200819567 九、發明說明： 【發明所屬之技術領域】 € 本發明是有關於一種多孔性纖維布製造方法，且特別 ^ 是有關於一種具有高均一度之孔洞比表面積的多孔性纖 維布製造方法。 【先前技術】 鲁 活性奴材料由於其多孔性質’可提供良好的吸附、導 電、再生等特性，目前被廣泛應用於民生用品、環保用品、 工業及高科技產業。例如應用於化學、醫療、軍事防護市 場，製作口罩、防護衣、防毒面具等防護用途，或用於一 般的紡織品、淨水、廢水處理等用途。 活性％原料可大致分為顆粒狀活性碳、粉狀活性碳及 活性碳纖維等數種。其中顆粒狀活性碳、粉狀活性碳為傳 統型恶的活性碳材料，係以椰子殼、褐煤或泥煤等原料經 ^ 高溫碳化而成，其原料取得容易、成本低廉，但缺點是雜 貝含量高，性能不佳。活性碳纖維布則可分為木質素系、 ^树月曰系、瀝青系及聚丙烯腈系（p〇lyaCryl〇nitrile; PAN) 等數種。其中木質素系原料成本最低，但其纖維機械性質 差；酚樹脂系不但成本高，機械性質亦不佳；瀝青系則因 機械性質極差故以致加工性不佳；唯有聚丙烯腈系不但具 有良好的機械性質，成本也居中，較適宜開發使用。 聚丙烯腈系活性碳纖維原料之型態可為氧化纖維長 絲、紗所形成的非織物布或氇，經過活化及碳化過程形成 5 200819567 聚丙烯腈系活性碳纖維布。活化工程—般利用化學活化法 或物理活化法來進行。化學活化法即是利用添加化學藥劑 (如ZnCl2、H3P〇4、KOH、K2S等）處理氧化纖維布，其優 點為反應溫度低且焦油產生量低，但缺點是活性碳純度不 夠’製程中容易產生有毒物質、污染性高且需增加水洗製 程，反而造成二次污染。物理活化法則是使用含氧氣體進 行活化，其特色是製成之活性碳純度高且製程中污染性 低，但缺點疋製程温度高較耗能且焦油產生率高。 前人有利用將消防衣用之丙烯腈系纖維布，將含水之 二氧化碳作為活化劑，導入一高溫爐中以活化產生丙烯腈 系活化纖維布。然而，由於係利用含水之二氧化碳進行活 化工程，需預先將二氧化碳與水混合再送入高溫爐中，因 此，除需多一道混合的程序外，二氧化碳中所含的飽和蒸 汽亦難以精確的控制，造成活化後產生的奈米孔洞分佈不 均’成品品質無法一致的情形。 因此’需要有一種更簡便有效的活化製程，來解決丙 烯腈系活化纖維布奈米孔洞分佈不均，影響產品效能的問 題0 【發明内容】 因此本發明的目的就是在提供一種多孔性纖維布製 造方法’用以改善傳統多孔性纖維布製造方法製成之成口 孔洞分佈不均的缺點。 根據本發明之上述目的，提出一種多孔性纖維布製造 6 200819567 方法，係以聚丙烯腈系氧化纖維布作為原料，進行一活碳 化製程（activated Carb〇nation pr〇cess)，利用具有多管式= 應管路之熱處理爐，分別將活化氣體及/或活化液體^不 同管路通人處理爐中，並將聚㈣㈣氧化纖維布以羅拉 (roller)裝置輸送入處理爐中，以介於1〇1〇^〜ΐ5〇〇£^之溫 度處理-段時間’得到孔洞分佈均—且比表面積（bet)維 持在800〜1500平方公尺/公克之多孔性纖維布，可適用於 實際量產。 依照本發明之實施例，活化氣體可為含氧之氣體，例 如氧氣、二氧化碳、一氧化碳、水蒸氣、空氣或含上述氣 體之混合物。活化液體可為含氧之液體，例如純水、自來 水、雙氧水、酸性電解水或含上述液體之混合物。 為了使本發明之構成特徵、操作方法、目的及優點更 加容易了解，故於下文中配合圖示及文字敘述，說明本發 明之實施例。200819567 IX. Description of the Invention: [Technical Field to Be Invented by the Invention] The present invention relates to a method for producing a porous fibrous cloth, and particularly to a method for producing a porous fibrous cloth having a specific surface area of a hole having a high uniformity. [Prior Art] Lu active slave materials are widely used in people's livelihood, environmental protection, industrial and high-tech industries due to their porous properties, which provide good adsorption, conductivity, and regeneration. For example, it is used in chemical, medical, and military protection markets to make protective covers such as masks, protective clothing, and gas masks, or for general textiles, water purification, and wastewater treatment. The active % raw material can be roughly classified into several types such as granular activated carbon, powdered activated carbon, and activated carbon fiber. Among them, granular activated carbon and powdered activated carbon are traditional activated carbon materials, which are made of high-temperature carbonized materials such as coconut shell, lignite or peat. The raw materials are easy to obtain and low in cost, but the disadvantage is miscellaneous shellfish. High content and poor performance. Activated carbon fiber cloth can be divided into lignin, ^ tree sap, asphalt and polyacrylonitrile (p〇lyaCryl〇nitrile; PAN). Among them, lignin-based raw materials have the lowest cost, but their fiber mechanical properties are poor; phenolic resin is not only costly, but also has poor mechanical properties; asphaltic products are poor in mechanical properties due to poor mechanical properties; only polyacrylonitrile is not only It has good mechanical properties and is also cost-effective. It is suitable for development and use. The polyacrylonitrile-based activated carbon fiber raw material may be a non-woven fabric or a crucible formed by oxidized fiber filaments or yarns, which is formed by activation and carbonization process. 