TWI554474B - Mesoporous adsorption material manufactured by waste calcium fluoride and glass, the manufacturing method and the method for processing acetone - Google Patents
Mesoporous adsorption material manufactured by waste calcium fluoride and glass, the manufacturing method and the method for processing acetone Download PDFInfo
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本發明係有關於一種環保中孔洞吸附材料，特別是指一種利用廢棄氟化鈣與廢玻璃製備之中孔洞吸附材料及其製備方法，以及該中孔洞吸附材料用於低溫處理丙酮的方法。 The invention relates to an environmentally-friendly hole adsorption material, in particular to a hole adsorption material prepared by using waste calcium fluoride and waste glass, a preparation method thereof, and a method for the low-temperature treatment of acetone by the medium hole adsorption material.
隨著高科技業的發展，延伸出許多的污染物處理的問題，污染物包括漿狀的污泥、液態的廢水和各種製程排放的尾氣等。 With the development of the high-tech industry, many problems of pollutant treatment have been extended. The pollutants include slurry sludge, liquid waste water and exhaust gas discharged from various processes.
根據統計，台灣地區每年所產生之氟化鈣(CaF2)污泥量約為10900噸。此外，由於氟化鈣污泥中的氟化鈣含量低(大約20-40%)，其中含有其他不純物質，故較不利於經濟上的再使用及再循環利用，或是更近一步的應用，且氟化鈣污泥很明顯會對健康造成危害，故現行之處理技術主要利用水泥固定化來解決重金屬污泥的處理問題。然而，處理水泥固化產物亦需找到適合的掩埋處置場，在人口稠密的台灣，掩埋場的使用範圍受到限制，故水泥固化程序勢必逐漸不適用，而有必要另闢其他能夠 將污泥中氟化鈣再利用的處理方法。 According to statistics, the amount of calcium fluoride (CaF 2 ) sludge produced in Taiwan every year is about 10,900 tons. In addition, due to the low calcium fluoride content (about 20-40%) in calcium fluoride sludge, which contains other impurities, it is not conducive to economical reuse and recycling, or a further application. And calcium fluoride sludge is obviously harmful to health, so the current treatment technology mainly uses cement immobilization to solve the problem of heavy metal sludge treatment. However, the treatment of cement solidified products also needs to find a suitable landfill disposal site. In densely populated Taiwan, the scope of use of landfills is limited, so the cement curing process is bound to be gradually unsuitable, and it is necessary to add another to be able to remove fluoride from the sludge. Calcium reuse treatment.
此外，揮發性有機化合物(Volatile Organic Compounds,VOCs)是指在標準狀態下(20℃，760mmHg)，其蒸氣壓大於0.1mmHg以上之有機化合物。產生VOCs主要來源包括光電材料及元件製造業、半導體業、煉油工業、表面塗裝業、乾洗業等。由於VOCs無時無刻揮發散佈於空氣中，對人體健康造成直接或間接的傷害，甚至具有致癌的可能。目前處理VOCs的方法大致可分為：冷凝法、熱焚化法、觸媒焚化法、電漿破壞法以及觸媒吸附法。其中，冷凝法處理效率有限；觸媒焚化法及熱焚化法由於需要較高的溫度來破壞VOCs，所以需要大量的燃料，而且會產生微粒問題造成增加二次處理之費用；電漿破壞法易干擾機台，維修費用高，另電源供應器製造費用昂貴且製造技術仍有瓶頸；而觸媒吸附法可以較短的滯留時間及較低的溫度下來操作，而且設備較不佔空間、亦較節省燃料、處理量大，也不會因高溫而產生二次污染物的困擾，故觸媒吸附法是目前處理VOCs技術中最具發展潛力的。 Further, Volatile Organic Compounds (VOCs) refer to organic compounds having a vapor pressure of more than 0.1 mmHg or more in a standard state (20 ° C, 760 mmHg). The main sources of VOCs include photovoltaic materials and component manufacturing, semiconductors, oil refining, surface coating, and dry cleaning. Since VOCs are volatilized in the air all the time, it causes direct or indirect damage to human health and even has the potential for carcinogenesis. At present, the methods for processing VOCs can be roughly classified into a condensation method, a thermal incineration method, a catalyst incineration method, a plasma destruction method, and a catalyst adsorption method. Among them, the condensation treatment efficiency is limited; the catalyst incineration method and the thermal incineration method require a large amount of fuel because of the need for higher temperatures to destroy VOCs, and the problem of particulate matter is increased to increase the cost of secondary treatment; Interfering with the machine, the maintenance cost is high, the power supply is expensive to manufacture and the manufacturing technology still has bottlenecks; and the catalyst adsorption method can operate with shorter residence time and lower temperature, and the equipment is less space-consuming and less Fuel saving, large processing capacity, and no secondary pollutants caused by high temperature, so the catalyst adsorption method is currently the most potential development in the processing of VOCs technology.
