TWI738565B - Method for recovery and reuse of glass polishing waste - Google Patents

Method for recovery and reuse of glass polishing waste Download PDF

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TWI738565B
TWI738565B TW109139758A TW109139758A TWI738565B TW I738565 B TWI738565 B TW I738565B TW 109139758 A TW109139758 A TW 109139758A TW 109139758 A TW109139758 A TW 109139758A TW I738565 B TWI738565 B TW I738565B
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glass
solid
polishing waste
silicate
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TW202219281A (en
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王立邦
劉佩鑫
陳彥彰
張添晉
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國立臺北科技大學
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Abstract

Disclosed is a method for recovery and reuse of glass polishing waste including steps of alkaline roasting, leaching, separating solid and liquid , and recovering silicate to recover glass powder and cerium oxide abrasive contained in the glass polishing waste. In particular, high purity cerium oxide abrasive, water glass, calcium silicate, and potassium silicate are respectively recovered from the glass polishing waste for subsequent reuse, wherein cerium oxide abrasive is able to be utilized in the polishing process, and water glass, calcium silicate, and potassium silicate are provided for related industries. Thus, it is indeed implemented to fully recover and reuse the precious resources from the glass polishing waste.

Description

玻璃拋光廢棄物的回收再利用方法Method for recycling glass polishing waste

本發明係有關於一種玻璃拋光廢棄物的回收再利用方法，尤其是利用鹼焙燒處理、浸漬處理、回收矽酸鹽處理，用以回收玻璃拋光廢棄物中的玻璃粉屑以及氧化鈰拋光粉以供再利用，達成完全回收及資源化之功效。The present invention relates to a method for recycling glass polishing waste, in particular using alkali roasting treatment, immersion treatment, and recycling silicate treatment to recover glass flakes and cerium oxide polishing powder in glass polishing waste. For reuse, to achieve the effect of complete recycling and resource utilization.

眾所周知，稀土金屬已廣泛應用在許多電子、機械、航太工業上，其中鈰(Ce)可做為氧化劑、拋光粉、玻璃和瓷器的黃色染料、石油提煉液體催化過程(FCC)催化劑，因而更加引起業界對於回收，再利用技術的注意。As we all know, rare earth metals have been widely used in many electronics, machinery, and aerospace industries. Among them, cerium (Ce) can be used as an oxidant, polishing powder, yellow dye for glass and porcelain, and a catalyst for the liquid catalytic process (FCC) of petroleum refining. Arouse the industry's attention to recycling and reuse technologies.

尤其，於面板玻璃、光學鏡片等玻璃的生產製造過程中，常使用氧化鈰拋光粉進行拋光研磨，以去除經蝕刻減薄處理後所產生的微細紋痕。使用一段時間後，因玻璃碎屑粉混入拋光粉中，無法維持原有的拋光研磨速度且造成玻璃表面的損傷而被廢棄，因而產生玻璃拋光廢棄物。In particular, in the production process of glass such as panel glass and optical lens, cerium oxide polishing powder is often used for polishing and grinding to remove the fine traces produced by the etching and thinning process. After using for a period of time, because the glass shards powder is mixed into the polishing powder, the original polishing speed cannot be maintained and the glass surface is damaged and is discarded, thus producing glass polishing waste.

對於玻璃拋光廢棄物，目前最常用的處置方式是直接進行掩埋處理，並未進行有效的分離回收，導致稀土金屬資源的浪費，相當可惜。For glass polishing waste, the most commonly used method of disposal is to bury it directly, without effective separation and recycling, which leads to waste of rare earth metal resources, which is quite a pity.

