201018645 六、發明說明： * 【發明所屬之技術領域】 . 本發明是有闕於一種無機膜的製造方法，特別是指一 種沸石薄膜的製造方法。 【先前技術】 ’可以改善傳統分離程序費時、，且操作程序複 雜…等缺點’所近年高度精密的分離程序已多改採薄膜分離 技術。常見薄膜分離技術的薄膜大致可區分為有機薄膜與 • 錢薄膜兩大類，由於有機薄膜的使用範圍受溫度、屢力 、使用環境···等限制；而無機膜則具有耐高溫、耐腐钱、化 ㈣^、機械強度高、結構财、易於再生等特點，因此 • ，近年已有愈來愈多人開始投入無機薄膜的研發。其中， 沸石薄膜即為常見的一種無機薄膜。 沸石（Ze〇lite)M 1756年為瑞典礦物學家FAF Cron滅㈣現，是一種具有均勻微孔結構的結晶石夕銘酸 鹽，其微孔結構是具一致性之分子級大小之孔洞與管道， # 1具有高度選擇性，更同時還具有可調整的親、疏水性和 催化性能。 利用沸石中的陽離子可與其它離子交換、⑽丨比能夠 做調節，以及Si或A1原子亦可被其它原子取代的特性進 而形成不同結構類型、不同孔徑大小、不同表面性質的沸 石賴可以適用於不同的分離，因此沸石膜可以有吸附如 γ水π、f 、乙醇...等較小分子，而排除如：丙醇、笨 等較大刀子的特性’所以沸石膜又被稱為分子篩（ 201018645 molecular sieves )，而被廣範的應用於石化工業、分離、過 濾…等作業上。 此外，沸石膜本身是一種催化劑，製備成沸石膜反應 器，可將反應過程和分離過程组合，既提高了反應轉化率 ，同時也强化了反應過程。 現今最常見用以合成人工沸石薄膜的方法即為水熱合 成法（Hydrothermal Synthesis),所謂的水熱合成法是將基材 直接浸入-金屬化合物的水溶液中，以高壓釜密封後控 制在一特定溫度下，使水溶液產生飽合蒸氣壓，造成金屬 化合物的原子結構發生重整，經由分解、組合、排序，及 結晶等步驟合成出人工沸石薄膜。 仁是目$以水熱合成法所製成之沸石薄膜除備製時 間極為費時之外’更容易發生膜厚不均的現象而且其表 面更會在㈣後形錢裂，造成人工合成沸石薄膜的效果 遠不及天然彿石，在愈來愈多產業採用無機薄膜的今日， 實有其必要對人工合成沸石的製程加以改善。 【發明内容】 因此’本發明之目的’即在提供—種可使所產出之膜 厚均勻且耐高溫之沸石薄膜的製造方法。 於是，本發明沸石薄膜的製造方法是包含將水、里丙 氧基铭、四甲基氫氧化錄，及二氧化石夕溶膠依設定比例混 合成一混合液，並將該混合液於室溫下進行攪拌水解，之 後予以加熱再經離心過濾，接著’添加去離子水而獲得所 一彿石懸浮溶液，然後，準備並清洗—基材，再將清洗後 201018645 的基材置於一腔體内，並將沸石懸浮溶液霧化，接著，利 用惰性乳體將霧化後之沸石懸浮溶液中粒徑較小的沸石矣士 晶帶入該腔體内，最後，利用一電漿產生器依據一設定電 壓所產生之電漿產生電漿化學反應，而於該基材上沉積一 沸石薄膜。 本發明之功效在於利用惰性氣體配合電漿所產生的電 漿化學反應，使霧化後的沸石沉積於該基材上，進而獲得 一膜厚均勻且耐高溫之沸石薄膜，不但可以改善水熱合成 法膜厚不均與煅燒後表面易形成龜裂的缺點，而且製程亦 較水熱合成法簡單，可以有效縮短合成沸石薄膜的時間， 控制方式亦更為簡單，極具有大量生產之商業價值。 【實施方式】 有關本發明之前述及其他技術内容、特點與功效，在 以下配合參考圖式之一個較佳實施例的詳細說明中，將可 清楚的呈現。 參閱圖1、2,本發明沸石薄膜的製造方法之較佳實施 例包含下列步驟：首先進行步驟21，將水、異丙氧基鋁、 四甲基氫氧化銨，及二氧化矽溶膠依設定比例混合成—混 合液，並將該混合液於室溫下進行24小時的攪拌水解，接 著以100°C的溫度加熱75小時再經離心過濾，然後添加去 離子水（deionized water )而獲得一沸石懸浮溶液丨丄。 在本較佳實施例中是將該混合液重覆地離心過濾與添 加去離子水3〜4次後以獲得酸鹼值近於中性的沸石懸浮溶 液11。 5 201018645 此外，本較佳實施例中，該混合液的設定比例是以莫 爾比的 〇.15Na2〇 : 5·5(ΤΜΑ)2〇 : 2.3A1203 : l〇Si〇2 : 570H2〇進行調配’且清洗過濾後之沸石懸浮溶液丨丨中碎紹 比值是介於1.5〜3.0之間，當然，該沸石懸浮溶液u的組 成比例亦可依據需求進行調整，只要沸石的組成比例可以 符合Mx/n[(Al〇2)x(Si〇2)y].mH20的一般沸石結構式即可達 成相同的功效，並不應為本實施例的揭露所囿限。 接著’進行步驟22，準備並清洗一基材12，且將該基 材12置於一腔體13内，並利用超音波震盪器14使沸石懸 浮溶液11霧化。 其中，該基材12之選用可以是矽基材、氧化鋁基材或 是其它工業用的各種基材，並無限制，於本較佳實施例中 ，是選用矽晶片作為基材《且本較佳實施例中是利用超音 波震盪器來霧化沸石懸浮溶液u’當然，我們也可以利 用其他的方式來霧化沸石懸浮溶& u，此為熟悉液體霧化 領域之人所能輕易思及，故在此不多加贅述。 …最後，進行步驟23，利用情性氣體15將霧化後之濟石 懸淨溶液11中粒徑較小㈣石結晶帶人該腔體13内，並剩 用一電漿產生胃17依據-設定電壓所產生之電聚產生電黎 化學反應，而於該基材12上沉積—彿石賴。其中，於本 ，佳實施例中，所選用的惰性氣體15為氯氣，且利用一流 I控制器16來控制情性氣肖15的流量為每分鐘 5〇cc〜職e’在本較㈣施财最佳㈣鐘15流量為每 分鐘而該電漿產生w定電壓可介於％至1〇( 201018645 伏特之間，在本較佳實施例中最佳設定電壓為80伏特。 增加惰性氣體15流量可以增加沸石懸浮溶液u霧化 蒸氣含量進入該腔體13内；提昇電漿產生器17設定電 壓’則提高通過該腔體13之電漿中電子與分子的相互碰 撞機率’使其增高電漿化學反應。搭配理想的惰性氣體 15流量與電漿產生器17設定電壓，可以獲得理想之沸 石薄膜。 利用惰性氣體15將霧化後的沸石懸浮溶液U帶入腔體 ❹ 13中’再配合電漿所產生的電漿化學反應，使沸石沉積於 該基材12上，而獲得一沸石薄膜，而鍍膜時間與薄膜膜厚 間的關係如圖3所示，由圖3可知，縱轴為膜厚其單位為 奈米（nm)，橫轴為鍍膜時間其單位為分鐘（min)，利用本 發明彿石薄膜的製造方法可製成奈米級厚度的沸石薄膜， 而且製成速度快，僅須20分鐘即可獲得250奈米厚的彿石 薄膜。 值得一提的是’由圖3更可知道，本發明沸石薄模的 ® 製造方法所製成之沸石薄膜的膜厚，與鍍膜時間概呈線性 關係’亦即’在相同的電漿操作條件下，鍍膜時間愈久所 獲得之沸石薄膜的膜厚也就愈厚，也就是說，沸石薄膜的 膜厚可以利用改變鍍膜時間或改變電漿操作條件加以控制 ’因此’在沸石薄膜的膜厚控制上也較現有製造沸石薄膜 的方式更為簡單與容易控制。 為驗證本發明沸石薄膜的製造方法所製造出的彿石薄 膜與水熱合成法所製成之沸石薄膜間粗糙度的差異，發明 201018645 人以原子力顯微鏡（Atomic Force Microscope, AFM)，觀察本 發明與水熱合成法所製成之沸石薄膜的粗糙度，其結果如 附件1所示，其中，水熱合成法所製成之沸石薄膜是採用 與本發明沸石薄膜的製造方法相同的沸石懸浮液，在於烘 箱中以100°C製備12小時，以本發明所製成之沸石薄膜的 粗糙度為8.6784nm，而以水熱合成法所製成之沸石薄膜的 粗糙度為0.65544nm。