1286492 九、發明說明： [發明所屬之技術領域】 一種適用於吸附與分 本叙明係關於一種無機膜，尤指 解污染物之無機膜。 5 【先前技術】 具奈米孔洞之無機膜可而$高溫（>2〇〇。〇、耐酸驗、耐 化予品、容易逆洗再生等優點，因此在石化工業的 序、永續發展領域、新能源製程以及環保技術的應用，皆 有積極的研究與開發。 …枝膜之材貝可分為結晶性及非結晶性兩種，其中沸 石（⑽hte)為、結晶性物f，屬於—具有規則性微孔洞結構 之結晶性矽酸鹽或鋁矽酸鹽類，且不同的孔洞大小、形狀 以及化學組成，皆會對吸附分子產生不同之選擇性的交互 15作用力，因❿此作用力可應用在一些分離與反應程序上。 傳統上以吸附劑（如活性碳）來去除污染物時，常因吸 附劑粒彼較大（約為mm)且填充密度不均，會有渠流 (channeling)的現象而造成吸附效果變差；而以無機膜滲透 吸附方式去除污染物時，則可藉由無機膜之奈米孔洞及滲 20透吸附特性，提高污染物之去除效率；且對於飽和吸附劑 之吸附物的去除，傳統上大多以高溫或觸媒來加以分解破 壞之’但此方式往往需耗費大量能源及成本。 習知技術提出以多孔吸附物質與多孔性基材結合之複 合膜來分離氣體混合物，其多孔吸附物質係由塗佈一層先驅 1286492 物質在基材上，再經由惰性氣氛下加熱轉化而得；除此之外 ，亦可由沸石、鋁磷酸鹽、鋁矽酸鹽、金屬氧化物、黏土、 活化石夕石及活化氧化料物質來製備；而多孔性基材則包括 陶究、碳質、金屬性及聚合性物質及其混合物；此技術所揭 5不之複合膜主要藉由多孔吸附物質對各種氣體之吸附能力不 同而造成選擇性分離。 ^另一習知技術則提出以多孔吸附物質與多孔性基材結合 之複合膜及其整合性分離I统，·整個系統包括吸附分離與脫 附再生兩步‘ ’即藉由複合膜之多孔吸附物質將氣體混合物 加以遥擇性分離後，再導人變屢吸附系統將複合膜上之吸附 物貝進订脫附（再幻程序，如此複合膜便可循環使用。 冬、不觀岫木技術’以多孔吸附物質與多孔基材結合之複合 膜應用在污染物去除時，目只具有韻效果而無法同時分解 皮A污木物，故需另外加熱或加入觸媒分解之丨另外，前案 b所述之整合性分離系統為兩階段式，即包括吸附分離與脫附 再生兩步驟，系統在操作時，往往需耗費大量能源及成本， 不符合經濟效益。 【發明内容】 2 本务明以一觸媒無機膜應用於污染物之吸附分解，即 利用無機膜之滲锈哄^ 〜透及附特性，將液相或氣相污染物吸附在 膜f’再以膜上觸媒同時分解破壞之，可提高污染物 f除放率，同時減少傳統吸附劑再生之問題，亦能降低 飽和吸附劑之處理成本，提升處理效益。 · 25本發明之觸媒無機膜包括：-具有多孔洞之基材，孔 1286492 洞直徑為0.1 μπι至Ιμηι之間；—吸附層；以及一觸媒分解層 :其中，吸附層係分佈於基材之表面，部分吸附層係夹^ 於基材與觸媒分解層之間，且觸媒分解層係呈一不連續之 表面。 、 5 本發明更包括一種觸媒無機膜之製備方法，其步驟包 括：（a)提供一具有多孔洞之基材，其孔洞直徑為〇1 至Ιμιη之間；（b)形成一吸附層，使吸附層材料分佈於基 材之表面；以及（c)形成一觸媒分解層於吸附層上，且^ 媒分解層係呈一不連續之表面。 10 於本發明製造方法中，較佳可於步驟（C)之後更包括一 步驟（d)，煅燒含觸媒分解層以及吸附層之基材；步驟卬) 中吸附層之形成方法不限，較佳為水熱法；此水熱法係指 將基材置於含吸附層材料（如鋁與矽）成分之水溶液中，溫度 控制在10(M5(TC之間，持溫low小時；步驟⑷之觸媒分解 15層形成方法不限，較佳係以含浸方式形成於吸附層與具有 多孔洞之基材上，即將基材浸在二氧化鈦溶膠溶液中，含浸 後進行备燒程序，锻燒條件較佳係在空氣氣氛下，溫度為 200-450 C，持溫1-6小時，加熱速率為〇.5-5t/min。 本發明亦包括一種去除流體内污染物之方法，其步驟 20包括提供一含具有多孔洞之基材，一吸附層以及一觸 媒分解層之觸媒無機膜，其中，基材孔洞直徑為〇1 μιη至 Ιμιη之間；吸附層係分佈於該基材之表面，部分之吸，附層 係爽置於基材與觸媒分解層之間，且觸媒分解層係呈一不 連續之表面；(b)將流體通過觸媒無機膜，或使流體與觸 1286492 媒無機膜接觸；以及（c)排出經觸媒無機膜吸附過之流體 〇 適用於本發明之基材不限制，較佳係陶竟、金屬或玻 璃，且為使口及附層材料可於基材上分佈均勻，㈣本身孔 5洞之直徑較大者，可藉由改質方式填補較大孔洞’·例如基 材為多孔不銹鋼基材，其改質方式較佳係以粒徑為1〇〜5〇〇 nm之二氧化矽溶膠填補多孔不銹鋼基材之孔洞後，再進行 锻燒程序；锻燒條件較佳係在空氣氣氛下，溫度為·_ C ’持溫1-6小時，加熱速率為i°c/min。 1〇 適用於本發明之吸附層材料不限，較佳係選自至少一 :沸石、鋁磷酸鹽、鋁矽酸鹽、金屬氧化物、黏土、活性 碳、活化矽石及活化氧化鋁等物質所構成之群組，且為發 揮吸附效率，吸附層上之平均孔徑大小為lnm至2〇〇nm: 更佳之吸附層材料為彿石薄膜，其均一孔洞分佈特性使其 15具有分子篩之性質，可對滲透分子加以純化與分離。/、 於本發明之觸媒分解層中所使用之觸媒不限，較佳的 疋光觸媒、金屬觸媒或金屬氧化物觸媒；且最佳之觸媒分 解層係一光觸媒層，如二氧化鈦（Ti〇2)，且為具光觸媒活 性之銳鈦礦（Anatase)結構。 ' 20 本發明可用以吸附並分解一流體中之一污染物，流體 係包括氣體或液體，且污染物包括揮發性有機化合物 氫化合物、六氟化硫、含氯之碳氫化合物、含氟之碳氫化 合物，或是揮發性有機化合物（volatile 〇rganic c〇mp〇unds， VOCs)戴奥辛、全氟化碳（perfluorocarbons, PFCs)、=氯 1286492 乙稀（trichl〇r〇ethyiene，tCE)等。 同 物之去除率。 無機膜上料層之⑽能力依不同的污染 因此’可針對污染物的種類來改變觸媒I 2所不 以提高觸媒無機膜對不同污染物之吸:==特性， 廼而增加污染 【實施方式】 10 之 本實施例之無機膜係利用多孔不錄鋼為基材，卜 化鈦薄膜作為觸媒分解層，而—乳 r兼具吸附與分解功能之複合膜广為及附層所形成 實施例1、多孔不銹鋼基材之改質 為使不錄鋼基材上之孔徑適於覆上一連續而無缺 吸附層，此基材必須經過改質 ^ ，切割成5em長度，外M G3 多孔不錄鋼管 15 瓦厌工為1.03 cm，厚度為〇 〇9 cm 端焊接不銹鋼管，其中一端末端封閉；此多孔不錄鋼管以 液體孔徑量測法測得其平均孔徑為12 pm。 將此多孔不錄鋼管以稀鹽酸及氫氧化納溶液清洗後，浸 =一平均孔徑為2Gnm，固含量為4()%，邱值為之二氧化: 20 /合膠洛液中；含浸30秒後，取出在怪溫恒溼箱中，渔度為 95%以上乾燥；!天；將含浸二氧化硬溶膠之多孔不銹鋼管置 於=燒爐中，升溫速率為rc/分鐘，溫度為55〇。〇，持溫2 J呤，改貝後之多孔不鎊鋼管以液體孔徑量測法量測其平 均孔徑為〇·7μιη。 ' 由平均孔徑分佈之改變可知，二氧化矽改質可縮減多 25孔不錄鋼基材之孔徑，而有利於後續鑛覆一層厚度較薄且 1286492 ίο 15 20 無缺陷之沸石薄膜。 實施例2、沸石薄膜之鍍覆 在鍵覆彿石薄膜之前，需先在基材上預植彿石晶種。 彿石晶種溶液之製備如下，㈣·85g氫氧化棒調加入 6〇 1111之四丙基氫氧化銘（tetrapr〇pyi娜咖以腿hydr〇xide， TPAOH，1M)溶液中；持續授拌直到氫氛化鈉完全溶解後， 加入15g二氧化石夕（Si〇2);在贼下授掉混合3〇分鐘，秋後 將此料倒入鐵氟龍（Tefl〇n)容器令，在常溫下授料小時 即可得到-均勻溶液，其組成為1G Si〇2_ Μ Μ⑽U NaOH- 11〇 η2〇 ;接著將此均勻溶液置於高壓反應器 (autodave)中，溫度為，持溫8小時；之後取出重複 離心、水洗數次即可得到膠狀之沸石晶種溶液。 字只施例1改貝後之多孔不銹鋼管，浸在上述製備完成 之晶種溶液中5分鐘，便可將彿石晶種預植在多孔不錄鋼 基材上著將預植晶種之多孔不銹鋼置於—含有仙 s1〇2- U) TPA0H_ 2_ h2〇溶液之鐵氟龍容器中，然後置 於南壓反應器内加熱至13(rc ’持溫18小時；經過18小時 水熱合成彿石薄膜後，將高麼反應器快速冷卻至室溫，以 二段水清洗多孔不錄鋼管表面，最後在6代的供箱=乾燥 。將上述乾燥之多孔不_管置於锻燒爐中，以加敎 1C/分鐘加熱至55(rc，持溫6小時即可得到滞石 鋼複合膜。 