film.
  • the treated NaA zeolite molecular sieve membrane is installed in a membrane separator, and both ends are sealed with a corrosion-resistant fluorine rubber O-type gasket, and an aqueous solution of ethanol or an aqueous solution of isopropanol having a concentration of 50.0-99.0 wt.% is separated and supplied to the mixture.
  • the shell of the membrane is evacuated from the tube side of the membrane.
  • the flux and separation factor of the membrane were measured at a temperature of 70 ° C and a vacuum of 200-400 Pa on the permeate side.
  • the raw material component, the permeation component and the retentate component are analyzed by gas chromatography, and the flux of the membrane is determined by collecting the permeate condensed by liquid nitrogen for 10 to 60 minutes at a specific time to determine the composition of the weight and the permeation component. Calculated.
  • the pervaporation performance of the membrane is represented by the permeation flux J and the separation factor ⁇ , respectively.
  • the composition of the raw material liquid and the permeate was analyzed by HP6890+ gas chromatograph produced by Agilent.
  • Thermal conductivity detection Permeate flux J Separation coefficient ⁇ Calculated as follows:
  • M is the total weight (kg) collected on the permeate side of the membrane for a certain period of time ⁇ t (h)
  • A is the effective area of the membrane (m 2 )
  • J is the total permeate flux of the membrane
  • the permeate flux is calculated from the total permeate flux and its composition.
  • i is the component water
  • j is the mass percentage of the material side and the permeate side material which are not easily permeated through the component ethanol or isopropanol
  • ⁇ is a separation coefficient, indicating the water-to-alcohol separation coefficient of the membrane.
  • Example 1 and Example 2 were respectively subjected to pervaporation performance of an ethanol/water system or an isopropanol/water system, and the flow thereof is shown in Fig. 3, wherein (a) a magnetic stirrer (b) constant temperature oil Bath (c) membrane tube (d) membrane module (e) ethanol/water raw material liquid (f) cold trap (g) liquid nitrogen (h) silicon vacuum tube (i) vacuum buffer bottle (j) iron frame (k) vacuum gauge ( l ) Vacuum pump.