是以，綜合以上種種因素，本案發明人設想提出一種利用氟化鈣與廢玻璃製備之中孔洞吸附材料及其製備方法以及其用於處理VOCs廢氣的方法。 Therefore, in combination with the above various factors, the inventor of the present invention contemplates a method for preparing a pore adsorbing material using calcium fluoride and waste glass, a preparation method thereof, and a method for treating the exhaust gas of VOCs.
本發明之目的在於提供一種利用廢棄氟化鈣與廢玻璃製備之中孔洞吸附材料及其製備方法，藉此，達到提供一種廢棄物再利用、環保且活性吸附量高而具有相當商業價值的中孔洞吸附材料。 The object of the present invention is to provide a pore adsorbing material for preparing waste calcium fluoride and waste glass, and a preparation method thereof, thereby providing a waste with reuse, environmental protection and high active adsorption amount, and having considerable commercial value. Hole adsorption material.
緣是，為達上述目的，本發明所提供一種利用廢棄氟化鈣與廢玻璃製備之中孔洞吸附材料的製備方法，其中，該方法步驟包括：(1)製備一矽源溶液，係由廢玻璃粉末溶於氫氧化鈉溶液製成；(2)製備一有機溶液，係由十六烷基三甲基溴化銨(CTABr)溶於去離子水並加入氫氧化銨製成；(3)製備一混合溶液，係將步驟(1)的矽源溶液逐滴加入步驟(2)的有機溶液中，再加入廢棄氟化鈣製成，並調整該混合溶液的pH值至4；(4)製備一初成品，係將步驟(3)的混合溶液依序進行過濾、洗滌及乾燥；以及(5)鍛燒，將步驟(4)的初成品進行高溫鍛燒，去除有機模板後，製得一中孔洞吸附材料(CF-MCM吸附材料)。 Therefore, in order to achieve the above object, the present invention provides a method for preparing a pore adsorbing material in the preparation of waste calcium fluoride and waste glass, wherein the method comprises the following steps: (1) preparing a helium source solution, which is waste The glass powder is prepared by dissolving in a sodium hydroxide solution; (2) preparing an organic solution prepared by dissolving cetyltrimethylammonium bromide (CTABr) in deionized water and adding ammonium hydroxide; (3) Preparing a mixed solution, the step source solution of step (1) is added dropwise to the organic solution of step (2), and then added with waste calcium fluoride, and the pH of the mixed solution is adjusted to 4; (4) Preparing a preliminary product, the mixed solution of the step (3) is sequentially filtered, washed and dried; and (5) calcining, the preliminary product of the step (4) is subjected to high temperature calcination, and the organic template is removed, and then obtained. A medium pore adsorption material (CF-MCM adsorption material).