7个场 以氮氣（⑹、氫氣⑽及六氟化硫（SF6)測試此複合膜 之氣體透過性與選擇率’結果如表i所示；氣體透過率定1286492 IX. Description of the invention: [Technical field to which the invention pertains] An inorganic membrane suitable for adsorption and separation, relating to an inorganic membrane, in particular to a pollutant. 5 [Prior Art] Inorganic membranes with nanopores can be used at high temperatures (>2〇〇, 耐, acid resistance, chemical resistance, easy backwashing, etc.), so the order and sustainable development in the petrochemical industry The field, the new energy process and the application of environmental protection technology have positive research and development. ... The material of the dendritic membrane can be divided into two kinds of crystalline and non-crystalline, among which zeolite ((10)hte) is a crystalline substance f, belonging to - crystalline bismuth or aluminosilicates with regular microporous structures, and different pore sizes, shapes, and chemical compositions all exert different selective interactions on the adsorbed molecules, because This force can be applied to some separation and reaction procedures. Traditionally, when adsorbents (such as activated carbon) are used to remove contaminants, the adsorbent particles are often larger (about mm) and the packing density is uneven. The phenomenon of channeling causes the adsorption effect to be deteriorated. When the inorganic membrane is used to remove the pollutants by the osmotic adsorption method, the removal efficiency of the pollutants can be improved by the nanopore and the osmotic adsorption characteristics of the inorganic membrane; And for The removal of the adsorbate of the saturated adsorbent has been conventionally mostly decomposed and destroyed by high temperature or a catalyst. However, this method often requires a large amount of energy and cost. The prior art proposes a combination of a porous adsorbent and a porous substrate. Membrane to separate the gas mixture, the porous adsorbent material is obtained by coating a layer of precursor 1286492 on the substrate and then heating and converting under an inert atmosphere; in addition, it can also be composed of zeolite, aluminophosphate, aluminosilicate , metal oxides, clay, activated Shishi stone and activated oxide materials to prepare; and porous substrates include ceramics, carbonaceous, metallic and polymeric substances and mixtures thereof; The selective separation is mainly caused by the different adsorption capacities of the porous adsorbing substances for various gases. Another conventional technique proposes a composite membrane in which a porous adsorbent is combined with a porous substrate and an integrated separation system thereof. The system consists of two steps of adsorption separation and desorption regeneration, that is, the gas mixture is separated by remote separation by the porous adsorbent of the composite membrane, and then Leading the adsorption system to desorb the adsorbent on the composite membrane (re-programming, so the composite membrane can be recycled. Winter, non-observation of the eucalyptus technology] combined with porous adsorbent and porous substrate When the membrane is used for the removal of contaminants, it has only a rhyme effect and cannot decompose the skin A at the same time. Therefore, it needs to be heated separately or added to the decomposition of the catalyst. In addition, the integrated separation system described in the previous case b is a two-stage type. It includes two steps of adsorption separation and desorption regeneration. When the