  • the operating temperature is 70 °C
  • the M1 of the permeate side is 200-400 Pa
  • the separation factor of the M2 after the second repair is Between 5000 and ⁇
  • the permeate flux is between 1.45-1.81 kg/m 2 h. It exhibits good separation performance and has important industrial application value and practical significance.

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  • Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Geology (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Silicates, Zeolites, And Molecular Sieves (AREA)
  • Separation Using Semi-Permeable Membranes (AREA)

Description

一种在大孔载体上NaA沸石分子筛膜的合成方法
技术领域
本发明涉及一种沸石分子筛膜的合成方法，尤其是涉及在大孔载体上利用热浸渍法预涂晶种后制备性能优良的 NaA 沸石分子筛膜。
背景技术
渗透蒸发（ PV ）是近二十年迅速发展起来的一种膜分离技术，它利用二元或多元液体混合物中各组分在分离膜上的吸附（或溶解或筛分）及扩散性能的不同实现混合物的分离，由渗透蒸发的原理可知，渗透蒸发膜分离过程不受汽液平衡的限制，因此对于那些用传统分离手段难以处理的近沸、共沸物的分离具有独特的优越性。另外，对于混合物中某些微量组分的脱除，渗透蒸发更显示出高的分离效率，同时与传统的精馏、吸收、萃取等分离方法相比，渗透蒸发具有无法比拟的优点，如设备和操作简单、污染小、能耗低、分离效率高等优点。然而现在所用的渗透蒸发膜多为有机高分子膜，此类材料存在着化学稳定性、热稳定性和机械稳定性差的缺点，而且难以获得高的通量和选择性，从而使其应用领域受到了限制。
沸石分子膜是利用多孔材料作为载体，将沸石分子筛生长在其表面，它具有均一的孔径且孔径大小与分子尺寸相近、表面特性可调、耐高温，化学稳定性好，抗溶剂性和微生物腐蚀能力强，强度高耐磨损、易清洗等优良特性、使得其在高温 , 较大的压力梯度 , 以及处于具有一定强度的酸碱介质或生物侵蚀等苛刻的操作环境下使用 , 具有了得天独厚的优势。沸石分子筛膜成为最具潜力最有前途膜之一，其制备与应用研究成为膜科学与技术的研究热点和前沿。
NaA 沸石分子筛膜是具有三维八元环孔道体系，结晶孔道直径为 4.1Å×4.1Å ，组成中 Si/Al 比（指摩尔比）为 1:1 ，具有极强的亲水性，这些特性使其在广泛的浓度范围内对有机物脱水中表现了优异的理想的分子筛分选择性和极高的渗透通量，从而在分离有机溶剂混合物时，从 NaA 膜中透过的组分只有水，渗透通量是有机膜 1-2 两个数量级，这使 NaA 沸石膜在处理有机物脱水时，可以包含共沸物在内的广泛的浓度区域进行高效分离，使其应用范围广阔，使产品的纯度能达到更高的需求。同样重要的是，由于分子筛本身固有的耐高温，化学稳定性好，抗溶剂性和微生物腐蚀能力强等优异的物理特性， NaA 沸石膜可以用在高温，强溶剂，生物腐蚀性强等条件和环境下的操作。 NaA 沸石分子筛的这些优异特性是有机膜无可比拟的，使其在脱除各种有机物中的水及精制有机物中具有广泛应用。
发明内容
本发明要解决的技术问题是针对市场提供的 大孔载体， 通过提供一种新型的晶种涂覆方法即两步晶种法辅助的二次生长法，在 大孔载体表面上制备了高性能、高重复性的 NaA 沸石分子筛膜，并将其应用于渗透蒸发脱除乙醇中的水。
将 NaOH 、 NaAlO2 、硅溶胶和去离子水按顺序添加，并通过剧烈搅拌和陈化得到合成液 , 然后将处理好的载体管通过两步晶种法即首先用热浸渍法将 NaA 大晶种涂敷至载体表面，然后用提拉或旋转涂晶法将 NaA 小晶种涂敷到 α-Al2O3 、不绣钢或莫来石等大孔载体上；或采用涂敷大晶种、不涂敷小晶种，而后通过二次修补合成法得到高性能 NaA 沸石分子筛膜。通过晶种晶粒大小的不同所起作用的不同，调控合成膜的生长及膜的分离性能，在旋转烘箱中进行动态水热晶化合成分离性能优异的 NaA 沸石分子筛膜。大晶种的晶粒大小比载体平均孔径稍小，该晶种起修饰大孔孔径减小载体孔径的作用，使 NaA 沸石能在载体表面形成一致密连续的 NaA 沸石膜，同时防止大量 NaA 沸石分子筛在载体孔内生成，导致膜的通量减小，同时起诱导 NaA 沸石分子筛生长的作用，小晶种则主要起诱导 NaA 沸石分子筛在载体表面生成一致密性和分离性能更佳的 NaA 沸石分子筛膜。用扫描电镜和 XRD 来表征制备的膜，用 NaA 膜渗透蒸发分离乙醇中的水来评价膜的分离性能。