在習知技術中，回收玻璃拋光廢棄物的方法一般是包括強酸-雙氧水浸漬法、氯化揮發法、強鹼浸漬法、泡沫浮選法及熱處理、強鹼法加氟化鈉、混凝法，等等，尤其，大多是直接利用強酸或強鹼，將含有鈰、鑭等稀土金屬的氧化鈰拋光粉或將玻璃碎屑粉選擇性溶解之後，再利用離子交換、溶媒萃取、沉澱析出等濕法冶金方法進行回收。In the prior art, the methods for recycling glass polishing waste generally include strong acid-hydrogen peroxide impregnation method, chlorination volatilization method, strong alkali impregnation method, foam flotation method and heat treatment, strong alkali method plus sodium fluoride, and coagulation method. , Etc., especially, most of them directly use strong acid or alkali to selectively dissolve cerium oxide polishing powder containing rare earth metals such as cerium and lanthanum or glass shard powder, and then use ion exchange, solvent extraction, precipitation, etc. Hydrometallurgical method for recycling.

雖然上述習知技術的方法可從玻璃拋光廢棄物中回收稀土金屬，惟亦存在著須使用大量強酸強鹼等化學藥品，以及高溫處理消耗大量能源，且回收過程中亦產生二次污染廢水等問題，比如伴隨後續大量廢酸、廢鹼等廢液，因而所耗費用不眥，不具經濟效益，再者，部分方法雖可從玻璃拋光廢棄物直接分離氧化鈰拋光粉及玻璃碎屑粉，惟回收物之拋光粉中仍含量有少量玻璃碎屑粉，無法獲得高純度之氧化鈰拋光粉，很難被產業界接受、使用。Although the above-mentioned conventional technology can recover rare earth metals from glass polishing waste, there are also the need to use a large amount of strong acids and alkalis and other chemicals, and high temperature treatment consumes a lot of energy, and the recycling process also produces secondary pollution wastewater, etc. Problems, such as the subsequent large amount of waste acid, waste alkali and other waste liquids, which are not costly and economical. Furthermore, although some methods can directly separate the cerium oxide polishing powder and glass shards from the glass polishing waste, However, there is still a small amount of glass shards in the recycled polishing powder, and high-purity cerium oxide polishing powder cannot be obtained, and it is difficult to be accepted and used by the industry.

因此，很急需一種創新的玻璃拋光廢棄物的回收再利用方法，利用鹼焙燒處理、浸漬處理、固液分離處理、回收矽酸鹽處理，用以回收玻璃拋光廢棄物中的玻璃粉屑以及氧化鈰拋光粉以供再利用，達成完全回收及資源化之功效，藉以解決上述習用技術的問題。Therefore, there is an urgent need for an innovative recycling method for glass polishing waste, which uses alkali roasting treatment, immersion treatment, solid-liquid separation treatment, and recycling silicate treatment to recover glass powder and oxidation in glass polishing waste. Cerium polishing powder can be reused to achieve the effect of complete recycling and resource utilization, so as to solve the above-mentioned conventional technology problems.

本發明之主要目的在於提供一種玻璃拋光廢棄物的回收再利用方法，包含進行鹼焙燒處理、浸漬處理、固液分離處理、回收矽酸鹽處理，用以對包含玻璃粉屑以及氧化鈰拋光粉的一玻璃拋光廢棄物進行回收再利用。The main purpose of the present invention is to provide a method for recycling glass polishing waste, including alkali roasting treatment, immersion treatment, solid-liquid separation treatment, and recycling silicate treatment, which is used to treat glass powder and cerium oxide polishing powder. One of the glass polishing waste is recycled and reused.

具體而言，在鹼焙燒處理中，是對玻璃拋光廢棄物添加鹼劑以及進行熱處理，其中鹼劑包含氫氧化鈉、碳酸鈉或氫氧化鉀，而熱處理是將添加鹼劑後的玻璃拋光廢棄物加熱到焙燒溫度，並維持焙燒時間，且經冷卻後形成鹼焙燒處理混合物。Specifically, in the alkali roasting treatment, an alkali agent is added to the glass polishing waste and heat treatment is performed, wherein the alkali agent includes sodium hydroxide, sodium carbonate or potassium hydroxide, and the heat treatment is to discard the glass polishing after adding the alkali agent. The material is heated to the calcination temperature and maintained for the calcination time, and after cooling, it forms an alkali calcination treatment mixture.