5 200819567 Polyacrylonitrile-based activated carbon fiber cloth. Activation engineering is generally carried out by chemical activation or physical activation. Chemical activation method is to treat oxidized fiber cloth by adding chemical agents (such as ZnCl2, H3P〇4, KOH, K2S, etc.), which has the advantages of low reaction temperature and low tar production, but the disadvantage is that the purity of activated carbon is not enough. Produce toxic substances, high pollution and need to increase the washing process, but cause secondary pollution. The physical activation method is activated by using an oxygen-containing gas, which is characterized in that the activated carbon produced is high in purity and low in pollution in the process, but the disadvantage is that the process temperature is higher than the energy consumption and the tar generation rate is high. The former has used an acrylic fiber-based cloth for fire-fighting clothes, and introduced carbon dioxide as an activator into a high-temperature furnace to activate and produce an acrylic-based actinated fiber cloth. However, since the carbon dioxide is used for the activation process, it is necessary to mix the carbon dioxide with the water and then feed it into the high temperature furnace. Therefore, in addition to the one more mixing procedure, the saturated steam contained in the carbon dioxide is difficult to accurately control, resulting in The distribution of nanopores generated after activation is not uniform. Therefore, there is a need for a more simple and effective activation process to solve the problem of uneven distribution of the pores of the acrylic fiber-activated fiber, and affect the product efficiency. [The present invention] Therefore, the object of the present invention is to provide a porous fiber cloth. The manufacturing method 'is used to improve the disadvantage of uneven distribution of the pores formed by the conventional porous fiber cloth manufacturing method. According to the above object of the present invention, a method for producing a porous fiber cloth 6 200819567 is proposed, which uses a polyacrylonitrile-based oxidized fiber cloth as a raw material to carry out an activated carbonization process (multi-tube type). = The heat treatment furnace of the pipeline shall be respectively used to treat the activated gas and/or the activated liquid into different furnaces, and the poly(tetra)(tetra) oxidized fiber cloth shall be conveyed into the treatment furnace by a roller device to be between 1 〇1〇^~ΐ5〇〇£^The temperature treatment - the period of time to obtain a porous fiber cloth with a uniform pore distribution and a specific surface area (bet) of 800 to 1500 m ^ 2 / g, can be applied to actual mass production . According to an embodiment of the invention, the activating gas may be an oxygen-containing gas such as oxygen, carbon dioxide, carbon monoxide, water vapor, air or a mixture containing the above gases. The activating liquid may be an oxygen-containing liquid such as pure water, tap water, hydrogen peroxide, acidic electrolyzed water or a mixture containing the above liquid. In order to make the features, operation, objects, and advantages of the present invention more comprehensible, the embodiments of the present invention are described below in conjunction with the drawings.