由此可知，以本發明所製成之沸石薄 膜的粗糙度確實優於以水熱合成法所製成之沸石薄膜。 再者，為驗證本發明與水熱合成法所製成之沸石薄膜 間抗熱性的差異，發明人同時將本發明與水熱合成法所製 成之沸石薄膜於350°C下煅燒八小時後，利用掃描式電子顯 微鏡（Scanning Electron Microscope, SEM)觀察兩者間的差異 ，如附件2所示，其中，可以清楚觀察到，以水熱合成法 所製成的沸石薄膜表面除了龜裂外，更形成有崩塌現象， 而本發明所製成的沸石薄膜除了些微龜裂外，並無明顯的 結構破壞。此外，另附上以X光繞射儀（X-ray diffraction， XRD)分析圖、穿透式電子顯微鏡（Transmission Electron Microscope，TEM)，及掃描式電子顯微鏡斷面掃描圖的分析 結果如附件3、4、5所示。 綜上所述，本發明之沸石薄膜的製造方法，是利用惰 性氣體15將霧化後沸石懸浮溶液11中粒徑較小的沸石結晶 帶入腔體13中，配合電漿所產生的電漿化學反應，使沸石 沉積於該基材I2上而製成沸石薄膜，由於霧化的沸石結晶 顆粒小且較均勻，所以可改善水熱合成法因沉積不均造成 201018645 膜厚不均的缺點，連帶改善了沸石薄膜的抗熱性，使煅燒 後之沸石薄骐的表面不易形成龜裂與明顯的結構破壞，， 而且製程亦較水熱合成法簡單’可以有效縮短合成沸石薄 膜的時間，再者利用改變鍍膜時間或改變電漿操作條件即 可加以控，錄媒厚度，控制方式也較現有製造彿石薄膜的 方式更為簡單，故確實能達成本發明之目的。 惟以上所述者，僅為本發明之較佳實施例而已，當不 能以此限定本發明營始 # m a貫施之範圍，即大凡依本發明申請專利 • 範圍及發明說明内宠拼从#雜k 合所作之簡單的專效變化與修飾，皆 屬本發明專利涵蓋之範圍内。 【圖式簡單說明】 圖疋步驟流程圖，說明本發明沸石薄膜的製造 法之較佳實施例；及 圖2是一系統示意圖，輔助說明圖1;及 圖3是一比較圖，說明該較佳實施例之沸石薄膜 與鍍膜時間的關係》 又 響 9 201018645 【主要元件符號說明】 11 •… …‘沸石懸浮溶液 1 X ♦ X ♦ X ♦ je •-惰性氣體 12*"* •…基材 1 »*«**»* ··流量控制器 1 β ♦ K ♦ X —腔體 21 〜23-· -·步驟 14"… •…超音波震盪器201018645 VI. Description of the invention: * [Technical field to which the invention pertains] The present invention relates to a method for producing an inorganic film, and more particularly to a method for producing a zeolite film. [Prior Art] It is possible to improve the time-consuming and complicated operation procedures of the conventional separation procedure. In recent years, the highly sophisticated separation procedure has been changed to the membrane separation technology. The film of common film separation technology can be roughly divided into two types: organic film and money film. The use range of organic film is limited by temperature, force, and environment. The inorganic film has high temperature resistance and corrosion resistance. , (4) ^, high mechanical strength, structural wealth, easy to regenerate, etc., therefore, in recent years, more and more people have begun to invest in the development of inorganic thin films. Among them, the zeolite film is a common inorganic film. Zeolite (Ze〇lite) M 1756 is a Swedish mineralogist FAF Cron (4), is a crystalline microlithic structure with a uniform microporous structure, the microporous structure is a uniform molecular size pores and The pipe, #1 is highly selective and, at the same time, has adjustable affinity, hydrophobicity and catalytic properties. The use of cations in zeolites can be exchanged with other ions, (10) ruthenium ratio can be adjusted, and Si or A1 atoms can also be substituted by other atoms to form different structure types, different pore sizes, different surface properties of zeolites can be applied to Different separations, so the zeolite membrane can have smaller molecules such as γ water π, f, ethanol, etc., and exclude the characteristics of larger knives such as propanol and stupidity. Therefore, the zeolite membrane is also called molecular sieve ( 201018645 molecular