本发明的技术方案如下：
将处理好的载体管通过两步晶种法即首先用热浸渍法将 NaA 大晶种涂敷至载体表面，然后用提拉或旋转涂晶法将 NaA 小晶种涂敷到 α-Al2O3 、不绣钢或莫来石等大孔载体上；或采用涂敷大晶种、不涂敷小晶种，其它合成条件与同时涂敷大小晶种法的两步晶种法保持相同，而后通过二次修补合成法得到高性能 NaA 沸石分子筛膜； NaA 沸石 分子筛 膜按照如下方式制备： Al2O3:SiO2:Na2O:H 2O=1:2.5-5:25-50:500-1000 摩尔比配制成合成液，利用水热合成 在大孔载体 上 制得；合成温度为 80-100 ℃ ，合成时间为 3-6h ； 对于存在 二次修补合成的情况，二次修补时晶化温度、晶化时间为 90-100 ℃ 、 2-4h , 其摩尔比配方为： Al2O3:SiO2:Na2O:H 2O=1:2:2:100-150 ， 最终也可获得高性能的 NaA 沸石膜。 制备好的 NaA 分子筛 膜用去离子水浸泡至中性， 合成好的膜用去离子水反复冲洗至中性后自然晾干，也可以放入 20-100 ℃烘箱中干燥 6-24h 后保存待用。
其中载体管的孔尺寸可以介于 0.1μm 到 4μm ， 孔隙率为30-50%。 NaA 大晶种是指尺寸可以为 1 - 3μm 的NaA沸石分子筛晶粒。 NaA 小晶种是指尺寸可以为 50 - 600nm 的 NaA 沸石分子筛晶粒。
所述热浸渍法是指把在温度为 50-200 ℃ 的条件下预热过的载体管放入配制好的大晶种溶液中，浸渍时间为 10-50s ， 晶种液中晶种的浓度为 2-10wt.% ， 将晶种涂敷至载体表面；该方法是利用载体管内热空气的急剧冷却形成负压，使晶种液中的晶种吸附到载体管的表面孔道中。
所合成 NaA 沸石分子筛膜渗透蒸发进行乙醇脱水时，在乙醇的浓度为 50-99wt.% 的范围内，分离性能优良、重复性高，适合规模化应用。
本发明的效果益处是：提供了一种晶种负载在大孔载体上的方法，并通过晶种的大小来调控 NaA 沸石膜的生长，克服了在大孔载体上不易成膜的难点，在国内市场上可得的膜的长度为 5-120cm 的大孔 α-Al2O3 等材质的载体表面上制备了 致密连续高性能的 NaA 沸石膜，该膜渗透蒸发进行乙醇脱水时，在乙醇的浓度为 50-99wt.% 的范围内，分离性能优良、重复性高、适合规模化应用，具有重要的工业应用价值及实际意义。
附图说明
图 1 是α -Al2O3 载体管 SEM 图片的表面图 a 和截面图 b 。
图 2 是合成的 NaA 膜的 SEM 图片的表面图 a 和截面图 b 。
图 3 是合成的 NaA 膜的 SEM 图片的表面图 a 和截面图 b 。
图 4 是合成的 NaA 膜的 XRD 图片。
图中： * 为载体管 Al2O3 特征峰。
图 5 是渗透蒸发流程图。
具体实施方式
实施例 1
步骤 1 、载体管预处理
为 本发明实施例中所用载体管为南京工业大学提供的公称孔径为 2-3 μm ，孔隙率为 30-40% α-Al2O3 管，或广东佛山陶瓷研究所或揭西顺利科技公司提供的公称孔径为 2-3 μm ，孔隙率为 30-40% 的 α-Al2O3 管，管长为 80cm 。
将载体管表面依次用 600# 与 800# 的防水砂纸进行打磨，直至载体表面光滑，然后分别用酸、碱超声震荡以清除载体孔内残留物，并用去离子水洗至中性后自然晾干，最后在 150 ℃ 温度下烘干备用。
步骤 2 、载体晶种层的制备
  1. （1） 采用热浸渍法，在处理好的载体管上涂敷大晶种：将自制的晶粒尺寸为 1~3μm 的 NaA 分子筛以 1K/min 的速度升温至 550 ℃ ，并保持 4h ，以除去分子筛中有机模板剂，然后将其配置成 10% 的晶种水溶液，迅速将已经在 180 ℃ 温度下烘了 4h 的载体管浸渍到上述的晶种液中，浸渍时间为 20s ，之后将涂有晶种的载体管放在 50~100℃的烘箱中干燥，最后用脱脂棉轻轻擦除载体表面多余的分子筛。
  1. （2） 利用提拉法对上述的载体管二次涂敷小晶种：将自制的小晶粒平均尺寸 400 nm 的 NaA 分子筛，同样以 1K/min 的速度升温至 550 ℃ ，并保持 4h ，以除去分子筛中的模板剂，然后配制成 2% 的晶种水溶液，接着将涂完大晶种的载体管浸渍到该晶种液中，浸渍时间为 20s ，最后将该载体放在 50 ～ 100 ℃烘箱中干燥，以备合成之用。
步骤 3 、 NaA 沸石分子筛膜的制备
称取 1.9g 的 NaAlO2 和 35.6g 的 NaOH 溶解于 156.5g 的去离子水中，待澄清后缓慢滴加 9.3g 硅溶胶 (SiO2 wt.% = 26.0, Na2O wt.%=0.05) 并充分搅拌直至变为澄清溶液，该溶液即为合成膜用的母液，其各组分组成为 Al2O3:SiO2:Na2O:H 2O=1:5:50:1000 。之后，将涂有晶种的载体两端用聚四氟乙烯塞堵住两端垂直放进不锈钢反应釜中，并加入上述配置好的合成液，密封后将釜固定在 80 ℃ 旋转烘箱中加热晶化 5h 后取出，冷却至室温，取出膜管并用去离子水洗涤至中性，烘干。烘干后的 NaA 沸石分子筛膜晶体结构和膜表面形貌经由 SEM 照片（附图 2 ）与 XRD （附图 4 ）分析得以证实，得到的 NaA 膜计为 M1.
