201136677 、 六、發明說明： 【發明所屬之技術領域】 本發明關於一種調濕型材料，尤指一種具優異調濕 性能及抗折性強的調濕型材料。 【先前技術】 台灣的平面顯示器產業自1998年起投入大面積薄 膜式電晶體型液晶顯示器面板製造，根據行政院衛生署 公佈資料顯示’每年所掩埋的50〜60萬公頓的廢玻璃 • 廢棄物中’其中有Μ00公噸係為薄膜式液晶螢幕（ThinBACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a humidity-conditioning material, and more particularly to a humidity-conditioning material having excellent humidity control properties and strong folding resistance. [Prior Art] Taiwan's flat panel display industry has been manufacturing large-area thin-film transistor type liquid crystal display panels since 1998. According to the information released by the Department of Health of the Executive Yuan, it shows that 50-600,000 metric tons of waste glass is buried every year. Among them, 00 metric tons is a thin film LCD screen (Thin
Film Transistor Liquid，TFT-LCD)之廢玻璃；現今台灣 使用廢棄玻璃回收再利用之方式多為先將玻璃分為分 色玻璃及混色玻璃，再以熔融方式重新將玻璃再製，其 中分色玻璃用途多再製成玻璃容器，而混色玻璃多再利 用於土木、建築骨材、二次製品製造及景觀園藝等，但 TFT-LCD產業所使用之玻璃成份較為特殊，多為無鹼硼 矽玻璃，回收後無法如一般傳統產業之玻璃進入熔融再 製’因此如何將此類廢玻璃善加利用即為一亟待開發的 ❿ 課題。 目前台灣較為成熟之TFT-LCD產業廢玻璃資源化 技術係為將廢玻璃經由分類、去雜質、碎筛選、洗條、 及震動筛選等流程後，再控制粒度與顏色分選等條^， 最後產出玻璃碎砂。玻璃碎砂可作為「再生玻璃砂」， 亦可應用為「綠建桌材料」，其中再生玻璃砂可供手工 玻璃製造廠製造玻璃藝品、玻璃製轴廠及燒製陶磁地 磚、面磚、建材。而綠建築材料常被稱為環保建材，可 作為建材、裝潢材料，包括亮彩琉璃、玻璃地磚、玻璃 201136677 大理石專，也可作為水泥製品添加物，包括輕質骨材、 高壓地磚、水泥連鎖磚及玻璃紅磚等，也可供公共工程 使用，包括玻璃瀝青鋪路、輕質骨材等。 另一方面，石油產業中，會以不同製程生產或提升 油品，而觸媒在油品煉製過程中，由於表面堆積雜質會 造成其活性下降，為維持系統内觸媒的反應效率，將^ 補充新的觸媒，而移除使用過後其催化功能喪失之觸 媒，這些催化功能喪失之觸媒即為廢觸媒。目前將廢觸 媒再利用之方式多為回收釩鉬等有價金屬、製碑或路面 紗石級配料添加使用等，但經處理後之含鎳殘渣（俗稱 藍泥）則進行掩埋處理，目前每年掩埋廢觸媒的量約達 10,000'•镇，為一亟待解決之環境問題。 綜上所述，將廢玻璃掩埋處理或熔融再製並非最有 效利用資源的方式，在環保越益受到重視的今日，迫切 的需要更為妥善的方式回收利用年產量節節升高的廢 玻璃與廢觸媒。 【發明内容】 有鑑於先刚技術之缺失，本發明之主要目的為提供 一種調濕型材料，其係以廢玻璃及廢觸媒為主要材料， 達到資源回收的目標。 本發明之又一目的為提供一種調濕型材料的製作 方法，其係以廢玻璃及廢觸媒為主要材料，以製得具有 優異調濕性和抗折度強之調濕型材料。 為達上述目的，本發明一種調濕型材料，其係包含 1 wt%〜60 wt%的廢玻璃及4〇 wt%〜99 wt%的廢觸 媒。 較佳地，前述廢玻璃係為液晶螢幕、太陽能板或容 201136677 器類之廢玻璃。 較佳地’前述廢觸媒係為失去活性之廢觸媒。 較佳地，前述失去活性之廢觸媒係為= 媒0 較佳地’前述材料尺寸面積範圍係為：〇〇〇16〜 10.00 m 〇 較佳地田其置於室溫且濕度為10%〜95%RH 下，24小時後之平衡含水率值為〇 〇i〜5kg/kg。 1佳地，當前述材料之抗折強度大於61.2]^/娜2 時’係用於建材。 本發明再提供一種製造調溼型材料的方法，其包 含：Film Transistor Liquid (TFT-LCD) waste glass; nowadays Taiwan uses waste glass for recycling and recycling. The method is mainly to divide the glass into dichroic glass and mixed glass, and then re-make the glass by melting. More glass containers are used, and the mixed-color glass is reused in civil engineering, building aggregates, secondary product manufacturing, and landscape gardening. However, the glass components used in the TFT-LCD industry are relatively special, mostly non-alkaline borosilicate glass. After recycling, it is impossible to enter the molten remanufactured glass as in the traditional industry. Therefore, how to make good use of such waste glass is an urgent issue to be developed. At present, Taiwan's more mature TFT-LCD industry waste glass resource technology technology is to control waste glass by sorting, impurity removal, crush screening, washing, and vibration screening, and then control particle size and color sorting. Finally, the glass is crushed. Glass crushed sand can be used as "recycled glass sand", and can also be applied as "green table material". Reclaimed glass sand can be used to manufacture glass art, glass shaft factory and fired ceramic floor tile, brick and building materials. . Green building materials are often referred to as environmentally-friendly building materials. They can be used as building materials and decorative materials, including bright colored glass, glass floor tiles, and glass 201136677 marble. They can also be used as cement product additives, including lightweight aggregates, high-pressure floor tiles, and cement chains. Bricks and glass red bricks are also available for public works, including glass asphalt paving and lightweight aggregates. On the other hand, in the petroleum industry, oil products will be produced or upgraded in different processes. In the process of oil refining, the catalyst will cause its activity to decrease due to surface accumulation of impurities. In order to maintain the reaction efficiency of the catalyst in the system, ^ Add a new catalyst, and remove the catalyst whose catalytic function is lost after use. The catalyst for the loss of these catalytic functions is the waste