system is operated, it often consumes a lot of energy and cost, which is not economical. [Inventive content] 2 The present invention uses a catalyst inorganic membrane for the adsorption of pollutants. Decomposition, that is, using the osmosis 〜^ permeable and attached characteristics of the inorganic film, the liquid phase or vapor phase pollutants are adsorbed on the film f' and then the catalyst on the film is simultaneously decomposed and destroyed, thereby increasing the removal rate of the pollutant f. At the same time, the problem of regenerating the traditional adsorbent can be reduced, and the treatment cost of the saturated adsorbent can be reduced, and the treatment efficiency can be improved. The catalytic inorganic film of the present invention comprises: - a substrate having a porous hole, a hole of 1 648 492 having a hole diameter of between 0.1 μm and Ιμηι; an adsorption layer; and a catalyst decomposition layer: wherein the adsorption layer is distributed on the base On the surface of the material, a part of the adsorption layer is sandwiched between the substrate and the catalytic decomposition layer, and the catalytic decomposition layer is a discontinuous surface. The invention further comprises a method for preparing a catalytic inorganic film, the steps comprising: (a) providing a substrate having a porous cavity having a pore diameter between 〇1 and Ιμιη; and (b) forming an adsorption layer, Disposing the adsorbent layer material on the surface of the substrate; and (c) forming a catalyst decomposition layer on the adsorption layer, and the dielectric decomposition layer is a discontinuous surface. In the manufacturing method of the present invention, preferably, after step (C), a step (d) is further included, and the substrate containing the catalyst decomposition layer and the adsorption layer is calcined; and the method for forming the adsorption layer in the step 卬) is not limited. Preferably, the hydrothermal method refers to placing the substrate in an aqueous solution containing the components of the adsorbent layer (such as aluminum and bismuth), and the temperature is controlled at 10 (M5 (TC), holding the temperature low hour; (4) The catalyst decomposition 15 layer formation method is not limited, and is preferably formed by impregnation on the adsorption layer and the substrate having the porous hole, that is, the substrate is immersed in the titania sol solution, and the preparation process is performed after impregnation, and calcination is performed. The condition is preferably in an air atmosphere, the temperature is 200-450 C, the temperature is maintained for 1-6 hours, and the heating rate is 〇5-5 t/min. The invention also includes a method for removing contaminants in a fluid, the step 20 The invention comprises a catalyst inorganic film comprising a substrate having a porous hole, an adsorption layer and a catalyst decomposition layer, wherein the substrate has a pore diameter of between 〇1 μηη and Ιμιη; and the adsorption layer is distributed on the substrate. Surface, part of the suction, the layer is cool placed on the substrate and catalyst Between the decomposing layers, and the catalytic decomposition layer is a discontinuous surface; (b) passing the fluid through the catalytic inorganic film, or contacting the fluid with the contact 1284494 inorganic film; and (c) discharging the catalytic inorganic film The adsorbed fluid 〇 is suitable for the substrate of the present invention without limitation, and is preferably ceramic, metal or