上述的浸漬處理是在特定的浸漬溫度下，對鹼焙燒處理混合物添加去離子水以及pH值調整劑，進而混合以形成浸漬液，其中浸漬液的液固比為至少25 ml/g，且浸漬液的pH值是特別調整至pH 4以下，尤其，浸漬溫度為不超過25℃。The above-mentioned immersion treatment is to add deionized water and a pH value adjuster to the alkali roasting treatment mixture at a specific immersion temperature, and then mix to form an immersion liquid, wherein the liquid-to-solid ratio of the immersion liquid is at least 25 ml/g, and the immersion liquid The pH value of the liquid is particularly adjusted to below pH 4, especially the immersion temperature is not more than 25°C.

在固液分離處理中，是利用固液分離裝置，對浸漬液進行固液分離而形成固體的固體分離物以及液體的水浸漬液，其中固體分離物即為氧化鈰拋光粉，而水浸漬液包含玻璃粉屑的矽酸鹽成份，換言之，矽酸鹽是包含矽酸鈉或矽酸鉀。In the solid-liquid separation process, a solid-liquid separation device is used to separate the immersion liquid from solid-liquid to form a solid solid separation and a liquid water immersion liquid. The solid separation is the cerium oxide polishing powder, and the water immersion liquid The silicate component containing glass frit, in other words, the silicate contains sodium silicate or potassium silicate.

此外，在回收矽酸鹽處理中，可包含對水浸漬液直接進行加熱蒸發，用以去除水浸漬液的水分及液體成份而回收、獲得稱為水玻璃的矽酸鈉或矽酸鉀，或者，也可包含先調整該水浸漬液的pH值至不低於pH 7，再利用添加氯化鈣(CaCl 2)至水浸漬液的方式以形成矽酸鈣的沉澱物，接著經液固分離而對分離後的固體物進行水洗以去除氯化鈉而回收、進而獲得固態的矽酸鈣。 In addition, the process of recycling silicate may include heating and evaporating the water immersion liquid directly to remove the water and liquid components of the water immersion liquid to recover and obtain sodium silicate or potassium silicate called water glass, or It can also include adjusting the pH value of the water immersion liquid to no less than pH 7, and then adding calcium chloride (CaCl 2 ) to the water immersion liquid to form calcium silicate precipitates, followed by liquid-solid separation The separated solids are washed with water to remove sodium chloride and recovered, thereby obtaining solid calcium silicate.

因此，本發明整體而言可從玻璃拋光廢棄物中分別回收高純度氧化鈰拋光粉、水玻璃、矽酸鈣、矽酸鉀，而回收高純度之氧化鈰拋光粉可供拋光研磨再次使用，或有助於後續鈰、鑭等稀土金屬的分離純化精製，且回收後的水玻璃、矽酸鈣、矽酸鉀可供相關產業利用，藉以達成玻璃拋光廢棄物的完全回收及資源化之功效。Therefore, as a whole, the present invention can separately recover high-purity cerium oxide polishing powder, water glass, calcium silicate, and potassium silicate from glass polishing waste, and the recovered high-purity cerium oxide polishing powder can be used for polishing and grinding again. It may be helpful for the subsequent separation, purification and refining of rare earth metals such as cerium and lanthanum, and the recovered water glass, calcium silicate, and potassium silicate can be used by related industries to achieve the complete recovery and resource utilization of glass polishing waste .

以下配合圖示及元件符號對本發明之實施方式做更詳細的說明，俾使熟習該項技藝者在研讀本說明書後能據以實施。The following is a more detailed description of the implementation of the present invention in conjunction with the drawings and component symbols, so that those who are familiar with the art can implement it after studying this manual.