【實施方式】 請參照第1圖’其繪示依照本發明一實施例之製備多 孔性纖維布的製程示意圖。 製備多孔性纖維布之設備包含一熱處理爐100,具有 複數個反應管路採多管式分佈於爐内各區域，活化劑可以 氣態或液態直接經由這些反應管路通入熱處理爐10〇中。 熱處理爐1 00之入口端及出口端以鈍氣作為隔絕氣體。 依照本發明之一實施例，熱處理爐100中可僅導入液 7 200819567 雙氧水、酸性電 可同時自複數個 態形式之活化劑。例如：純水、自來水 解水或含上述液體之混合物等含氡液體 反應管路通入熱處理爐1 00中。 依照本發明之另-實施例，熱處理爐100中可僅導入 氣態形式之活化劑。例如：氧氣、二氧化碳、-氧化碳、 水蒸氣、空氣或含上述氣體之混合物等含氧氣體，可同時 自複數個反應管路通入熱處理爐10Ό中。 依照本發明之又一實施例，熱處理爐100中可同時導 入氣態及液態形式之活化劑。例如，反應管路110可用以 通入活化氣體111，例如氧氣、二氧化碳、一氧化碳、水 条氣、空氣或含上述氣體之混合物等含氧氣體；反應管路 120可用以通入活化液體121，例如純水、自來水、雙氧 水、酸性電解水或含上述液體之混合物等含氧液體。值得 注意的是，反應管路110及反應管路12〇在第1圖中之數 量、外型及配置方式僅為例示，熱處理爐100依實際需要 ¥ 可設置複數個反應管路，藉以同時通入所需的活化液體及 氣體。 此外，由於活化氣體111及活化液體121係各別通入 熱處理爐100，因此不需將氣體與液體預先混合，因此不 需氣體混合裝置，相對減少操作及設備之成本。 依照本發明之一實施例，製備多孔性纖維布之原料為 聚丙烯腈系氧化纖維布130，可利用複數組羅拉裝置14〇 並沿箭頭方向將原料送入熱處理爐1〇〇中，進行一活碳化 工程。 8 200819567 熱處理爐100需加熱至101(rc〜15〇〇c>c之間，加熱之 ’ 1域如第1圖之虛線區域160所示，反應時間可為i分鐘 呈〇刀鐘由於本發明之活碳化工程進行時，活化氣體 111及活化液體121可各別自反應管路11G及反應管路㈣ 通入熱處理爐100,因此可以精確控制氣體及液體之濃度 與流量，因此製備出的多孔性纖維布15〇所含之奈米孔洞 肖勾度較傳統製程高’利用本發明之方法製作之多孔性纖 φ 維布可確保連續式送人的原料在不同長度位置的孔洞均 勻度皆一致，其比表面積（BET)可維持在8〇〇〜15〇〇平方公 尺/公克。 請參照第2圖及第3圖，為利用本發明之方法生產的 多孔性纖維布於不同取樣長度下的孔洞均—度測試。分别 以相同生產速度，在101{rc、1〇5(rc、n5〇t：、12〇〇。〇之 活碳化溫度條件下，通入7jc 5分鐘作用得到多孔性纖维 布。再於第1〇0公尺、1000公尺及5〇〇〇公尺長處取3〇〜 5〇公分長之多孔性纖維布樣品，分別剪成5〜1〇公分之寬 度，以ASTM D3663-03標準之方法，利用比表面積·微孔 • 洞測定儀(Micro_dtiCS ASAP2020)進行分析，觀察製程中 不同階段在多孔性纖維布表面所產生的孔洞之ΒΕτ變化。 結果顯示，於各溫度條件下生產之樣品，其不同長度 處的BET皆可維持在poo—uoo平方公尺/公克之間广= 不應用本發明之方法生產的多孔性纖維布在整個製程中 攸一開始到最後所產生的成品之孔洞分佈差異性極小，孔 洞均勻度高。亦由此可知，本發明之製備多孔性纖維布的 9 200819567 方法不但適用於連續式量產，更能精確控制成品品質，產 生孔洞均一度高之多孔性纖維布。 r 自上述本發明較佳實施例可知，應用本發明具有下列 ^ 優點： 首先’本發明之製備多孔性纖維布的方法，係利用於 高溫的活化處理爐中導入活化劑，可同時進行聚丙稀猜系 氧化碳纖維布的碳化及活性化製程，大幅縮減製程時間， # ㉟加產能。而且，本發明之活碳化工程中不需使用化學藥 劑，利用含氧氣體及/或含氧液體作為活化劑，原料容易取 得且無二次污染。 此外，由於活化劑可由不同管路分別通入活碳化爐 中，因此不需要使用氣體混合器，相對的降低初設備之成 〇 再者，也是最重要的一點，本發明之熱處理爐反應氣 體管路，係採多管式分佈於爐内各區域，除可精確控制氣 W 體及液體的流量及濃度外（不需預先混合），活化劑分別導 ♦ 入後更可於聚丙烯腈系氧化纖維布表面各區域充分反 ^ 應，使應用本發明之方法製造出的多孔性纖維布的奈米孔. 洞均勻分佈於多孔性纖維布表面。由於多孔性纖維布為連 續式生產，因此本發明之方法可維持量產時的品質控制， 使成品品質具有良好之一致性，可應用於實際量產。 雖然本發明已以一較佳實施例揭露如上，然其並非用 以限定本發明，任何熟習此技藝者，在不脫離本發明之精 神和範圍内，當可作各種之更動與潤飾，因此本發明之保 200819567 護範圍當視後附之申請專利範圍所界定者為準。 【圖式簡單說明】 ▲為讓本發明之上述和其他目的、特徵、優點與實施例 月&更明顯易懂，所附圖式之詳細說明如下： 第1圖係緣示本發明-實施例之製備多孔性纖維[Embodiment] Please refer to Fig. 1 for a schematic view showing a process for preparing a porous fiber cloth according to an embodiment of the present invention. The apparatus for preparing a porous fiber cloth comprises a heat treatment furnace 100 having a plurality of reaction tubes distributed in various portions in the furnace, and the activator can be directly introduced into the heat treatment furnace through the reaction tubes in a gaseous state or a liquid state. The inlet end and the outlet end of the heat treatment furnace 100 are blunt gas as an insulating gas. According to an embodiment of the present invention, only the liquid can be introduced into the heat treatment furnace 100. 200828567 Hydrogen peroxide, acid electricity can simultaneously self-complex the activator of the state. For example, pure water, tap water, or a liquid containing a mixture of the above liquids, the reaction line is passed through a heat treatment furnace 100. According to another embodiment of the present invention, only the activator in gaseous form can be introduced into the heat treatment furnace 100. For example, oxygen-containing gas such as oxygen, carbon dioxide, carbon oxide, water vapor, air or a mixture containing the above gases can be simultaneously introduced into the heat treatment furnace 10 from a plurality of reaction lines. According to still another embodiment of the present invention, an activator in a gaseous state and a liquid form can be simultaneously introduced into the heat treatment furnace 100. For example, the reaction