sieves ), and is widely used in petrochemical industry, separation, filtration, etc. In addition, the zeolite membrane itself is a catalyst which is prepared into a zeolite membrane reactor which combines the reaction process with the separation process, thereby improving the reaction conversion rate and strengthening the reaction process. The most common method for synthesizing artificial zeolite membranes today is Hydrothermal Synthesis. The so-called hydrothermal synthesis method is to directly immerse the substrate in an aqueous solution of a metal compound, and control it in a specific state after sealing with an autoclave. At the temperature, the aqueous solution is subjected to a saturated vapor pressure, and the atomic structure of the metal compound is reformed, and an artificial zeolite film is synthesized through decomposition, combination, sorting, and crystallization. The zeolitic film made by the hydrothermal synthesis method is more prone to film thickness unevenness than the preparation time, and its surface is more likely to be cracked after the (4) shape, resulting in a synthetic zeolite film. The effect is far less than natural Buddha stone. In today's increasingly industrial use of inorganic thin film, it is necessary to improve the process of synthetic zeolite. SUMMARY OF THE INVENTION Therefore, the object of the present invention is to provide a method for producing a zeolite film which can produce a uniform film thickness and high temperature resistance. Therefore, the method for producing the zeolite film of the present invention comprises mixing water, propylene glycol, tetramethyl hydrate, and cerium oxide in a predetermined ratio to form a mixed solution, and mixing the mixture at room temperature. Agitating and hydrolyzing, then heating and then centrifuging, followed by 'adding deionized water to obtain a suspension solution of the Buddha stone, then preparing and cleaning the substrate, and then placing the substrate of 201018645 after cleaning in a cavity And atomizing the zeolite suspension solution, and then using an inert emulsion to bring the smaller particle size zeolite in the atomized zeolite suspension solution into the cavity, and finally, using a plasma generator according to The plasma generated by the set voltage produces a plasma chemical reaction, and a zeolite film is deposited on the substrate. The utility model has the advantages that the plasma chemical reaction generated by the inert gas and the plasma is used to deposit the atomized zeolite on the substrate, thereby obtaining a uniform and high temperature resistant zeolite film, which can not only improve the water heat. The method of synthesizing film thickness unevenness and the surface of calcination is easy to form cracks, and the process is simpler than hydrothermal synthesis method, which can effectively shorten the time of synthesizing zeolite film, and the control method is simpler, and has great commercial value for mass production. . The above