实施例 2
步骤 1 、载体管预处理同实施例 1 中步骤 1 。
步骤 2 、载体晶种层的制备：本次只采用热浸渍-擦涂法将大晶种涂覆至载体表面，不涂覆小晶种。步骤同实施例 1 中步骤 2 中过程 (1) 。
步骤 3 、 NaA 沸石分子筛膜的制备
同实施例 1 中步骤 3 ，得到的 NaA 膜为 M2, 即为修补前 M2 。由于只涂覆了大晶种，一步晶化合成的 NaA 沸石膜的分离选择性有待提高，为了进一步提高 NaA 沸石膜的分离性能，采用两步晶化合成。如上所述，第一步合成过程完全同于实施例 1 中步骤 3 。而第二步合成则改变条件及配方，具体实施过程如下： 在 200 ml 的烧杯中将 6.80 g NaAlO2 和 2.072 g NaOH 充分溶解于 107.875 g 水中，强烈搅拌 1 h ，再将 15.385 g 硅溶胶 (SiO2 wt.% = 26.0 wt.%, Na2O=0.05%) 缓慢加入到上面搅拌好的铝酸盐中 , 然后继续搅拌 3 h 制成白色乳状溶胶合成液，其各组分的组成为 Al2O3:SiO2:Na2O:H 2O=1:2:2:120 。 将第一步合成的膜管两端用聚四氟乙烯塞子堵死并垂直放入不锈钢反应釜中，然后将上述合成液转移到晶化釜中，接着将釜固定到 100 ℃ 的旋转烘箱中，晶化一定时间后取出，冷却至室温，取出膜管并用去离子水洗涤至中性，烘干。烘干后的 NaA 沸石分子筛膜表面形貌经由 SEM 照片（附图 3 ）分析得以证实 , 得到的 NaA 膜为修补后的 M2 。从图中可以看出第二步合成只是对第一不合成的膜存在的缺陷进行了修补。
实施例 3
将处理好的 NaA 沸石分子筛膜安装到膜分离器中，两端用耐腐蚀的氟胶 O 型垫圈密封，分离原料液浓度为 50.0-99.0wt.% 的乙醇水溶液或异丙醇水溶液循环供至膜的壳层，膜的管侧抽真空。在温度为 70 ℃时，渗透侧的真空度为 200-400Pa 的条件下，测定膜的通量和分离系数。 经气相色谱对原料组分、渗透组分和渗余组分进行分析， 膜的通量是通过收集特定时间 10-60 分钟间经液氮冷凝的渗透物测定其重量和 渗透组分的组成而计算获得。膜的渗透汽化性能分别用渗透通量 J 及分离系数 α 表示。 原料液和渗透液的组成用 Agilent 公司生产的 HP6890 ＋型气相色谱进行分析，色谱柱 HP-5 ，固定相为苯甲基硅烷，柱长 30 m ，内径 0.32 mm ， H2 为载气，使用热导检测。渗透通量 J 分离系数 α 按下式计算：
Figure PCTCN2011077183-appb-I000001
(1)
Figure PCTCN2011077183-appb-I000002
(2)
其中， M 为经过一定时间Δ t （ h ），膜的透过侧收集到的总重量（ kg ）， A 为膜的有效面积（ m2 ）， J 为膜的总渗透通量，组分的渗透通量由总渗透通量和其组成算出。 i 为组分水， j 为不易透过组分乙醇或异丙醇料侧和透过侧物质的质量百分比组成，α为分离系数，表示膜的水对醇类分离系数。
对实施例 1 和实施例 2 合成的膜管分别进行乙醇 / 水体系或异丙醇 / 水体系 渗透蒸发性能研究，其流程如图 3 所示，其中 (a) 磁力搅拌器（ b ）恒温油浴（ c ）膜管（ d ）膜组件（ e ）乙醇 / 水原料液（ f ）冷阱（ g ）液氮（ h ）硅真空管（ i ）真空缓冲瓶（ j ）铁架台（ k ）真空表（ l ）真空泵。对于乙醇或异丙醇质量分数为 90wt.% 的乙醇 / 水体系，操作温度为 70 ℃ ，渗透侧的真空度为 200-400Pa 的条件下合成的 M1 和二次修补后膜 M2 的分离系数在 5000- ∞之间，渗透通量在 1.45-1.81kg/m2h 。表现出良好的分离性能，具有重要的工业应用价值和实际意义。