line 110 can be used to pass an activating gas 111, such as oxygen, carbon dioxide, carbon monoxide, water strips, air, or an oxygen-containing gas containing a mixture of the above gases; the reaction line 120 can be used to pass the activating liquid 121, for example An oxygen-containing liquid such as pure water, tap water, hydrogen peroxide, acidic electrolyzed water or a mixture containing the above liquid. It should be noted that the number, shape and arrangement of the reaction line 110 and the reaction line 12 in FIG. 1 are merely examples, and the heat treatment furnace 100 can set a plurality of reaction lines according to actual needs, thereby simultaneously Enter the required activating liquid and gas. Further, since the activating gas 111 and the activating liquid 121 are separately introduced into the heat treatment furnace 100, it is not necessary to premix the gas and the liquid, so that the gas mixing device is not required, and the cost of the operation and equipment is relatively reduced. According to an embodiment of the present invention, the raw material for preparing the porous fiber cloth is a polyacrylonitrile-based oxidized fiber cloth 130, and the raw material can be fed into the heat treatment furnace 1 by using a multi-array roller device 14 沿 in the direction of the arrow. Live carbonization project. 8 200819567 The heat treatment furnace 100 needs to be heated to between 101 (rc~15〇〇c>c, the heated '1 domain is as shown by the dashed line area 160 of Fig. 1, and the reaction time can be i minutes as a sickle clock. When the living carbonization process is carried out, the activation gas 111 and the activation liquid 121 can be separately introduced into the heat treatment furnace 100 from the reaction line 11G and the reaction line (4), so that the concentration and flow rate of the gas and the liquid can be precisely controlled, and thus the porous body is prepared. The nanofiber hole included in the fiber cloth 15〇 is higher than the conventional process. The porous fiber φ fabric made by the method of the invention ensures that the uniformity of the continuous feed material is uniform at different lengths. The specific surface area (BET) can be maintained at 8 〇〇 to 15 〇〇 m ^ 2 / gram. Please refer to Figures 2 and 3 for the porous fiber cloth produced by the method of the present invention at different sampling lengths. The hole uniformity test was carried out at the same production rate at 101{rc, 1〇5 (rc, n5〇t:, 12〇〇. at the carbonization temperature of the crucible, and 7jc was applied for 5 minutes to obtain porosity. Fiber cloth. Then at the first 〇0 meters A sample of porous fiber cloth of 3 〇 5 5 cm long at a length of 1000 m and 5 ft. is cut into a width of 5 to 1 cm, and the specific surface area is determined by the method of ASTM D3663-03. The micropore • hole analyzer (Micro_dtiCS ASAP2020) was used to analyze the ΒΕτ changes in the pores generated on the surface of the porous fiber cloth at different stages of the process. The results show that the samples produced at various temperatures have BET at different lengths. It can be maintained between poo-uoo square meters/gram wide. The porous fiber cloth produced by the method of the present invention has little difference in pore distribution and uniform pores in the whole process from the beginning to the end of the whole process. It is also known that the method of preparing the porous fiber cloth of the present invention 9 200819567 