catalyst. At present, the recycling of waste catalysts is mostly for the recovery of valuable metals such as vanadium and molybdenum, the use of monuments or pavement grades, etc., but the treated nickel-containing residue (commonly known as blue mud) is buried and is currently buried every year. The amount of waste catalyst is about 10,000'• town, which is an environmental problem to be solved. In summary, the disposal of waste glass or melt remanufacturing is not the most effective way to use resources. Today, when environmental protection becomes more and more important, there is an urgent need to recycle waste glass with increasing annual output. Waste catalyst. SUMMARY OF THE INVENTION In view of the lack of prior art, the main object of the present invention is to provide a humidity-controlling material which uses waste glass and waste catalyst as main materials to achieve the goal of resource recovery. Another object of the present invention is to provide a method for producing a humidity-controlling material which uses waste glass and a waste catalyst as main materials to obtain a humidity-controlling material having excellent humidity control property and high folding resistance. To achieve the above object, the present invention relates to a humidity-conditioning type material comprising 1 wt% to 60 wt% of waste glass and 4 wt% to 99 wt% of waste catalyst. Preferably, the waste glass is a liquid crystal screen, a solar panel or a waste glass of the type 201136677. Preferably, the aforementioned waste catalyst system is an inactive waste catalyst. Preferably, the aforementioned deactivated waste catalyst system is = medium 0. Preferably, the foregoing material size area ranges from 〇〇〇16 to 10.00 m. Preferably, the field is placed at room temperature and the humidity is 10%. At ~95% RH, the equilibrium moisture content after 24 hours is 〇〇i~5kg/kg. 1 good land, when the flexural strength of the above materials is greater than 61.2] ^ / Na 2 ' is used for building materials. The present invention further provides a method of making a humidity-conditioning material comprising:
Ja)提供一原料，其係包含廢玻璃及廢觸媒； (b )將如述原料研磨並過|争； (c) 將前述步驟（b)處理過後的原料加壓成型；及 (d) 將經前述加壓成型之材料進行燒結。 車父佳地’前述步驟（a)進一步包含將前述原料烘 乾。 較佳地，前述磨碎並過筛的廢玻璃或廢觸媒之顆粒 大小係為：300〜1400 m2/kg 。 _ 較隹地，進行前述步驟（c)之前可進一步調整前 述廢破螭和前述廢觸媒之相對比例。 2 較隹地’前述步驟（c)的壓力為20〜250 kg f/cm ο 分 較佳地’前述步驟（d)之升溫速率為5〜20 °c/ 較隹地，前述步驟（d)之燒結溫度為600〜1400。(：。 較隹地’前述燒結溫度係為9〇〇。(3〜95(TC。 201136677 較佳地，前述燒結時間係為〇1〜6小時。 ’ ί述?結之方法係為高溫爐燒結。 前述高溫爐燒結之係為電窯、瓦斯黨或材 媒4=本==型材料係以廢玻續和廢觸 作為主原料’以不同比例的廢觸媒ί代 廢玻璃’紐行燒結及加壓而料本發明娜型材料。 【實施方式】 調濕型材料係指一種可以吸濕及抗折之材料，其可 作為環境之吸濕產品、建材或建材之填充材料等用^， 其中當其重金屬的含量、平衡含水率、吸濕性能及抗折 強度皆需符合標準，方得以作為建材。 本發明係關於將廢玻璃和廢觸媒回收並加工而製 得之調濕型材料，其中廢玻璃係作為主成分，以廢觸媒 取代而改變燒結體之特性，以製得吸濕性佳及抗折性強 的調濕型材料；其中前述廢玻璃及廢觸媒之含量比例 為· 1 wt%〜60 wt%的廢玻璃及40 wt%〜99 wt%的廢 觸媒；於較佳實施例中，前述廢玻璃係含有6〇 wt%的 廢玻璃及40 wt%的廢觸媒。 本發明之調濕型材料，較佳為符合標準之12小時 之吸濕量（依照日本調濕建材判定基準之規定）至少29 g/rri以上； 本發明調濕型材料之平衡含水率值測定係為將成 品置於室溫之濕度為10%〜95%RH環境下24小時做測 域’所得平衡含水率值為0.01〜5 kg/kg ;當置於室溫 之中濕域環境下（濕度為53%〜75%RH，）測試時’ 201136677 較佳實施態樣所測得之平衡含水率值為〇.5〜2 k (台灣氣候屬於中濕域環境，可參考此值）；當】、t 濕域環境（濕度約為75%〜95%RH)下，較‘银T = 樣所測得之平衡含水率值為2〜5 kg/kg。 a知態 CNS3298 R2064規範陶瓷壁磚之抗折標準為至小 61.2 kg f/cm 2以上，當本發明調濕型材料符合，ζ 時，可作為建材用。 知竿 本發明調濕型材料之尺寸面積範圍係依昭 調整，以適用於各種建築用建材，其較佳為：〇〇〇 == 10.00 rri。 〜 本發明所述之「廢玻璃」係指含有二氧化矽、 妈、氧化結、氧化納、氧化鐵、氧化鎮、氧化硫、^匕 卸或其組合之成份的玻璃，進—步表示在—般使 製品之產業中’製造完成品所產生之廢棄副產品， 經由機器設備運作後所產生之玻璃剪切碎料或瑕疵 品；例如，但不限於製造液晶螢幕、太陽能板或容器類 所產生之廢玻璃，於本發明之較佳實施例中，係以製造 TFT-LCD廢玻璃後所產生之廢棄職品，其成份主要為 鲁 二氧化石夕（Si〇2)及氧化舞（ca〇)。 本發明所述之「廢觸媒」係指含有氧㈣、二氧化 碎、氧化鉀、氧化辑或其組合之成份的觸媒，進一步表 不為失去活性之賴媒；例如，但不限於煉油廠之廢觸 媒，於本發狀較佳實施_巾，似煉油廠精煉原油 製程時造成觸媒活性降低，失去活性的廢觸媒，其主要 成伤為氧化銘（Al2〇3)及二氧化石夕（Si〇2)。 本發明亦提供-調濕型材料之製造方法，請參第二 圖，其係包含下列步驟： 首先取得所需原料（廢玻璃及廢觸媒），龙將前述 201136677 原料烘乾並研磨，前述研磨可採用習知的研磨方式， 不需加以限制，較佳為球磨。接下來，將研磨後 過筛，過_目的係為了採耻徑平均的原料顆粒'，、 將有助於後續燒結過程中調濕型材料結構的強化與穩 定性，因此原則上無須限制使用之篩網，只要能篩 相似粒徑的原料顆粒即可，例如：6〇〜4〇〇目之篩網γ 較佳地，係使用100號篩網；較佳地，經前述過篩步驟 後，所篩選的原料顆粒的細度為300〜1400 M/kg。 接著，調整原料中廢玻璃和廢觸媒的配比，廢玻 為本發明主要成份’其所占比例在Iwt%〜60 wt% ;廢 觸媒提供本發明調濕型材料的吸附功能’其所占比例在 40 〜99 wt% ;於較佳實施例中，其廢玻璃含量為 60 wt% ’廢觸媒含量為4〇 wt%。 經選擇適當配比後，將前述原料加壓成型，使用壓 力為20〜250 kg f/αη2’但所屬領域具有通常知識者， 當可視情況使用適合之壓力以將前述原料固定為所需 之形狀。前述形狀不需加以限制，可視本發明調濕型材 料的運用需求，加壓為任何幾何形狀，其包含：矩形、 長方形或圓形。 然後，將前述加壓成型後的原料進行燒結。