本發明另一目的在於，將前述本發明利用氟化鈣污泥製備之該中孔洞吸附材料用於處理丙酮的方法，達到在低溫下進行含丙酮氣體吸附反應，不僅降低以往處理VOCs氣體所需耗費的能源，利用廢棄氟化鈣製成之中孔洞吸附材料處理VOCs氣體亦更具有環保之功效。 Another object of the present invention is to provide the method for treating acetone by using the medium pore adsorbing material prepared by using the calcium fluoride sludge in the foregoing invention, thereby achieving the adsorption reaction of the acetone-containing gas at a low temperature, which not only reduces the need for the conventional treatment of VOCs gas. The energy consumed, the use of waste calcium fluoride to make the VOCs in the hole adsorption material is also more environmentally friendly.
為達上述目的，本發明所提供一種前述中孔洞吸附材料用於處理丙酮的方法，其中，該方法步驟包括：(1)提供含丙酮(C3H6O)之氣體至一吸附材料反應器；(2)提供適量之該中孔洞吸附材料、該含鐵中孔洞吸附材料或該含銅中孔洞吸附材料並置入該吸附材料反應器；(3)令該中孔洞吸附材料在25至70℃的溫度下，經吸附法與該含丙酮之氣體進行低溫吸附反應。 In order to achieve the above object, the present invention provides a method for treating acetone in the above-mentioned mesoporous adsorption material, wherein the method step comprises: (1) providing a gas containing acetone (C 3 H 6 O) to an adsorbent material reactor (2) providing an appropriate amount of the medium pore adsorbing material, the iron-containing pore adsorbing material or the copper-containing pore adsorbing material and placing the adsorbent material reactor; (3) making the medium pore adsorbing material at 25 to 70 At a temperature of ° C, a low temperature adsorption reaction is carried out with the acetone-containing gas by an adsorption method.
較佳的，前述中孔洞吸附材料用於處理丙酮的方法中，步驟(1)的氣體具有500至2000ppm之丙酮濃度，且該氣體之流量為100至 800mL/min，該氣體在吸附材料反應器停留的時間為2.4至0.4秒。 Preferably, in the method for treating acetone in the medium pore adsorbing material, the gas of the step (1) has an acetone concentration of 500 to 2000 ppm, and the flow rate of the gas is 100 to At 800 mL/min, the gas stayed in the adsorbent reactor for a period of 2.4 to 0.4 seconds.
有關於本發明為達成上述目的，所採用之技術、手段及其他功效，茲舉較佳可行實施例並配合圖式詳細說明如后。 The preferred embodiments of the present invention, as well as the accompanying drawings, are set forth in the accompanying drawings.
〔本發明〕 〔this invention〕
無 no
圖1A、圖1B係本發明中孔洞吸附材料及其製備材料CaF2的SEM特性分析圖。 1A and 1B are SEM characteristic diagrams of the hole adsorbing material and the preparation material CaF 2 of the present invention.
圖2係本發明中孔洞吸附材料在不同溫度對丙酮進行吸附之變化曲線圖。 Fig. 2 is a graph showing the adsorption of acetone adsorbing materials at different temperatures in the present invention.
圖3係本發明中孔洞吸附材料在不同流量對丙酮進行吸附之變化曲線圖。 Fig. 3 is a graph showing the change of adsorption of acetone in different flow rates of the pore adsorbing material in the present invention.
圖4係本發明中孔洞吸附材料在不同濃度對丙酮進行吸附之變化曲線圖。 Fig. 4 is a graph showing the adsorption of acetone adsorption materials at different concentrations in the present invention.
圖5係本發明中孔洞吸附材料使用CF-MCM實測值與弗羅因德利奇(Freundlich)及朗繆爾(Langmuir)模式預測值之比較曲線圖。 Fig. 5 is a graph comparing the measured values of the CF-MCM with the predicted values of the Freundlich and Langmuir modes in the pore adsorbing material of the present invention.
圖6係本發明中孔洞吸附材料的阿瑞尼斯模型(Arrhenius model)圖。 Figure 6 is a diagram of the Arrhenius model of the pore sorbent material of the present invention.