is not only suitable for continuous mass production, but also can accurately control the quality of the finished product, and produces a porous fiber cloth having a uniform hole height. The preferred embodiment of the invention shows that the application of the present invention has the following advantages: First, the method for producing a porous fibrous cloth of the present invention is utilized at a high temperature activation point. The activator is introduced into the furnace to simultaneously carry out the carbonization and activation process of the oxidized carbon fiber cloth, and the process time is greatly reduced, and the production capacity is increased by #35. Moreover, the chemical carbonization project of the present invention does not require the use of chemical agents, and the use thereof The oxygen gas and/or the oxygen-containing liquid act as an activator, and the raw materials are easily obtained without secondary pollution. Furthermore, since the activator can be separately introduced into the living carbonization furnace from different pipelines, it is not necessary to use a gas mixer, and the relative reduction is early. Furthermore, the most important point of the equipment is that the reaction gas pipeline of the heat treatment furnace of the present invention is distributed in various regions of the furnace in addition to precisely controlling the flow rate and concentration of the gas body and the liquid ( Without pre-mixing, the activator can be fully reacted in various areas on the surface of the polyacrylonitrile-based oxidized fiber cloth to make the nanopores of the porous fiber cloth produced by the method of the present invention. It is evenly distributed on the surface of the porous fiber cloth. Since the porous fiber cloth is continuously produced, the method of the present invention can maintain quality control in mass production, and has good consistency in finished product quality, and can be applied to actual mass production. Although the present invention has been described above in terms of a preferred embodiment, it is not intended to limit the invention, and it is obvious to those skilled in the art that various changes and modifications can be made without departing from the spirit and scope of the invention. The scope of the invention 200819567 is subject to the definition of the scope of the patent application. BRIEF DESCRIPTION OF THE DRAWINGS In order to make the above and other objects, features, advantages and embodiments of the present invention more obvious and obvious, the detailed description of the drawings is as follows: Figure 1 shows the invention - implementation Preparation of porous fiber
奉 製程示意圖。 ' 第2圖為利用本發明之方法生產的多孔性纖維布尤 同取樣長度下的孔洞均一度測試結果。 、 第3圖為利用本發明之方法生產的多孔 同取樣長度下的耐變化曲線圖。 ^布於不 【主要元件符號說明】 1G0 :熱處理爐 1 1 1 :活化氣體 121 :活化液體 14〇 :羅拉裝置 160 :虛線區域 π 〇 :反應管路 120 :反應管路 130 ··氧化纖維布 150 ··多孔性纖維布 11A schematic diagram of the process. Fig. 2 is a view showing the uniformity test of the hole in the porous fiber cloth produced by the method of the present invention at the sampling length. Fig. 3 is a graph showing the change in the resistance of the porous sample produced by the method of the present invention at the same sampling length. ^布未不 [Main component symbol description] 1G0: heat treatment furnace 1 1 1 : activation gas 121 : activation liquid 14 〇: roller device 160 : dotted line region π 〇: reaction line 120: reaction line 130 · oxidized fiber cloth 150 ··Porous fiber cloth 11