因高溫 燒結將使燒結體趨向緻密化，並且會封閉燒結體中的孔 洞結構，造成孔洞關閉影響其吸附性能，成長因此前述 燒結的溫度會影響本發明調濕型材料之平衡含水率，當 燒結溫度越高，平衡含水率越低；而前述燒結之緻密化 現象會造成燒結體的機械強度。於本發明之燒結步驟可 以任何所屬領域習知的高溫燒結方式進行，包括，但不 限於.電窯、瓦斯窯或材窯。前述燒結的溫度為6〇〇〜 1400C ;於較佳實施例中，前述燒結溫度係為9〇〇。〇〜 201136677 950°C ;升溫速率為5〜20°C/min，而燒結停留時間約 為〇. 1〜6小時，並接著自然冷卻至室溫。 於燒結後，即完成本發明之調濕型材料，其成品之 面積可視需求而為不同大小，較佳為0.0016〜10.00 m2。 以下實施例係用於進一步了解本發明之優點，並非 用於限制本發明之申請專利範圍；其各別以TFT-LCD 廢玻璃及廢觸媒之不同比例燒結並加壓而成之調濕型 材料的各種性能測試。 實施例一：本發明調濕型材料之原料的成分及特性分析 首先以X-ray螢光分析儀（X-ray Fluorescence Spectrometer，XRF)分析本發明之TFT-LCD廢玻璃和 廢觸媒之成分，其結果係列於下表一： 表一：本發明調濕型材料之原料的成分分析 成分（wi%) 廢觸媒 ❿Ja) providing a raw material comprising waste glass and a waste catalyst; (b) grinding and arranging the raw material as described; (c) press molding the raw material treated in the foregoing step (b); and (d) The material subjected to the aforementioned press molding is sintered. The aforementioned step (a) further comprises drying the aforementioned raw materials. Preferably, the particle size of the previously pulverized and sieved waste glass or waste catalyst is 300 to 1400 m2/kg. _ In a relatively short manner, the relative proportions of the aforementioned waste chopper and the aforementioned spent catalyst can be further adjusted before the aforementioned step (c). 2 隹 ' 'The pressure of the aforementioned step (c) is 20~250 kg f / cm ο preferably 'the heating rate of the aforementioned step (d) is 5~20 °c / 隹, the aforementioned step (d) The sintering temperature is 600 to 1400. (:. The above sintering temperature is 9 〇〇. (3~95 (TC. 201136677 Preferably, the sintering time is 〇1~6 hours. ' ί ? 结 之 之 之 之 之 之 之 之 之 之Sintering. The above-mentioned high-temperature furnace is sintered by electric kiln, gas party or material medium. 4=This == type of material is based on waste glass and waste touch as the main raw material 'different proportion of waste catalyst ί waste glass' Sintering and pressurizing the material of the present invention. [Embodiment] A humidity-control material refers to a material that can absorb moisture and resist, and can be used as an environmental moisture-absorbing product, a building material or a building material filling material, etc. The invention relates to a humidity-control type obtained by recycling and processing waste glass and waste catalyst when the content of heavy metal, the equilibrium moisture content, the moisture absorption property and the flexural strength are all in accordance with the standard. The material, in which the waste glass is used as a main component, and the characteristics of the sintered body are changed by replacing with the waste catalyst to obtain a humidity-controlling material with good hygroscopicity and strong folding resistance; wherein the waste glass and the waste catalyst are contained in the above materials; The ratio is · 1 wt% ~ 60 wt% waste glass and 40 wt% ~ 9 9 wt% of the spent catalyst; in the preferred embodiment, the waste glass contains 6 wt% waste glass and 40 wt% waste catalyst. The humidity-control material of the present invention preferably conforms to the standard. The moisture absorption amount of 12 hours (according to the Japanese Standard for Determination of Humidity Building Materials) is at least 29 g/rri or more; the equilibrium moisture content of the humidity-control material of the present invention is determined by placing the finished product at room temperature with a humidity of 10%~ The equilibrium moisture content obtained in the measurement field of 24 hours in 95% RH environment is 0.01~5 kg/kg; when it is placed in a wet environment at room temperature (humidity is 53%~75% RH), it is tested 201118677 The equilibrium moisture content measured by the preferred embodiment is 〇.5~2 k (Taiwan climate belongs to the medium-humidity environment, and can be referred to this value); when], t wet environment (humidity is about 75%~95) Under %RH), the equilibrium moisture content measured by 'silver T = sample is 2~5 kg/kg. a. The CNS3298 R2064 specification ceramic wall brick has a folding standard of 61.2 kg f/cm 2 or less. When the humidity-control material of the present invention conforms to ζ, it can be used as a building material. The size range of the humidity-control material of the present invention is