and other technical contents, features, and advantages of the present invention will be apparent from the following detailed description of the preferred embodiments. Referring to Figures 1 and 2, a preferred embodiment of the method for producing a zeolite membrane of the present invention comprises the steps of first performing step 21 of setting water, aluminum isopropoxide, tetramethylammonium hydroxide, and cerium oxide. The mixture was mixed into a mixture, and the mixture was subjected to stirring and hydrolysis at room temperature for 24 hours, followed by heating at a temperature of 100 ° C for 75 hours, followed by centrifugal filtration, and then deionized water was added to obtain a mixture. Zeolite suspension solution 丨丄. In the preferred embodiment, the mixture is subjected to repeated centrifugal filtration and addition of deionized water for 3 to 4 times to obtain a near-neutral zeolite suspension solution 11 having a pH value. 5 201018645 In addition, in the preferred embodiment, the set ratio of the mixed liquid is formulated by 〇.15Na2〇: 5·5(ΤΜΑ)2〇: 2.3A1203: l〇Si〇2: 570H2〇 of Moire ratio. 'And the ratio of the crushing ratio of the zeolite suspension solution after washing and filtering is between 1.5 and 3.0. Of course, the composition ratio of the zeolite suspension solution u can also be adjusted according to requirements, as long as the composition ratio of the zeolite can conform to Mx/ The general zeolite structure of n[(Al〇2)x(Si〇2)y].mH20 can achieve the same effect and should not be limited by the disclosure of the embodiment. Next, step 22 is performed to prepare and clean a substrate 12, and the substrate 12 is placed in a cavity 13, and the zeolite suspension solution 11 is atomized by the ultrasonic oscillator 14. The substrate 12 may be selected from a ruthenium substrate, an alumina substrate or other industrial substrates, and is not limited. In the preferred embodiment, a ruthenium wafer is selected as the substrate. In a preferred embodiment, the ultrasonic suspension is used to atomize the zeolite suspension solution. Of course, we can also use other methods to atomize the zeolite suspension solution & u, which is easy for people familiar with the field of liquid atomization. Thinking about it, so I won't add more details here. Finally, step 23 is carried out, and the particle size of the atomized suspension solution 11 is atomized by the inert gas 15 (4) stone crystal is brought into the cavity 13 and a plasma is left to produce the stomach 17 basis - The electrocoagulation generated by the set voltage generates an electro-chemical reaction, and the substrate 12 is deposited on the substrate 12. In the present embodiment, the selected inert gas 15 is chlorine gas, and the flow rate of the emotional Qi Xiao 15 is controlled by the first-class I controller 16 to be 5 〇 cc per minute. The best (four) clock 15 flow rate is per minute and the plasma produces w constant voltage between % and 1 〇 (between 201018645 