請參考第一圖，本發明實施例玻璃拋光廢棄物的回收再利用方法的操作流程示意圖。如第一圖所示，本發明實施例玻璃拋光廢棄物的回收再利用方法包含依序進行的步驟S10、S20、S30、S40，分別進行鹼焙燒處理、浸漬處理、固液分離處理、回收矽酸鹽處理，用以對包含玻璃粉屑以及氧化鈰拋光粉的玻璃拋光廢棄物進行回收再利用。Please refer to the first figure, which is a schematic diagram of the operation flow of the method for recycling and reusing glass polishing waste according to an embodiment of the present invention. As shown in the first figure, the method for recycling glass polishing waste according to the embodiment of the present invention includes steps S10, S20, S30, and S40 in sequence, which are respectively subjected to alkali roasting treatment, immersion treatment, solid-liquid separation treatment, and recovery of silicon. Salt treatment is used to recycle the glass polishing waste containing glass flakes and cerium oxide polishing powder.

首先，本發明實施例玻璃拋光廢棄物的回收再利用方法是由步驟S10開始，對玻璃拋光廢棄物進行鹼焙燒處理而形成鹼焙燒處理混合物，而鹼焙燒處理實質上是依序包含添加鹼劑以及熱處理。First, the method for recycling glass polishing waste in the embodiment of the present invention starts from step S10, the glass polishing waste is subjected to alkali roasting treatment to form an alkali roasting treatment mixture, and the alkali roasting treatment essentially includes the addition of an alkali agent in sequence. And heat treatment.

具體而言，在添加鹼劑中主要是將玻璃拋光廢棄物置於容器中，比如鎳坩鍋，再添加包含氫氧化鈉(NaOH)、碳酸鈉(Na 2CO 3)或氫氧化鉀(KOH)的鹼劑而與玻璃拋光廢棄物混合，其中鹼礦比為至少1：1，而鹼礦比是指鹼劑對玻璃拋光廢棄物的重量比例。熱處理的目的在於利用加熱到焙燒溫度以達到將玻璃碎屑粉轉換成矽酸鹽的功效，進而提高玻璃粉屑的去除率，尤其，焙燒溫度是至少400℃，且整個熱處理的焙燒時間是至少30分鐘。再經冷卻後，形成前處理混合物。 Specifically, in adding the alkali agent, the glass polishing waste is placed in a container, such as a nickel crucible, and then added containing sodium hydroxide (NaOH), sodium carbonate (Na 2 CO 3 ) or potassium hydroxide (KOH) The alkali agent is mixed with the glass polishing waste, wherein the alkali-ore ratio is at least 1:1, and the alkali-ore ratio refers to the weight ratio of the alkali agent to the glass polishing waste. The purpose of heat treatment is to use heating to the firing temperature to achieve the effect of converting glass shards into silicate, thereby improving the removal rate of glass frits. In particular, the firing temperature is at least 400°C, and the firing time of the entire heat treatment is at least 30 minutes. After cooling again, a pretreatment mixture is formed.

在步驟S20的浸漬處理中，是對步驟S10所形成的鹼焙燒處理混合物，添加去離子水以及pH值調整劑而形成浸漬液，以溶解矽酸鹽，其中整體浸漬液的液固比為至少25 ml/g，而pH值調整劑是包含氯化氫(HCl)，用以調整浸漬液的pH值至pH 4以下，亦即浸漬液為酸性，尤其，形成浸漬液時的浸漬溫度為不超過25℃，可大幅提高浸漬功效。In the immersion treatment in step S20, deionized water and a pH adjuster are added to the alkali roasting treatment mixture formed in step S10 to form an immersion liquid to dissolve silicate, wherein the liquid-to-solid ratio of the overall immersion liquid is at least 25 ml/g, and the pH adjuster contains hydrogen chloride (HCl) to adjust the pH of the immersion liquid to below pH 4, that is, the immersion liquid is acidic, especially, the immersion temperature when the immersion liquid is formed is not more than 25 ℃, can greatly improve the efficiency of impregnation.