adjusted according to Zhao, For use in various building materials, it is preferably: 〇〇〇 == 10.00 rri. ~ "Waste glass" as used in the present invention means cerium oxide, mother, oxidation, sodium oxide, iron oxide, oxidation town The glass of the composition of sulphur oxide, slag, or a combination thereof, and the step of showing the waste by-product produced by the finished product in the industry of the product, the glass cutting scrap produced after the operation of the machine equipment Or a defective product; for example, but not limited to, the production of waste glass produced by a liquid crystal screen, a solar panel or a container; in a preferred embodiment of the present invention, the waste product produced by manufacturing the TFT-LCD waste glass, Its main components are Lu Shihua Xi Xi (Si〇2) and Oxidation Dance (ca〇). The term "waste catalyst" as used in the present invention means a catalyst containing oxygen (tetra), oxidized ash, potassium oxide, oxidized or a combination thereof, and further indicates that it is a carrier which loses activity; for example, but not limited to refining The waste catalyst of the factory is better implemented in this hair style. It is like a refinery that refines the crude oil process and causes the activity of the catalyst to decrease. The active catalyst is lost. The main injury is Oxidation (Al2〇3) and II. Oxide oxide (Si〇2). The invention also provides a method for manufacturing a humidity-controlling material, which is referred to in the second figure, which comprises the following steps: First, obtaining the required raw materials (waste glass and waste catalyst), the dragon dries and grinds the aforementioned 201136677 raw material, the aforementioned The grinding can be carried out by a conventional grinding method, and is not limited, and is preferably ball milling. Next, the sieve is ground after grinding, and the purpose is to use the raw material particles of the shaved diameter average, which will contribute to the strengthening and stability of the structure of the humidity-conditioning material in the subsequent sintering process, so there is no need to limit the use in principle. The screen may be sieved as long as it can sieve raw material particles of similar particle size, for example: 6 〇 4 mesh mesh γ. Preferably, a 100 mesh screen is used; preferably, after the aforementioned sieving step, The fineness of the raw material particles to be screened is 300 to 1400 M/kg. Next, adjusting the ratio of waste glass and waste catalyst in the raw material, the waste glass is the main component of the invention, and its proportion is in the range of 1 wt% to 60 wt%; the waste catalyst provides the adsorption function of the humidity-control material of the present invention. The proportion is 40 to 99 wt%; in the preferred embodiment, the waste glass content is 60 wt% 'the waste catalyst content is 4 〇 wt%. After selecting an appropriate ratio, the above-mentioned raw materials are press-formed to a pressure of 20 to 250 kg f/αη2', but those skilled in the art, if appropriate, use suitable pressure to fix the aforementioned raw materials into a desired shape. . The foregoing shape is not limited, and may be pressurized to any geometric shape, including: rectangular, rectangular or circular, depending on the application requirements of the humidity-conditioning material of the present invention. Then, the raw material after the press molding described above is sintered. The high temperature sintering will make the sintered body tend to densify, and will close the pore structure in the sintered body, causing the pore closure to affect its adsorption performance, so the temperature of the above sintering will affect the equilibrium moisture content of the humidity-conditioning material of the present invention, when sintering The higher the temperature, the lower the equilibrium moisture content; and the densification of the aforementioned sintering causes the mechanical strength of the sintered body. The sintering step of the present invention can be carried out in any high temperature sintering manner known in the art including, but not limited to, an electric kiln, a gas kiln or a material kiln. The sintering temperature is 6 Torr to 1400 C; in the preferred embodiment, the sintering temperature is 9 Torr. 