glass, and the mouth and the layer material can be uniformly distributed on the substrate, and (4) the diameter of the hole 5 hole itself is larger. The larger pores can be filled by modification. For example, the substrate is a porous stainless steel substrate, and the modification method is preferably to fill the porous stainless steel base with a cerium oxide sol having a particle diameter of 1 〇 5 5 nm. After the hole of the material, the calcination process is carried out; the calcination condition is preferably under an air atmosphere, the temperature is _ C 'temperature 1-6 hours, and the heating rate is i ° c / min. 1 〇 is suitable for the present invention The adsorbing layer material is not limited, and is preferably selected from the group consisting of at least one of zeolite, aluminophosphate, aluminosilicate, metal oxide, clay, activated carbon, activated vermiculite and activated alumina. In order to exert adsorption efficiency, the average pore size on the adsorption layer is from 1 nm to 2 Å. Nm: The better adsorbent layer material is a Foshan thin film, and its uniform pore distribution characteristics make it 15 molecular sieve properties, which can purify and separate the permeating molecules. /, The catalyst used in the catalytic decomposition layer of the present invention Not limited to, preferred photocatalyst, metal catalyst or metal oxide catalyst; and the best catalyst decomposition layer is a photocatalyst layer, such as titanium dioxide (Ti〇2), and is photocatalytic active anatase ( Anatase) structure. ' 20 The present invention can be used to adsorb and decompose one of the pollutants in a fluid, the flow system includes a gas or a liquid, and the pollutant includes a volatile organic compound hydrogen compound, sulfur hexafluoride, a chlorine-containing hydrocarbon Fluorine-containing hydrocarbons, or volatile organic compounds (volatile 〇rganic c〇mp〇unds, VOCs), dioxin, perfluorocarbons (PFCs), = 1,280,492 bis (trichl〇r〇ethyiene, tCE) and so on. The removal rate of the same substance. The (10) ability of the inorganic film upper layer depends on the different pollution. Therefore, the catalyst I 2 can be changed according to the type of the contaminant to improve the absorption of different pollutants by the catalytic inorganic film: == characteristics, but increase pollution [ Embodiments 10 The inorganic film of the present embodiment uses a porous unrecorded steel as a base material, a titaniumized titanium thin film as a catalytic decomposition layer, and a latex composite film having both adsorption and decomposition functions. Forming Example 1, the porous stainless steel substrate is modified so that the pore diameter on the unrecorded steel substrate is suitable for coating a continuous and intact adsorption layer, the substrate must be modified, cut into 5 cm length, and the outer M G3 The perforated non-recorded steel pipe has a wear resistance of 1.03 cm and a thickness of 〇〇9 cm. The welded stainless steel pipe is closed at one end. The porous non-recorded steel pipe has an average pore diameter of 12 pm measured by liquid pore size measurement. After the porous non-recorded steel pipe is washed with dilute hydrochloric acid and sodium hydroxide solution, the immersion = an average pore diameter of 2Gnm, the solid content is 4 ()%, the Qi value is dioxide: 20 / in the gum solution; impregnation 30 After the second, take out in the strange temperature and humidity box, the fishing degree is more than 95% dry;! Day; the porous stainless steel tube impregnated with the oxidized hard sol is placed in the = furnace, the heating rate is rc / minute, the temperature is 55 Hey. 