請配合參閱圖1A至圖6所示，說明本發明利用氟化鈣與廢玻璃製備之中孔洞吸附材料及其製備方法以及其用於處理丙酮的方法。 Please refer to FIG. 1A to FIG. 6 to illustrate the pore adsorbing material in the preparation of calcium fluoride and waste glass according to the present invention, a preparation method thereof and a method for treating acetone.
本發明主要是將廢玻璃加入廢棄氟化鈣研製高表面積矽酸鹽中孔洞吸附材料，簡稱為CF-MCM(CaF2+MCM-41)，藉此，製得具有多 孔隙、高比表面積、均勻的孔隙大小分佈與晶粒分佈，並有良好的吸附能力的中孔洞吸附材料。 The invention mainly comprises adding waste glass to waste calcium fluoride to develop a high surface area silicate salt adsorption material, referred to as CF-MCM (CaF 2 + MCM-41), thereby obtaining a porous, high specific surface area, Uniform pore size distribution and grain distribution, and good adsorption capacity of the mesoporous adsorption material.
以下說明本發明中孔洞吸附材料CF-MCM(以下簡稱CF-MCM吸附材料)的製備方法，該CF-MCM吸附材料的材料主要包括廢棄氟化鈣及廢玻璃，該廢棄氟化鈣係取自半導體廠的氟化鈣污泥，並經乾燥形成塊狀並研磨成粉狀後製成；其中，該方法步驟包括： The preparation method of the pore-adsorbing material CF-MCM (hereinafter referred to as CF-MCM adsorbing material) in the present invention is described below. The material of the CF-MCM adsorbing material mainly includes waste calcium fluoride and waste glass, and the waste calcium fluoride is taken from The calcium fluoride sludge of the semiconductor factory is formed by drying to form a block and grinding into a powder; wherein the method steps include:
(1)製備一矽源溶液，係由廢玻璃粉末溶於氫氧化鈉溶液製成；於本實施例中，步驟(1)的矽源溶液，係取40克廢玻璃粉末溶於100毫升濃度為99wt%的氫氧化鈉溶液，在150±5℃的溫度下，透過磁石攪拌器以攪拌速度660rpm連續攪拌24小時製成。 (1) preparing a ruthenium source solution, which is prepared by dissolving waste glass powder in a sodium hydroxide solution; in the present embodiment, the ruthenium source solution of step (1) is obtained by dissolving 40 g of waste glass powder in a concentration of 100 ml. The 99 wt% sodium hydroxide solution was prepared by continuously stirring at a stirring speed of 660 rpm for 24 hours at a temperature of 150 ± 5 ° C through a magnet stirrer.
(2)製備一有機溶液，係由十六烷基三甲基溴化銨(CTABr)溶於去離子水並加入氫氧化銨製成；於本實施例中，步驟(2)的有機溶液，係取2.5克十六烷基三甲基溴化銨(CTABr)溶於125毫升去離子水，加入10毫升濃度為28wt%的氫氧化銨溶液，在室溫下，透過磁石攪拌器連續攪拌15分鐘，使十六烷基三甲基溴化銨(CTABr)完全溶解後製成。 (2) preparing an organic solution prepared by dissolving cetyltrimethylammonium bromide (CTABr) in deionized water and adding ammonium hydroxide; in this embodiment, the organic solution of step (2), 2.5 g of cetyltrimethylammonium bromide (CTABr) was dissolved in 125 ml of deionized water, 10 ml of a 28 wt% ammonium hydroxide solution was added, and the mixture was continuously stirred by a magnet stirrer at room temperature. In minutes, the cetyltrimethylammonium bromide (CTABr) was completely dissolved.