〇~ 201136677 950 ° C; the heating rate is 5 to 20 ° C / min, and the sintering residence time is about 1 to 6 hours, and then naturally cooled to room temperature. After the sintering, the humidity-conditioning material of the present invention is completed, and the area of the finished product may be different in size depending on the demand, and is preferably 0.0016 to 10.00 m2. The following examples are intended to further understand the advantages of the present invention, and are not intended to limit the scope of the patent application of the present invention; the humidity-control type which is sintered and pressurized by different ratios of TFT-LCD waste glass and waste catalyst. Various performance tests of materials. Example 1: Analysis of composition and characteristics of raw materials of the humidity-controlling material of the present invention First, the composition of the TFT-LCD waste glass and waste catalyst of the present invention was analyzed by X-ray Fluorescence Spectrometer (XRF). The results are shown in the following table 1: Table 1: Component analysis components (wi%) of the raw materials of the humidity-controlling materials of the present invention
Si02 ai2o3 Fe2〇3 CaO MgO S03 Na2〇 K,0 67.84 1.61 20.06 39 59 0.1 0.3 結果顯示TFT-LCD廢玻璃i 陶，約佔67.84wt% ’次要成份為氧:=二 約佔20.06 wt%，而廢觸媒則主要以氣化紹)’與 201136677 二氧化矽（Si〇2)居多。再以x-ray繞射分析儀（XRD) · 分析本發明之調濕型材料的晶相物種。請先參第一圖， 為本發明之TFT-LCD廢玻璃和廢觸媒的XRD圖譜，其 中波峰1代表二氧化石夕（Si〇2)而波峰2代表石夕化鐵 (FhSi)’由結果可知TFT_LCD廢玻璃並無定形之非結 晶結構，因此XRD分析結果無明顯繞射峰繞，而呈現 較多雜訊。而廢觸媒之晶相為二氧化矽（Si〇2)和矽化 鐵（Fe2Si)。 接下來，依據環檢所公告之NIEAR208.03C標準方 法，測試本發明所用之TFT_LCD廢玻璃和廢觸媒的酸 鹼值（pH值，固液比以1:10比例與蒸餾水混合）、密度· (density )、含水量（moisture )及燒失量（l〇ss 〇f ignition ) 等物理性質’其結果係列於下表二： 表二：本發明調濕型材料之原料的物理性質分析結果 PH .. 密度 含水量燒失量 ----LLLii)__(g/cm3) ( % ) ( % )Si02 ai2o3 Fe2〇3 CaO MgO S03 Na2〇K,0 67.84 1.61 20.06 39 59 0.1 0.3 The results show that TFT-LCD waste glass i ceramics, accounting for about 67.84wt% 'minor composition is oxygen:= two accounts for about 20.06 wt%, The waste catalyst is mainly based on gasification] and 201136677 cerium oxide (Si〇2). Further, an x-ray diffraction analyzer (XRD) was used to analyze the crystal phase species of the humidity-conditioning material of the present invention. Please refer to the first figure, which is the XRD pattern of the TFT-LCD waste glass and waste catalyst of the present invention, wherein the peak 1 represents the dioxide (Si〇2) and the peak 2 represents the Shihic iron (FhSi) As a result, it was found that the TFT_LCD waste glass had no amorphous structure, so the XRD analysis showed no significant diffraction peaks and more noise. The crystal phases of the spent catalyst are cerium oxide (Si〇2) and strontium iron (Fe2Si). Next, according to the NIEAR208.03C standard method announced by the Environmental Protection Institute, the pH value of the TFT_LCD waste glass and the waste catalyst used in the present invention (pH value, solid-liquid ratio mixed with distilled water in a ratio of 1:10), density· Physical properties such as (density), moisture (loss) and loss on ignition (l〇ss 〇f ignition)' The results are summarized in Table 2 below: Table 2: Physical property analysis results of the raw materials of the humidity-conditioning materials of the present invention PH .. density water loss loss----LLLii)__(g/cm3) ( % ) ( % )
TFT-LCD 廢玻璃 8·92 2 97 2·35 °·02 - 廢觸媒 7.45 1.40 1.11 0.12 0.01 % 結果顯示’ TFT-LCD廢玻璃之pH值為8.92，而並 利用比重瓶法測得TFT-LCD在煤油中比重（specific weight)為 2.97。 最後’分別依據環檢所公告之NIEA R317.10C和 NIEA R201.13C之標準方法，以原子吸收光譜儀（FLAA ) 測定本發明所用之TFT-LCD廢玻璃和廢觸媒的重金屬 總量和重金屬 TCLP ( Toxicity characteristic leaching procedure，毒性特性溶出程序）溶出濃度，其結果係列 201136677 於下表三： 表三：本發明調濕型材料之原料的重金屬分析結果TFT-LCD Waste Glass 8·92 2 97 2·35 °·02 - Waste Catalyst 7.45 1.40 1.11 0.12 0.01 % The results show that the pH of the TFT-LCD waste glass is 8.92, and the TFT is measured by the pycnometer method. The specific gravity of the LCD in kerosene is 2.97. Finally, the total amount of heavy metals and heavy metals TCLP of the TFT-LCD waste glass and waste catalyst used in the present invention were determined by atomic absorption spectrometry (FLAA) according to the standard methods of NIEA R317.10C and NIEA R201.13C published by the Environmental Protection Institute. (Toxicity characteristic leaching procedure) dissolution concentration, the result series 201136677 in the following table III: Table 3: Heavy metal analysis results of the raw materials of the humidity-conditioning material of the present invention