〇, holding a temperature of 2 J 呤, the porous non-pound steel pipe after the change of shell is measured by liquid pore size measurement method, and its average pore diameter is 〇·7μιη. From the change of the average pore size distribution, the ruthenium dioxide modification can reduce the pore size of the 25-hole unrecorded steel substrate, and facilitate the subsequent mineral coating with a thin layer of 1,648,492 ίο 15 20 defect-free zeolite membrane. Example 2. Plating of Zeolite Film Before the Foshan film is bonded, the Foshan seed crystal must be pre-planted on the substrate. The preparation of the solution of the buddha seed crystal is as follows. (4) · 85g of hydroxide rod is added to the solution of 6 〇 1111 tetrapropyl hydrazine (tetrapr〇pyi café to leg hydr〇xide, TPAOH, 1M); After the sodium hydride is completely dissolved, add 15g of sulphur dioxide (Si〇2); and mix it for 3 minutes under the thief. After the autumn, pour the material into the Teflon container, at room temperature. Under the hour of feeding, a homogeneous solution having a composition of 1G Si〇2_Μ(10)U NaOH- 11〇η2〇 is obtained; then the homogeneous solution is placed in a high-pressure reactor (autodave) at a temperature of 8 hours; After that, the mixture is repeatedly centrifuged and washed several times to obtain a gelatinous zeolite seed solution. The word only 1 modified porous stainless steel tube, immersed in the above prepared seed solution for 5 minutes, the Buddha stone seed can be pre-planted on the porous unrecorded steel substrate to pre-plant seed crystal The porous stainless steel was placed in a Teflon container containing a solution of s1〇2- U) TPA0H_ 2_ h2 ,, and then placed in a south pressure reactor to be heated to 13 (rc 'temperature for 18 hours; after 18 hours of hydrothermal synthesis) After the Foshan film, the reactor is rapidly cooled to room temperature, and the surface of the porous non-recorded steel pipe is cleaned with two stages of water, and finally the box of the sixth generation is dry = the above-mentioned dried porous tube is placed in the forging furnace. In the middle, it is heated to 55 (rc by heating at 1 C/min, and the composite steel film can be obtained by holding the temperature for 6 hours. The seven fields are tested with nitrogen ((6), hydrogen (10) and sulfur hexafluoride (SF6)). Gas permeability and selectivity rate results are shown in Table i; gas permeability is determined
10 1286492 =单位時間’單位面積’單位壓力下之氣體透過量、 擇率定義為兩種氣體之氣體透過率比 」埯 透過一分籬m臌％ ^ \ ϋ值辰不兩氣體 賴後之分離效果，越接近於丨表示分 =。由表】可知，本發明之滞石/多孔不 果 體透過性大且具有氣體選擇率。 的氧 合膜之氣體透過率與選擇率 改質後之多 — 虱乳π 孔不銹鋼 2.92xl〇·7 8.93xl〇·7 /弗石/多孔不 1銹鋼複合膜 2·45χ1〇·7 8.05χ1〇·7 1.84x 1 〇'7 3.29 :室溫 六氟化硫 3.06 ίο 1510 1286492=The gas permeation rate and unit rate under unit pressure per unit area are defined as the gas permeability ratio of the two gases. 埯 一 一 一 一 臌 臌 ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ The effect, the closer to 丨 indicates the score =. From the table, it is understood that the staghorn/porous body of the present invention has high permeability and gas selectivity. The gas permeability and selectivity of the oxygenated membrane are much more modified - 虱 π π pore stainless steel 2.92xl 〇 · 7 8.93xl 〇 · 7 / feldspar / porous non-steel composite film 2·45χ1〇·7 8.05 Χ1〇·7 1.84x 1 〇'7 3.29: room temperature sulfur hexafluoride 3.06 ίο 15