volts, in the preferred embodiment the optimum set voltage is 80 volts. Increase the inert gas 15 The flow rate can increase the atomized vapor content of the zeolite suspension solution into the cavity 13; raising the plasma generator 17 to set the voltage 'improves the probability of collision between electrons and molecules in the plasma passing through the cavity 13' Slurry chemical reaction. With the ideal inert gas 15 flow rate and the plasma generator 17 set voltage, the ideal zeolite film can be obtained. The inert gas 15 is used to bring the atomized zeolite suspension solution U into the cavity ❹ 13 The plasma chemical reaction generated by the plasma causes the zeolite to be deposited on the substrate 12 to obtain a zeolite film, and the relationship between the coating time and the film thickness is shown in Fig. 3. As can be seen from Fig. 3, the vertical axis is Membrane thickness Meter (nm), the horizontal axis is the coating time, the unit is minute (min), and the nanometer-thickness zeolite film can be prepared by the method for producing the Buddha stone film of the invention, and the production speed is fast, and only takes 20 minutes. A 250 nm thick Buddha stone film is obtained. It is worth noting that, as can be seen from Fig. 3, the film thickness of the zeolite film produced by the method for producing the zeolite thin mold of the present invention has a linear relationship with the coating time. That is, under the same plasma operating conditions, the longer the coating time, the thicker the film thickness of the zeolite film, that is, the film thickness of the zeolite film can be changed by changing the coating time or changing the plasma operating conditions. The control 'so that' is also simpler and easier to control than the conventional method for producing a zeolite film in the film thickness control of the zeolite film. To verify the film of the zeolite film produced by the method of the present invention, the film is prepared by hydrothermal synthesis. The difference in roughness between the formed zeolite films, the invention 201018645 Atomic Force Microscope (AFM), observe the coarseness of the zeolite film prepared by the present invention and the hydrothermal synthesis method The results are shown in Annex 1, wherein the zeolite film prepared by the hydrothermal synthesis method is the same as the zeolite suspension of the present invention, and is prepared in an oven at 100 ° C for 12 hours. The zeolite film prepared by the invention has a roughness of 8.6784 nm, and the zeolite film prepared by hydrothermal synthesis has a roughness of 0.65544 nm. Thus, the roughness of the zeolite film prepared by the invention is known. It is indeed superior to the zeolite film prepared by the hydrothermal synthesis method. Furthermore, in order to verify the difference in heat resistance between the zeolite film produced by the present invention and the hydrothermal synthesis method, the inventors simultaneously compared the