Total Metal (mg/kg ) Pb Cr Cu Zn Cd Ni TFT-LCD廢玻璃 n.d. N.D. N.D. 173.33 N.D. 38.33 廢觸媒 _N.D. N.D. N.D. 95.00 N.D. 4300.0 TCLP (mg/L) Pb Cr Cu Zn Cd Ni TFT-LCD廢玻璃 0.05 0.11 N.D. 0.25 N.D. 0.02 廢觸媒 n.d. N.D. N.D. N.D. N.D. 2.75 法規規範值 5.00 5.00 15.00 1.00Total Metal (mg/kg) Pb Cr Cu Zn Cd Ni TFT-LCD waste glass nd NDND 173.33 ND 38.33 Waste catalyst _NDNDND 95.00 ND 4300.0 TCLP (mg/L) Pb Cr Cu Zn Cd Ni TFT-LCD waste glass 0.05 0.11 ND 0.25 ND 0.02 Waste Catalyst nd NDNDNDND 2.75 Regulatory Value 5.00 5.00 15.00 1.00
N.D. :Not Detected ; Pb<〇.〇15 mg/L ; Cr< 0.009 mg/L ; Cd< 0.021 mg /L; Zn<〇.〇74mg/L; Cu<0.089 mg/L; Ni<〇.112mg/L 由上述表三可知，TFT-LCD廢玻璃之重金屬總量中 以鋅（Zn)含量最高，達173.33 mg/kg，其次為鎳（Ni) 含量為38.33 mg/kg，而TCLP溶出試驗結果顯示其重 金屬溶出濃度皆低於法規規範值。總合而言，本發明調 濕型材料之原料並無危害環境之疑慮。 實施例二：本發明調濕型材料之製備 請參第二圖’取得原料所需之TFT-LCD廢玻璃和 廢觸媒後，以l〇5°C的溫度將前述原料烘乾，接著以球 磨研磨前述原料3小時’以均勻粉碎前述原料。將前述 研磨後的原料通過100號篩網的篩網，以求粉體顆粒之 粒徑平均。接著调整原料的配比如下表四所示： 表四：本實施例么TFT-LCI)廢坡螭和廢觸媒的配比（重量百 分濃度） 11 201136677 樣本 A B C D TFT-LCD 廢玻璃 90 wt% 80 wt% 70 wt% 60 wt% 廢觸媒 10 wt% 20 wt% 30 wt% 40 wt% 將前述配比完成的樣本A〜D以50 kg f/cm 2的壓 力加壓成形’並放入電熏中，前述各樣本皆分別以 800°C、850°C、900°C和950°C的溫度燒結，升溫速率為 5°C/min。燒結完成後即得本實施例之調濕型材料。 實施例三：本發明之調濕型材料之性質分析 1·平衡含水率ND : Not Detected ; Pb < 〇. 〇 15 mg / L ; Cr < 0.009 mg / L ; Cd < 0.021 mg / L; Zn < 〇. 〇 74 mg / L; Cu < 0.089 mg / L; Ni < 〇. /L As can be seen from Table 3 above, the total amount of heavy metals in TFT-LCD waste glass is 173.33 mg/kg, followed by nickel (Ni) content of 38.33 mg/kg, and TCLP dissolution test results. It shows that the heavy metal dissolution concentration is lower than the regulatory value. In summary, the raw materials of the humidity-controlling material of the present invention have no doubts that are harmful to the environment. Example 2: Preparation of the humidity-controlling material of the present invention, as shown in the second figure, after obtaining the TFT-LCD waste glass and the waste catalyst required for the raw materials, the raw materials are dried at a temperature of 10 ° C, and then The above raw materials were ball milled for 3 hours to uniformly pulverize the aforementioned raw materials. The milled raw material is passed through a sieve of a No. 100 sieve to obtain an average particle size of the powder particles. Then adjust the distribution of the raw materials as shown in the following Table 4: Table 4: TFT-LCI of this example, the ratio of waste sloping and waste catalyst (weight percent concentration) 11 201136677 Sample ABCD TFT-LCD Waste glass 90 wt % 80 wt% 70 wt% 60 wt% Waste catalyst 10 wt% 20 wt% 30 wt% 40 wt% The samples A to D completed in the foregoing ratio were pressure-formed at a pressure of 50 kgf/cm 2 'and placed In the electric smoke, each of the above samples was sintered at 800 ° C, 850 ° C, 900 ° C and 950 ° C, respectively, and the heating rate was 5 ° C / min. The humidity-conditioning material of this embodiment is obtained after the sintering is completed. Example 3: Analysis of the properties of the humidity-conditioning material of the present invention 1. Balanced moisture content
首先依照JIS A1475建桌材料的平衡含水率測定方 法’測定本發明實施例二之調濕型材料樣本a〜d在 800°C、850°C、900°C和950°C燒結溫度下所製得之成品 在室溫下各種不同濕度環境（10%〜95%RH)之24小 時後的平衡含水率，其依照溫度不同而結果各如第三A 圖〜第三D圖所示，並藉由此結果得知本發明調濕型材 料之吸濕曲線。 圖中，X軸係為相對濕度（％)，表示在不同濕度環 境下所做的測試，Y軸係為平衡含水率（kg/kg)，由圖 中數據可知，無論在何燒結溫度下，平衡含水率的趨勢 =為··隨原料之廢觸媒取代量越高，其平衡含水率越 高。其中，樣本D (即廢觸媒取代量為4〇%之態樣）， 在燒結溫度為800°C下可得最佳之平衡含水率3 99跑 /kg (如第二A圖所示）。而樣本D在燒結溫度為 時’平衡含水率下降為3.62 kg/kg(如第三B圖所示）， 當燒結溫度為950°C時，平衡含水率下降至丨93吆/吆 12 201136677 ' (如第三D圖所示）。 2. 調濕性能 接著’依照JIS A1470-1調濕建材的吸放濕試驗方 法測定本發明實施例二之調濕型材料樣本a〜d在 80(TC、85〇t、9〇(rc和 950。〇燒結 在中濕域（53〜75%RH)下的調濕性能。 依照日本調濕建材判定基準規定，12小時後吸濕量 需符合2 9 g / πί以上才適合做為調濕建材。以χ轴為測 • 試時間（小時）’ Υ軸為吸放水量（g/nf)顯示各樣本 A (♦)、B ()、〇(▲)和 D(x)在⑽叱、85〇χ：、 900°C和950°C燒結溫度下所製得成品在48小時中的吸 放水量，其依照溫度不同而結果各如第四A圖〜第四D 圖所示。 