-^—7--L_ 1.53 一 壓力差 3 atm之 實施例3、二氧化鈦光觸媒之塗覆 …將貝W例2之彿石/多孔不錄鋼複合膜浸於—白色酸性 二氧化鈦溶液中，此溶液之ρΗ值為卜4，結晶為銳鈦礦， 二乳化鈦含量1〜6 wt%，粒徑：長軸：1〇〜6〇随，短轴： 5〜20 nm，粘度為1〜5 cps。 · 3〇秒後取出置於悝溫恒澄箱中，座度為95%以上 燥1天；然後置於煅燒爐中，以升溫速率為rc/分鐘加熱： 250 C ’持溫2小時，即可得至丨丨一与 丨侍到一乳化鈦/彿石/多孔不錄鋼 複合膜。 J 實施例4、對-二曱苯之滲透吸附實驗 將實施例2所製備之彿石/多孔;録鋼複合膜管％置於 無機膜反應裝置的氣體分離槽1〇中，如圖丨所示，另於氣 20體飽和器20中加入對-二曱笨液體。調整質量流量計赃^ 50及MFC2 6G的流量至設定進料濃度（㈡刪啊），待濃度-^—7--L_ 1.53 Example 3, a pressure difference of 3 atm, coating of titanium dioxide photocatalyst... immersing the fused stone/porous non-recording steel composite film of Example 2 in a white acidic titanium dioxide solution, the solution The value of ρ is 卜4, the crystal is anatase, the content of titanium emulsified by 1~6 wt%, the particle size: long axis: 1〇~6〇, short axis: 5~20 nm, viscosity is 1~5 cps . · After 3 seconds, take it out and place it in a constant temperature chamber with a seat of 95% or more for 1 day; then place it in a calciner and heat at a heating rate of rc/min: 250 C 'with a temperature of 2 hours. As for the emulsified titanium/fossil/porous non-recorded steel composite film. J Example 4, osmotic adsorption experiment of p-diphenylbenzene The phoenix/porous prepared in Example 2; the recording steel composite film tube % was placed in the gas separation tank 1〇 of the inorganic membrane reaction device, as shown in Fig. It is shown that a p-dioxin liquid is added to the gas 20 body saturator 20. Adjust the flow rate of the mass flow meter 赃^ 50 and MFC2 6G to the set feed concentration ((2) delete), wait for the concentration
11 1286492 穩定後’打開控制閥2丨使 々 ηίβΠΙΨ ^ CJ ^ , 枓亂體進入氣體分離槽10之進 笑」二相層析儀(圖未示)量測透過側12之對-二， 本/辰度皈¥間的變化，如圖2所示。 旦、目可知’在進料濃度為45()ppm時，5G分鐘後才可 1測到透過側12之對-二 伽、-人 一 T本。此代表本發明之沸石/多孔 不錄鋼：合膜可吸附對·二甲苯，而且在5〇分鐘後才達到飽 ^ 改變進㈣度可發現透過側之對-二甲苯出現時 =越短’且其濃度隨時間的上升速率越快。 ίο 實施例5、異丙醇之滲透吸附實驗 、如實施例4所述之裝置，於氣體飽和 器20中加入異丙醇 液體、1調整f量流量計MFC15G及臟2⑼的流量至設定 進料/辰度（G· 1 3G0Ppm) ’量測透過側i 2之異丙醇濃度隨時間 的變化，如圖3所示。 由0 3可知，在進料濃度為沖㈤時，2〇分鐘後才可 15量測到透過側之異丙醇。此代表本發明之沸石/多孔不錄鋼 複合膜亦可吸附異丙醇，而且在2〇分鐘後才達到飽和。另 外，改變進料濃度可發現透過側之異丙醇出現時間越短， 且其濃度隨時間的上升速率越快。 實施例6、丙酮之滲透吸附實驗 -〇 如實施例4所述之裝置，於氣體飽和器20中加入丙酮液 體，调整質量流量計％!?^ 5〇&MFC2 6〇的流量至設定進 料/辰度（0-7000 ppm)，量測透過側12之丙酮濃度隨時間的 變化，如圖4所示。 由圖4可知，在進料濃度為2040 ppm時，在開始3分鐘 12 1286492 y4 p可里測到透過側之丙_，此代表本發明之沸石/多孔不 _複合膜對丙_之吸附能力猶弱。另外，改變進料濃度 可發現透過侧之丙酉同出現時間越短，且其濃度隨時間的上 升速率越快。 5實施例7、對-二甲笨之吸附與分解 ^利用如貫施例4所述之裝置，惟無機膜反應器的氣體分 離槽10中之複合膜管30’係實施例3所製備之二氧化欽/沸 石/夕孔不銹鋼複合膜管，且氣體飽和器2〇中加入對-二甲 苯液體，调整質量流量計MFC1 5〇及MFC2 6〇的流量至設 10疋進料浪度（〇-2〇〇〇ppm)，溫度設定至45〇c，同時開&uv 燈官a，照射條件：1 mW/cm2，照射18小時，接著量測透 過側12之對-二甲苯濃度隨時間的變化，如圖$所示。 圖5甲新膜管之曲線代表以剛製備好之二氧化鈦/沸石 /夕孔不銹鋼複合膜管，進行對-二曱苯滲透吸附實驗。大 15約進饤75分鐘後，對_二曱苯即可透過複合膜，即表示複合 膜已達飽和吸附，對-二甲苯可透過複合膜。 uv未開啟之曲線代表飽和吸附之複合膜，經過丨8小時 空氣渡清後，再進行對·二曱苯之滲透吸附實驗。由圖可知 ’約25分鐘對-二曱苯即可透過複合膜。因複合膜已達飽和 2〇吸附’雖經1 8小時空氣濾清，但仍有部分吸附區域之活性 已再生，故可以短暫吸附對_二曱苯。 UV開啟之曲線代表飽和吸附之複合膜，經過1 8小時空 氣濾清及UV照射後’再進行對-二甲苯之滲透吸附實驗。 由圖5可知，約5〇分鐘後對-二曱苯即可透過複合膜；此代 13 1286492 在之對-二甲苯’由於受到光觸媒二氧化欽 二：解：：可使得複合膜之吸附能力再生，故可以大部分 灵合膜之吸附性能’其效率與新膜管不相上下。 由U V未開啟與U V開啟 有分解污染物之效果。 hi可知，光觸媒確實 過觸=:程序下，於初始操作時間内，並無污染物透 =觸=膜：此可以得到完全去除污染物之氣艚經 二=，污染物開始透過無機膜，此即為穿透點 (即breakthrough point)，而且读巩也丨4 ίο 15 20 ^ , 透過側之污染物濃度會隨操 乍:叫而增加，以迄最終達到與進料側相同之濃度。 卜^覆觸媒之無機膜進行操作時，污染物達到 、;=的日顧較無鑛覆觸媒之無機膜為長。此現象表示 匆吸附在觸媒無機膜上時，亦同時被觸媒分解破壞， 進而=長觸媒無機膜達到餘和吸附濃度的時間；因此，將 ==與觸媒相結合，既可減少傳統吸附劑再生之問題， 。能降低飽和吸附敎處_本，提升處理效益。 2本發明已讀佳實施例揭露如上，然其並非用以 疋X明，任何熟悉此技藝者，在不脫 ，内，當可作各種之更動與潤飾，因此，；：3: 濩靶圍’當視後附之申請專利範圍所界定者為準。 【圖式簡單說明】 圖1係本發明較佳實施例之無機膜反應裝置 圖2係本發明實施例4對_二ρ苯濃度變化圖。 25圖3係本發明實施例5異丙醇濃度變化圖。 14 1286492 圖4係本發明實施例6丙酮濃度變化圖。 圖5係本發明實施例7對-二甲苯濃度變化圖。 