(3)製備一混合溶液，係將步驟(1)的矽源溶液逐滴加入步驟(2)的有機溶液中，再加入廢棄氟化鈣製成，並調整該混合溶液的pH值至4；於本實施例中，步驟(3)的混合溶液，係加入1克廢棄氟化鈣(約佔10%)，並以4N硫酸溶液調整pH值至4後，在室溫下，透過磁石攪拌器連續攪拌8小時後製成。 (3) preparing a mixed solution, the solution of the step (1) is added dropwise to the organic solution of step (2), and then added to waste calcium fluoride, and adjust the pH of the mixed solution to 4; In this embodiment, the mixed solution of the step (3) is added with 1 gram of waste calcium fluoride (about 10%), and adjusted to a pH of 4 with a 4N sulfuric acid solution, and then passed through a magnet stirrer at room temperature. It was prepared by continuously stirring for 8 hours.
(4)製備一初成品，係將步驟(3)的混合溶液依序進行過濾、洗滌及乾燥；於本實施例中，步驟(4)的初成品，係以去離子水及酒精洗滌 後，再置於烘箱以100±5℃之溫度乾燥4至8小時後製成。 (4) preparing a preliminary product, the mixed solution of the step (3) is sequentially filtered, washed and dried; in the embodiment, the preliminary product of the step (4) is washed with deionized water and alcohol. Thereafter, it is further dried in an oven at a temperature of 100 ± 5 ° C for 4 to 8 hours.
(5)將步驟(4)的初成品進行高溫鍛燒，去除有機模板後，製得一中孔洞吸附材料(CF-MCM吸附材料)；於本實施例中，步驟(5)的中孔洞吸附材料，係將步驟(4)的初成品置於高溫爐中，以550℃的溫度鍛燒6小時後製成。 (5) The preliminary product of the step (4) is subjected to high-temperature calcination, and after removing the organic template, a mesoporous adsorption material (CF-MCM adsorption material) is obtained; in the embodiment, the mesopores of the step (5) are adsorbed. In the material, the preliminary product of the step (4) is placed in a high temperature furnace and calcined at a temperature of 550 ° C for 6 hours.
於本實施例中，經前述步驟製得之該中孔洞吸附材料具有合成材料莫爾比為CTMABr：NaOH：NH4OH：Si：CaF2=145：0.39：3.5：1.5：78。 In the present embodiment, the mesoporous adsorbent material obtained by the foregoing steps has a synthetic material molar ratio of CTMABr:NaOH:NH 4 OH:Si:CaF 2 =145:0.39:3.5:1.5:78.
以上所述即為本發明中孔洞吸附材料的製備方法實施例，以下說明本發明利用廢棄氟化鈣製備之中孔洞吸附材料用於處理丙酮的方法。 The above is the embodiment of the method for preparing the pore adsorbing material in the present invention. The following describes the method for preparing the acetone in the preparation of the void adsorbing material by using the waste calcium fluoride.
本發明前述CF-MCM吸附材料用於處理丙酮的方法，該方法步驟包括：(1)提供含丙酮(C3H6O)之氣體至一吸附材料反應器；於本實施例中，該氣體具有500至2000ppm之丙酮濃度，且該氣體之流量為100至800mL/min，該氣體在吸附材料反應器停留的時間為2.4至0.4秒；(2)提供適量之該中孔洞吸附材料、該含鐵中孔洞吸附材料或該含銅中孔洞吸附材料並置入該吸附材料反應器；(3)令該中孔洞吸附材料在25至70℃的溫度下，經吸附法與該含丙酮之氣體進行低溫吸附反應。 The method for treating acetone by the CF-MCM adsorbent of the present invention, the method comprising the steps of: (1) providing a gas containing acetone (C 3 H 6 O) to a adsorbent reactor; in the present embodiment, the gas Having a acetone concentration of 500 to 2000 ppm, and the flow rate of the gas is 100 to 800 mL/min, the gas staying in the adsorbent material reactor for 2.4 to 0.4 seconds; (2) providing an appropriate amount of the medium pore adsorbing material, the containing a hole in the iron or a porous material in the copper and placed in the adsorbent reactor; (3) the medium pore adsorbent is subjected to an adsorption method and the acetone-containing gas at a temperature of 25 to 70 ° C Low temperature adsorption reaction.