由圖中數據結果可知，樣本A (即廢觸媒取代量為 10%之態樣）在80(TC、85(TC、9〇(rc和95〇。〇以及樣本 B在950 C的燒結溫度下所製得之調濕型材料，調濕性 能皆不符合日本建材規定之12小時吸濕量，而其他樣 # 本皆符合規定，而可適用於建材。 3. 抗折強度 最後，測試本發明實施例二之調濕型材料樣本A〜 D之抗折強度’結果如第五圖所示。 一以X軸為樣本A〜D’Y轴為抗折強度（kgf/cm2) 顯示各樣本於 950t (^)4001、）、85〇τ： (▲)和 8〇〇°C (χ)下燒結所得調濕型材料的抗折強度。 根據CNS3298 R2064規範陶瓷壁磚之抗折標準為 61.2 kg f/cm 2以上。由圖中數據可知抗折強度基本上 201136677 P通者燒結溫度提兩而提面。結果顯示，在95〇。(3燒結溫 度下，除了樣本A不符合標準外，其他樣本皆符合標準， 而得以作為建材。 結合前述測試數據，調濕型材料之平衡含水率係隨 燒結溫度升高而降低，其係由於經高溫燒結呈現燒結體 趨向緻密化現象，並封閉燒結體中的孔洞結構，造成孔 洞關閉而影響其吸附性能。燒結緻密化現象會造成燒結 體機械強度的成長，因此在950°C燒結溫度下有較高的 抗折強度。 由此結果可知，以作為建材之用途而言，本發明較 佳之操作條件係為在950°C燒結溫度下以30 wt%或40籲 wt%廢觸媒取代量（即樣本C及〇之態樣）之調濕型材 料；最佳為950°C燒結溫度下以40 wt%廢觸媒取代量， 因為40 wt%觸媒含量之吸濕性能較好，故為最佳操作 條件。本發明中不符合建材標準之態樣，亦可用於其他 用途’例如：環境吸濕產品或建材之填充材料等。 所屬領域之技術人員當可了解，在不違背本發明精 神下’依據本案實施態樣所能進行的各種變化。因此， 顯見所列之實施態樣並非用以限制本發明，而是企圖在鲁 所附申請專利範圍的定義下，涵蓋於本發明的精神與範 疇中所做的修改。 【圖式簡單說明】 第一圖係顯示TFT-LCD廢玻璃和廢觸媒的xrd圖 譜。 第二圖係顯示本發明實施例二之調濕型材料的製 備流程。 第三A圖係顯示於800°C燒結之本發明實施例二調 201136677 ' 濕型材料的平衡含水率。 第三B圖係顯示於850°C燒結之本發明實施例二調 濕型材料的平衡含水率。 第三C圖係顯示於900°C燒結之本發明實施例二調 濕型材料的平衡含水率。 第三D圖係顯示於950°C燒結之本發明實施例二調 濕型材料的平衡含水率。 第四A圖係顯示於800°C燒結之本發明實施例二調 濕型材料的調濕性能。 φ 第四B圖係顯示於850°C燒結之本發明實施例二調 濕型材料的調濕性能。 第四C圖係顯示於900°C燒結之本發明實施例二調 濕型材料的調濕性能。 第四D圖係顯示於950°C燒結之本發明實施例二調 濕型材料的調濕性能。 第五圖係顯示本發明實施例二調濕型材料之抗折 強度。 φ 【主要元件符號說明】 無。 15First, according to the method for determining the equilibrium moisture content of the table material of JIS A1475, the sample a to d of the humidity-control material of the second embodiment of the present invention is prepared at 800 ° C, 850 ° C, 900 ° C and 950 ° C sintering temperature. The equilibrium moisture content of the finished product at room temperature in various humidity environments (10%~95% RH) after 24 hours, according to the temperature, the results are as shown in the third A figure to the third D figure, and borrowed From this result, the moisture absorption curve of the humidity-conditioning type material of the present invention was obtained. In the figure, the X-axis is the relative humidity (%), which indicates the test done under different humidity conditions. The Y-axis is the equilibrium moisture content (kg/kg). It can be seen from the data in the figure that no matter the sintering temperature, The trend of balancing the water content = the higher the amount of the replacement of the waste catalyst with the raw material, the higher the equilibrium moisture content. Among them, the sample D (that is, the amount of waste catalyst substitution is 4〇%), the best equilibrium moisture content at the sintering temperature of 800 ° C is 3 99 runs / kg (as shown in Figure 2A) . When sample D is at the sintering temperature, the equilibrium water content drops to 3.62 kg/kg (as shown in Figure B). When the sintering temperature is 950 °C, the equilibrium moisture content drops to 丨93吆/吆12 201136677 ' (as shown in the third D picture). 2. Humidity control performance Next, the sample a to d of the humidity-control material of the second embodiment of the present invention was measured in accordance with JIS A1470-1 moisture absorption and moisture absorption test method at a temperature of 80 (TC, 85 〇t, 9 〇 (rc and 950. The humidity control performance of bismuth sintering in the medium-humidity zone (53~75% RH). According to the benchmark of Japan's humidity-control building materials, the moisture absorption after 12 hours should meet the requirements of 2 9 g / πί, which is suitable for humidity control. Building materials. Measuring with the χ axis • Test time (hours) ' The axis of the suction and discharge (g/nf) shows that each sample A (♦), B (), 〇 (▲) and D (x) are at (10) 叱, 85〇χ: The water absorption and release amount of the finished product obtained at 900 ° C and 950 ° C sintering temperature in 48 hours, the results are shown in Fig. 4A to Fig. 4D according to the temperature. The results of the data show that sample A (ie, the amount of spent catalyst substitution is 10%) is at 80 (TC, 85 (TC, 9 〇 (rc and 95 〇. 〇 and sample B at 950 C sintering temperature) The humidity-control materials obtained have no humidity control performance that meets the 12-hour moisture absorption specified by Japanese Building Materials, while other samples are in compliance with the regulations and can be applied to building materials. 