present invention with hydrothermal synthesis. After the prepared zeolite film was calcined at 350 ° C for eight hours, the difference between the two was observed by a scanning electron microscope (SEM), as shown in Annex 2, in which it can be clearly observed that water is The surface of the zeolite membrane prepared by the thermal synthesis method has a collapse phenomenon in addition to cracking, and the zeolite membrane produced by the present invention has no obvious structural damage except for slight cracking. In addition, an X-ray diffraction (XRD) analysis chart, a transmission electron microscope (TEM), and a scanning electron microscope cross-sectional scan image are attached as shown in Annex 3. 4, 5 are shown. In summary, the method for producing the zeolite film of the present invention is to introduce the zeolite crystal having a smaller particle diameter in the atomized zeolite suspension solution 11 into the cavity 13 by using the inert gas 15, and the plasma generated by the plasma is mixed with the plasma. The chemical reaction causes the zeolite to be deposited on the substrate I2 to form a zeolite film. Since the atomized zeolite crystal particles are small and relatively uniform, the disadvantages of the film thickness unevenness of the 201018645 caused by the uneven deposition of the hydrothermal synthesis method can be improved. The heat resistance of the zeolite film is improved, so that the surface of the calcined zeolite is less likely to form cracks and obvious structural damage, and the process is simpler than the hydrothermal synthesis method, which can effectively shorten the time for synthesizing the zeolite film, and further It can be controlled by changing the coating time or changing the plasma operating conditions. The thickness of the recording medium and the control method are also simpler than the conventional method of manufacturing the Buddha stone film, so the object of the present invention can be achieved. However, the above description is only a preferred embodiment of the present invention, and it is not possible to limit the scope of the present invention to the present invention, that is, the patent application scope and invention description in the invention The simple special effects and modifications made by the hybrids are within the scope of the present invention. BRIEF DESCRIPTION OF THE DRAWINGS FIG. 2 is a flow chart showing a preferred embodiment of a method for producing a zeolite membrane of the present invention; and FIG. 2 is a schematic view of a system for assisting in explaining FIG. 1; and FIG. 3 is a comparative diagram illustrating the comparison. The relationship between the zeolite film and the coating time of the preferred embodiment is again 9 201018645 [Explanation of main component symbols] 11 •... 'The zeolite suspension solution 1 X ♦ X ♦ X ♦ je •-Inert gas 12*"* •... Material 1 »*«**»* ··Flow controller 1 β ♦ K ♦ X — Chamber 21 ～23-· -·Step 14"... •...Ultrasonic oscillator
1010