以上係本發明利用廢棄氟化鈣製備之中孔洞吸附材料及其製備方法以及其用於處理丙酮的方法，以下請配合參閱圖1A至圖6，說明 本發明製得之中孔洞吸附材料的SEM特性分析、氮氣等溫吸附/脫附儀特性分析、溫度、停留時間、濃度對材料吸附能力的影響等分析結果，並以弗羅因德利奇模型(Freundlich model)、朗繆爾模型(Langmuir model)及阿瑞尼斯模型(Arrhenius model)探討本發明中孔洞吸附材料用於處理丙酮的吸附行為。 The above is the use of the waste calcium fluoride in the preparation of the hole adsorption material and the preparation method thereof and the method for treating the same, please refer to FIG. 1A to FIG. The SEM characteristic analysis of the pore adsorption material, the characteristic analysis of the nitrogen isotherm adsorption/desorption instrument, the influence of the temperature, the residence time and the concentration on the adsorption capacity of the material, and the Freundlich model are obtained by the invention. (Freundlich model), Langmuir model and Arrhenius model are used to investigate the adsorption behavior of the pore adsorbing material in the present invention for treating acetone.
圖1A、圖1B顯示本發明CF-MCM吸附材料及所取用的原料CaF2的SEM特性分析圖。在SEM中可明顯看出CaF-MCM吸附材料是屬於球狀的材料，而原料CaF2也一樣是球狀的。CF-MCM吸附材料的生成是由界面活性劑和矽酸鹽共同合成，CF-MCM吸附材料觀察其外觀具有圓形、橢圓形等顆粒形狀，而CaF2觀察外觀具有團聚且微小顆粒狀。 1A and 1B are graphs showing SEM characteristics of the CF-MCM adsorbent of the present invention and the raw material CaF 2 taken . It is apparent in the SEM that the CaF-MCM adsorbent material is a spherical material, and the raw material CaF 2 is also spherical. The CF-MCM adsorbent was synthesized by a surfactant and a citrate. The CF-MCM adsorbent was observed to have a circular or elliptical particle shape, while the CaF 2 observation had agglomerated and fine particles.
如下表1所示，顯示中孔洞吸附材料MCM-41、本發明CF-MCM吸附材料及其所取用的原料CaF2的氮氣等溫吸附/脫附儀特性分析結果。由表1中可以得知MCM-41、CF-MCM吸附材料與CaF2之比表面積分別為1480、908.5及35m2g-1；其平均孔洞體積分別為0.987、0.598及0.155cm3g-1，其孔洞分佈分別集中於3.37、2.62與39.7nm。 As shown in Table 1 below, the results of the analysis of the characteristics of the nitrogen isotherm adsorption/desorption apparatus of the medium pore adsorption material MCM-41, the CF-MCM adsorption material of the present invention, and the raw material CaF 2 taken therein are shown. It can be seen from Table 1 that the specific surface areas of MCM-41, CF-MCM adsorbent and CaF 2 are 1480, 908.5 and 35m2g -1 , respectively; the average pore volume is 0.987, 0.598 and 0.155cm3g -1 , respectively. Focused on 3.37, 2.62 and 39.7 nm, respectively.
圖2顯示本發明中孔洞吸附材料在不同溫度對丙酮進行吸附之變化曲線圖。從圖2中可以看出，隨著溫度的升高，CF-MCM吸附材料的吸附能力逐漸增高。這種現象的產生可能是由於溫度的升高，分子間的熱運動加快，從而提升了丙酮分子與CF-MCM吸附材料材料之間碰撞的撞擊率。一方面丙酮分子吸附到CF-MCM吸附材料表面的速度加快了，使的吸附速率變快。 Fig. 2 is a graph showing the change of adsorption of acetone to the pore adsorbing material at different temperatures in the present invention. It can be seen from Fig. 2 that as the temperature increases, the adsorption capacity of the CF-MCM adsorbent material gradually increases. This phenomenon may be caused by an increase in temperature and an increase in thermal motion between molecules, thereby increasing the impact rate of collision between acetone molecules and CF-MCM adsorbent materials. On the one hand, the adsorption rate of acetone molecules on the surface of the CF-MCM adsorbent material is accelerated, and the adsorption rate is increased.