【主要元件符號說明】 ' 10氣體分離槽 11進料側 12透過側 · 20氣體飽和器 21控制閥 30複合膜管 50質量流量計MFC1 60質量流量計MFC2 L UV燈管11 1286492 After the stabilization, 'open the control valve 2丨 to make ίηίβΠΙΨ ^ CJ ^, the chaotic body enters the gas separation tank 10 into the laughter.” The two-phase chromatograph (not shown) measures the transmission side 12 pair - two, this The change between / Chen time 皈 ¥, as shown in Figure 2. Once, it can be seen that when the feed concentration is 45 () ppm, it can be measured after 5 G minutes 1 to measure the transmission side 12 - two gamma, - human one T. This represents the zeolite/porous non-recorded steel of the present invention: the film can adsorb p-xylene, and after 5 minutes, the saturation is reached. The change (four) degree can be found when the permeation side of the permeation side appears to be shorter = And the rate at which its concentration rises with time is faster. Ίο Example 5, osmotic adsorption experiment of isopropyl alcohol, the apparatus as described in Example 4, adding isopropyl alcohol liquid to the gas saturator 20, adjusting the flow rate of the f-flow meter MFC15G and the dirty 2 (9) to the set feed / Chen (G · 1 3G0Ppm) 'Measure the change in the concentration of isopropanol on the permeation side i 2 as shown in Figure 3. It can be seen from 0 3 that when the feed concentration is rush (five), the isopropyl alcohol on the permeate side can be measured after 2 minutes. This represents that the zeolite/porous unrecorded steel composite membrane of the present invention can also adsorb isopropanol and achieve saturation after 2 minutes. In addition, changing the feed concentration reveals that the shorter the time of occurrence of isopropanol on the permeate side, and the faster the rate of increase of its concentration with time. Example 6. Infiltration adsorption experiment of acetone - as in the apparatus of Example 4, adding acetone liquid to the gas saturator 20, adjusting the flow rate of the mass flow meter %!?^ 5〇&MFC2 6〇 to the setting The material/density (0-7000 ppm) was measured for the change in acetone concentration over the permeate side 12 as shown in Figure 4. As can be seen from Fig. 4, at the feed concentration of 2040 ppm, the permeation side of the zeolite was measured at the beginning of 3 minutes 12 1286492 y4 p, which represents the adsorption capacity of the zeolite/porous non-composite membrane of the present invention. It is still weak. In addition, changing the feed concentration reveals that the shorter the onset time of the permeate side, and the faster the concentration rises with time. 5, Example 7, adsorption and decomposition of p-dimethyl bromide; using the apparatus as described in Example 4, except that the composite membrane tube 30' in the gas separation tank 10 of the inorganic membrane reactor was prepared in Example 3. Dioxin/zeolite/Xikong stainless steel composite membrane tube, and the para-xylene liquid was added to the gas saturator 2〇, and the flow rate of the mass flow meter MFC1 5〇 and MFC2 6〇 was adjusted to set the feed wave of 10疋 (〇 -2〇〇〇ppm), the temperature is set to 45〇c, and the &uv lamp a, the irradiation condition: 1 mW/cm2, for 18 hours, and then the measurement of the p-xylene concentration on the permeate side 12 over time The change is shown in Figure $. The curve of the new membrane tube of Fig. 5 represents the osmotic adsorption experiment of p-diphenylbenzene with the newly prepared titanium dioxide/zeolite/Xikong stainless steel composite membrane tube. After the large 15 is about 75 minutes later, the p-biphenyl can pass through the composite film, which means that the composite film has reached saturated adsorption, and the p-xylene can penetrate the composite film. The