此外，步驟S30的固液分離處理是利用固液分離裝置，比如離心機，對步驟S20的浸漬液進行固液分離而形成固體的固體分離物以及液體的水浸漬液，其中固體分離物即為氧化鈰拋光粉，而水浸漬液包含玻璃粉屑的矽酸鹽成份，或者可視為矽酸鹽水溶液。由於固液分離裝置的操作及技術原理是屬於一般習知的領域，所以下文中不進一步詳細說明。In addition, the solid-liquid separation process in step S30 uses a solid-liquid separation device, such as a centrifuge, to perform solid-liquid separation of the immersion liquid in step S20 to form a solid solid separation product and a liquid water immersion liquid, where the solid separation product is Cerium oxide polishing powder, and the water immersion liquid contains the silicate component of glass flakes, or can be regarded as a silicate aqueous solution. Since the operation and technical principle of the solid-liquid separation device belong to the generally known field, it will not be described in further detail below.

再者，步驟S40的回收矽酸鹽處理是用以處理液體的水浸漬液而回收矽酸鹽，主要是直接利用加熱蒸發的方式而去除其中的水分及液體成份而獲得水玻璃，亦即矽酸鈉或矽酸鉀，或者，可先調整pH值至不低於pH 7，再利用添加氯化鈣(CaCl 2)的方式形成矽酸鈣的沉澱物，較佳的，水浸漬液以及氯化鈣的液固比為至多80ml/g，接著，經液固分離而對分離後的固體物進行水洗以去除氯化鈉，而獲得固態的矽酸鈣。換言之，回收矽酸鹽的具體實施方式可分為水玻璃回收、矽酸鈣回收、矽酸鉀回收，視後續的再利用需要而決定，所以應用上，非常具有彈性，明顯改善本發明的產業利用性。 Furthermore, the silicate recovery process in step S40 is used to process the water immersion liquid of the liquid to recover the silicate, mainly by directly using heating and evaporation to remove the water and liquid components in it to obtain water glass, that is, silicon Sodium or potassium silicate, or, adjust the pH to no less than pH 7, and then add calcium chloride (CaCl 2 ) to form calcium silicate precipitates, preferably, water immersion liquid and chlorine The liquid-to-solid ratio of calcium hydroxide is at most 80 ml/g, and then the separated solids are washed with water through liquid-solid separation to remove sodium chloride to obtain solid calcium silicate. In other words, the specific implementation methods for recycling silicate can be divided into water glass recycling, calcium silicate recycling, and potassium silicate recycling, depending on the subsequent reuse needs. Therefore, it is very flexible in application and significantly improves the industry of the present invention. Utilization.

為說明本發明方法的實施手段以及所達成的具體功能，下文中將舉例說明。In order to illustrate the implementation means of the method of the present invention and the specific functions achieved, examples will be given below.

首先參考第二圖，顯示鹼礦比對玻璃粉去除率的影響及變化，其中鹼礦比是表示成玻璃拋光廢棄物對NaOH的重量比(g/g)，例如，以玻璃拋光廢棄物1 g，在焙燒溫度450℃下經焙燒時間2 hr，且於鎳坩鍋中添加不同鹼礦比之NaOH以進行焙燒，此外，水浸漬pH 3、水浸漬溫度25℃、水浸漬液固比200 ml/g。結果如第二圖所示，當鹼礦比1：0.5時，玻璃粉去除率為73.4%，顯然玻璃粉還無法完全去除。不過隨著鹼礦比增加，玻璃粉去除率亦隨之增加。當鹼礦比達1：1以上時，玻璃粉去除率已達100%。因此，最佳鹼礦比為1：1，或者，鹼礦比最好是大於或等於1：1。First refer to the second figure, which shows the influence and change of the alkali-ore ratio on the removal rate of glass powder, where the alkali-ore ratio is expressed as the weight ratio of glass polishing waste to NaOH (g/g), for example, glass polishing waste 1 g, the baking time is 2 hr at a baking temperature of 450℃, and NaOH with different alkali-ore ratios is added to the nickel crucible for baking. In addition, the water immersion pH 3, the water immersion temperature 25℃, and the water immersion liquid-to-solid ratio 200 ml/g. The result is shown in the second figure. When the alkali-ore ratio is 1:0.5, the glass frit removal rate is 73.4%. Obviously, the glass frit cannot be completely removed. However, as the alkali-ore ratio increases, the glass powder removal rate also increases. When the alkali-ore ratio reaches more than 1:1, the glass frit removal rate has reached 100%. Therefore, the optimal alkali-ore ratio is 1:1, or the alkali-ore ratio is preferably greater than or equal to 1:1.