圖3顯示本發明中孔洞吸附材料在不同流量對丙酮進行吸附之變化曲線圖。本實施例以濃度為1000ppm之丙酮進行吸附測試，其操作條件為反應器溫度25℃、壓力1atm、1g m-3吸附材料，氣體流量分別控制於100、200、400及800mL min-1，停留時間分別為2.4、1.9、0.9與0.4sec，以探討於不同流量下，對丙酮去除效率之影響；結果顯示丙酮去除效率隨流量增加而隨之增加。CF-MCM吸附材料之貫穿時間分別約為620與460、290、210min，其吸附量順序為101.75、170.46、130.32及190.36mg g-1；由上述結果可得隨著丙酮入流流量提高，將增加丙酮分子與CF-MCM吸附材料材料之間的撞擊力，有利於CF-MCM吸附材料捕捉丙酮分子的行為，CF-MCM吸附材料吸附量相對增加，但會使吸附材料較早達到飽和。丙酮入流流量愈大愈早達到飽和狀態，入流流量愈小愈需要更多時間才能達到飽和狀態。CF-MCM吸附材料之貫穿時間分別約為620與460、290、210min。 Fig. 3 is a graph showing the change of the adsorption of the pore adsorbing material to acetone at different flow rates in the present invention. In this example, the adsorption test was carried out with acetone at a concentration of 1000 ppm, and the operating conditions were a reactor temperature of 25 ° C, a pressure of 1 atm, and a 1 g m -3 adsorbent material, and the gas flow rates were controlled at 100, 200, 400, and 800 mL min -1 , respectively. The time was 2.4, 1.9, 0.9 and 0.4 sec, respectively, to investigate the effect of acetone removal efficiency at different flow rates; the results showed that the acetone removal efficiency increased with increasing flow. The penetration time of CF-MCM adsorbent materials is about 620 and 460, 290, 210 min, respectively. The order of adsorption is 101.75, 170.46, 130.32 and 190.36 mg g -1 . From the above results, it will increase with the increase of acetone influx. The impact force between acetone molecules and CF-MCM adsorbent materials is beneficial to the behavior of CF-MCM adsorbent materials to capture acetone molecules. The adsorption capacity of CF-MCM adsorbent materials is relatively increased, but the adsorbent materials will reach saturation earlier. The earlier the influent flow rate of acetone reaches saturation, the smaller the inflow flow rate takes more time to reach saturation. The penetration time of the CF-MCM adsorbent material was about 620 and 460, 290, and 210 min, respectively.
圖4顯示本發明中孔洞吸附材料在不同濃度對丙酮進行吸附之變化曲線圖。本實施例是將吸附反應器溫度及壓力分別設定為25℃及1atm，進流流量為800mL min-1，停留時間為0.4sec，使用0.5g CF-MCM吸附材料材料，分別探討使用CF-MCM吸附材料對丙酮濃度為500、1000、1500 及2000ppm吸附能力之影響；實驗結果顯示，當丙酮濃度為500、1000、1500及2000ppm之初始濃度下，其吸附量分別為118.37、190.44、250.63與256.90mg g-1。由上述結果可得隨著丙酮入流濃度提高，氣流中可被CF-MCM吸附材料吸附的分子數目亦增加，故CF-MCM吸附材料吸附量相對增加，但會使吸附材料較早達到飽和。 Fig. 4 is a graph showing the change of the adsorption of the pore adsorbing material to acetone at different concentrations in the present invention. In this embodiment, the adsorption reactor temperature and pressure are respectively set to 25 ° C and 1 atm, the inflow flow rate is 800 mL min -1 , the residence time is 0.4 sec, and 0.5 g of CF-MCM adsorbent material is used, respectively, and CF-MCM is used for discussion. The effect of adsorbent materials on the adsorption capacity of acetone at 500, 1000, 1500 and 2000 ppm; the experimental results show that when the acetone concentration is 500, 1000, 1500 and 2000 ppm, the adsorption capacities are 118.37, 190.44, 250.63 and 256.90 respectively. Mg g -1 . From the above results, as the concentration of acetone inflow increases, the number of molecules adsorbed by the CF-MCM adsorbent in the gas stream also increases, so the adsorption amount of the CF-MCM adsorbent increases relatively, but the adsorbent material is saturated earlier.