3. Flexural strength Finally, test The results of the flexural strength of the samples A to D of the second embodiment of the present invention are shown in Fig. 5. The X-axis is the sample A~D'Y axis is the flexural strength (kgf/cm2). The flexural strength of the obtained humidity-control material is sintered at 950t (^) 4001), 85〇τ: (▲) and 8〇〇°C (χ). The bending standard of ceramic wall brick according to CNS3298 R2064 is 61.2. Kg f / cm 2 or more. From the data in the figure, it can be seen that the bending strength is basically increased by the sintering temperature of 201136677 P. The results show that at 95 〇 (3 sintering temperature, except that sample A does not meet the standard, Other samples are in line with the standard, and can be used as building materials. Combined with the above test data, the equilibrium moisture content of the humidity-conditioning material decreases with the increase of the sintering temperature, which is due to the tendency of the sintered body to densify due to high-temperature sintering, and closed sintering. The pore structure in the body causes the pores to close and affects its adsorption performance. The sintering densification phenomenon causes the mechanical strength of the sintered body to grow, so it has a high flexural strength at the sintering temperature of 950 ° C. The results show that Use as building materials The preferred operating conditions of the present invention are humidity-conditioning materials having a 30 wt% or 40% by weight of spent catalyst substitution (ie, sample C and hydrazine) at a sintering temperature of 950 ° C; The amount of substitution of 40 wt% waste catalyst at 950 ° C sintering temperature, because 40 wt% of the catalyst content of the moisture absorption performance is better, it is the best operating conditions. In the present invention does not meet the requirements of building materials standards, can also be used For other uses, such as: environmentally absorbent products or filler materials for building materials, etc. Those skilled in the art will recognize that various changes can be made in accordance with the embodiments of the present invention without departing from the spirit of the invention. Therefore, it is to be understood that the invention is not intended to limit the invention, but is intended to cover the modifications in the spirit and scope of the invention. [Simple description of the diagram] The first figure shows the xrd spectrum of the TFT-LCD waste glass and waste catalyst. The second figure shows the preparation process of the humidity-conditioning material of the second embodiment of the present invention. The third A graph shows the equilibrium moisture content of the wet type material of the embodiment of the present invention which is sintered at 800 ° C. The third B graph shows the equilibrium moisture content of the humidity-conditioning material of the second embodiment of the present invention sintered at 850 °C. The third C chart shows the equilibrium moisture content of the second embodiment of the humidity-controlling material of the present invention sintered at 900 °C. The third D pattern shows the equilibrium moisture content of the humidity-conditioning material of the second embodiment of the present invention sintered at 950 °C. Fig. 4A shows the humidity control performance of the second embodiment of the humidity-controlling material of the present invention sintered at 800 °C. φ Figure 4B shows the humidity control performance of the second embodiment of the humidity-controlling material of the present invention sintered at 850 °C. The fourth C chart shows the humidity control property of the second embodiment of the humidity-controlling material of the present invention sintered at 900 °C. The fourth D pattern shows the humidity control performance of the second embodiment of the humidity-controlling material of the present invention sintered at 950 °C. The fifth figure shows the flexural strength of the humidity-conditioning material of the second embodiment of the present invention. Φ [Main component symbol description] None. 15