unopened curve of uv represents the saturated adsorption composite membrane. After 8 hours of air clarification, the osmotic adsorption experiment of p-terphenylbenzene was carried out. As can be seen from the figure, the p-biphenylene can pass through the composite film in about 25 minutes. Since the composite membrane has reached saturation 2〇 adsorption, although it has been filtered by air for 18 hours, the activity of some of the adsorption zone has been regenerated, so it is possible to temporarily adsorb p-quinone benzene. The UV-on curve represents a saturated adsorption composite membrane. After 18 hours of air filtration and UV irradiation, the p-xylene adsorption adsorption experiment was performed. It can be seen from Fig. 5 that p-diphenyl can pass through the composite film after about 5 minutes; this generation 13 1286492 is in the para-xylene group due to photocatalytic dioxidation: solution: the adsorption capacity of the composite membrane can be regenerated Therefore, the adsorption performance of most of the membranes can be 'the efficiency is comparable to that of the new membrane tubes. The U V is not turned on and the U V is turned on to have the effect of decomposing pollutants. Hi knows that the photocatalyst does over-touch =: under the program, during the initial operation time, there is no contaminant penetration = touch = membrane: this can get the gas to completely remove the contaminant, the pollutants begin to pass through the inorganic membrane, this It is the breakthrough point, and the reading is also 丨4 ίο 15 20 ^ , and the concentration of the pollutant on the permeate side increases with the operation, so as to finally reach the same concentration as the feed side. When the inorganic film of the catalyst is operated, the pollutants reach the temperature of the inorganic film which is less than the mineral-free catalyst. This phenomenon indicates that when it is adsorbed on the catalytic inorganic film, it is also destroyed by the catalyst decomposition, and then the long catalyst inorganic film reaches the time of the adsorption concentration; therefore, the combination of == and the catalyst can reduce The problem of traditional adsorbent regeneration, It can reduce the saturation adsorption 敎 _ this, improve processing benefits. 2 The preferred embodiment of the present invention has been disclosed as above, but it is not intended to be used by those skilled in the art. Anyone who is familiar with the art can make various changes and retouching during the process. Therefore, 3: 濩 target circumference 'As defined in the scope of the patent application, the scope of the patent application shall prevail. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is an inorganic membrane reaction apparatus according to a preferred embodiment of the present invention. Fig. 2 is a graph showing changes in concentration of bis-bisbenzene in Example 4 of the present invention. Figure 3 is a graph showing the change in the concentration of isopropanol in Example 5 of the present invention. 14 1286492 Figure 4 is a graph showing the change in acetone concentration in Example 6 of the present invention. Fig. 5 is a graph showing changes in the concentration of p-xylene in Example 7 of the present invention. [Main component symbol description] '10 gas separation tank 11 feed side 12 permeate side · 20 gas saturator 21 control valve 30 composite membrane tube 50 mass flow meter MFC1 60 mass flow meter MFC2 L UV tube
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