圖5顯示本發明中孔洞吸附材料使用CF-MCM實測值與弗羅因德利奇(Freundlich)及朗繆爾(Langmuir)模式預測值之比較曲線圖。請配合參閱下表2，將四種濃度下之飽和吸附量代入Freundlich和Langmuir模式，可得到本發明CF-MCM吸附材料之等溫吸附方程式。研究結果顯示代入Freundlich與Langmuir模式經線性回歸後，回歸相關係數分別為0.995及0.993，其相關等溫吸附程式之參數匯整如表2所示。圖5是MCM-41於不同丙酮濃度之實際吸附量與Freundlich及Langmuir模式之比較，如圖5所示Langmuir模式的計算值與實際值十分接近，因此可以認定Langmuir模式對本實施例在單成份吸附系統中有不錯的適用性，最大吸附能力為500mg g-1，較適合描述MCM-41材料之吸附行為。 Fig. 5 is a graph showing the comparison of the measured values of the CF-MCM with the predicted values of the Freundlich and Langmuir modes in the pore adsorbing material of the present invention. Please refer to Table 2 below to substitute the saturated adsorption amount at four concentrations into the Freundlich and Langmuir modes to obtain the isotherm adsorption equation of the CF-MCM adsorbent of the present invention. The results show that after linear regression of the Freundlich and Langmuir modes, the regression correlation coefficients are 0.995 and 0.993, respectively. The parameters of the related isothermal adsorption program are shown in Table 2. Figure 5 is a comparison of the actual adsorption capacity of MCM-41 at different acetone concentrations with the Freundlich and Langmuir modes. The calculated values of the Langmuir mode shown in Figure 5 are very close to the actual values, so it can be determined that the Langmuir mode is single-component adsorption for this example. The system has good applicability, the maximum adsorption capacity is 500mg g -1 , which is more suitable for describing the adsorption behavior of MCM-41 material.
圖6顯示本發明中孔洞吸附材料的阿瑞尼斯模型(Arrhenius model)圖。如下表3所示，從阿瑞尼斯方程可以看出，lnk隨T的變化率與活化能Ea成正比。因此活化能越高，溫度升高時反應速率增加得越快，反應速率對溫度越敏感。如果同時存在多個活化能值不同的反應，則高溫對活化能高的反應有利，低溫對活化能低的反應有利。 Fig. 6 is a view showing an Arrhenius model of the pore adsorbing material of the present invention. As shown in Table 3 below, it can be seen from the Arenis equation that the rate of change of lnk with T is proportional to the activation energy Ea. Therefore, the higher the activation energy, the faster the reaction rate increases as the temperature increases, and the more sensitive the reaction rate is to temperature. If a plurality of reactions having different activation energy values exist at the same time, the high temperature is favorable for the reaction with high activation energy, and the low temperature is favorable for the reaction with low activation energy.
綜上所述，本發明透過上述利用廢棄氟化鈣與廢玻璃製備之中孔洞吸附材料及其製備方法以及其用於處理丙酮的方法，確實可達到上述諸項功效，誠已符合專利申請要件，爰依法提出專利申請，祈請惠予審查並早日賜准專利，實感德便。 In summary, the present invention can achieve the above-mentioned various effects by using the above-mentioned pore adsorbing material in the preparation of waste calcium fluoride and waste glass, and the method for treating the same, and the invention has met the requirements of the patent application.爰Proposed a patent application in accordance with the law, praying for a review and granting a patent at an early date.
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