表1 合成的NaA膜M1 渗透蒸发乙醇水溶液分离性能
Concentration [ wt.% ] Separation
Temperature [ ℃ ]		 Water Flux
[kg·m-2·h-1]		 Separation factor
αH2O/EtOH [-]
85.0 70 2.87 ∞
90.0 70 1.81 46246
95.0 70 1.00 37886
表2 合成的NaA膜M1 渗透蒸发异丙醇水溶液分离性能
Concentration [ wt.% ] Separation
Temperature [ ℃ ]		 Flux
[kg·m-2·h-1]		 Separation factor
αH2O/IPA [-]
85.0 70 2.15 ∞
90.0 70 1.60 ∞
95.0 70 0.88 10458
表3 合成的NaA膜M2渗透蒸发乙醇水溶液分离性能
Concentration [ wt.% ] Separation
Temperature
[ ℃ ]		 Flux
[kg·m-2·h-1]		 Separation factor
αH2O/ EtOH [-]
修补前
90.0 70 2.18 200
修补后
90.0 70 1.45 5000

Claims (1)

1 、一种在大孔载体上 NaA 沸石分子筛膜的制备方法，其特征在于如下步骤，
（ 1 ）将处理好的载体管利用两步晶种法预涂大小晶种得到高性能 NaA 沸石分子筛膜；或采用涂敷大晶种、不涂敷小晶种，而后通过二次修补合成法得到高性能 NaA 沸石分子筛膜；
（ 2 ） NaA 沸石 分子筛 膜按照如下方式制备： Al2O3:SiO2:Na2O:H 2O=1:2.5-5:25-50:500-1000 摩尔比配制成合成液，利用水热合成 在大孔载体 上 制得； NaA 沸石膜的晶化是在旋转烘箱中动态进行， 温度为 80 - 100 ℃ ，合成时间为 3 - 6h ；
对于存在 二次修补合成的情况，二次修补时晶化温度、晶化时间为 90-100℃ 、 2-4h , 其摩尔比配方分别为： Al2O3:SiO2:Na2O:H 2O=1:2:2:100-150 ；
（ 3 ）制备好的 NaA 分子筛 膜用去离子水浸泡至中性， 干燥。
2. 按照权利要求1所述的制备方法，其特征在于载体管的孔尺寸介于 0.1 μm 到 4 μm ，孔隙率为30-50%。
3 、按照权利要求1或2所述的制备方法，其特征在于 两步晶种法 涂敷的NaA晶种尺寸不同，大晶种是尺寸为1～3 μm 的 NaA 沸石分子筛晶粒，小晶种是尺寸为 50 ～ 600 nm 的 NaA 沸石分子筛晶粒。
4 、按照权利要求1或2的制备方法，其特征在于 两步晶种法 为热浸渍法，其浸渍用载体管的温度为 50-200℃ ， 浸渍时间为 10-50 s ， 晶种液中晶种的浓度为 2-10 wt.% 。
5 、按照权利要求3的制备方法，其特征在于 两步晶种法 为热浸渍法，其浸渍用载体管的温度为 50-200℃ ， 浸渍时间为 10-50 s ， 晶种液中晶种的浓度为 2-10 wt.% 。
6 、按照权利要求 1 或 2 的制备方法 ，其特征在于 制备的 NaA 沸石膜渗透蒸发进行乙醇脱水时，在乙醇的浓度为 50.0-99.0wt.% 的范围内，分离性能优良、重复性高，适合规模化应用。
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