關於焙燒溫度的影響，如第三圖所示，主要操作條件是玻璃拋光廢棄物1 g、鹼礦比1：1、焙燒時間2 hr、水浸漬pH 3、水浸漬溫度25℃、水浸漬液固比200 ml/g，顯而易見的是，在焙燒溫度達到300℃時，玻璃粉去除率已超過80%，而450℃以上時，玻璃粉去除率已達100%，所以較佳的焙燒溫度是大於或等於450℃。Regarding the influence of the roasting temperature, as shown in the third figure, the main operating conditions are 1 g of glass polishing waste, 1:1 ratio of alkali to ore, 1, roasting time 2 hr, water immersion pH 3, water immersion temperature 25℃, water immersion liquid The solid ratio is 200 ml/g. It is obvious that when the firing temperature reaches 300°C, the glass frit removal rate has exceeded 80%, and when the temperature is above 450°C, the glass frit removal rate has reached 100%, so the better firing temperature is Greater than or equal to 450°C.

第四圖是顯示鹼焙燒暨水浸漬後之氧化鈰玻璃拋光廢棄物之X光繞射(XRD)分析結果，其中的操作條件是玻璃拋光廢棄物1 g、鹼礦比1：1、焙燒時間2 hr。如第四圖所示，焙燒溫度於300℃時，出現CeO 2與SiO 2之特徵峰，表示玻璃粉尚未與NaOH反應完全，而焙燒溫度於400℃以上時，已無SiO 2之特徵峰，僅出現CeO 2之特徵峰，表示玻璃粉與NaOH已完全反應，亦即，固體物中僅剩氧化鈰系拋光粉。 The fourth figure shows the X-ray diffraction (XRD) analysis results of the cerium oxide glass polishing waste after alkali roasting and water immersion. The operating conditions are 1 g glass polishing waste, alkali-ore ratio 1:1, roasting time 2 hr. As shown in the fourth figure, when the firing temperature is 300°C, the characteristic peaks of CeO 2 and SiO 2 appear, indicating that the glass powder has not yet reacted completely with NaOH, and when the firing temperature is above 400°C, there is no characteristic peak of SiO 2. Only the characteristic peak of CeO 2 appears, indicating that the glass powder and NaOH have completely reacted, that is, only the cerium oxide-based polishing powder remains in the solid.

此外，焙燒時間對玻璃粉去除率的影響及變化如第五圖所示，其中操作條件是玻璃拋光廢棄物為1 g，礦鹼比為1：1、焙燒溫度450℃、水浸漬pH 3、水浸漬溫度25℃、水浸漬液固比200 ml/g。隨著焙燒時間增加，玻璃粉去除率隨之增加，並於焙燒時間1 min時，玻璃粉去除率為68.3%，而於30 min以上時，玻璃粉去除率已達100%。因此，最佳的焙燒時間是大於或等於30 min。In addition, the effect and change of the roasting time on the removal rate of glass powder are shown in Figure 5. The operating conditions are 1 g of glass polishing waste, 1:1 ratio of ore to alkali, roasting temperature of 450°C, water immersion pH 3, The water immersion temperature is 25℃, and the liquid-solid ratio of the water immersion is 200 ml/g. As the firing time increases, the glass frit removal rate increases, and when the firing time is 1 min, the glass frit removal rate is 68.3%, and when the firing time is more than 30 minutes, the glass frit removal rate has reached 100%. Therefore, the best firing time is greater than or equal to 30 min.

水浸漬pH值對玻璃粉去除率的影響及變化如第六圖所示，其中操作條件是氧化鈰系玻璃拋光廢棄物1 g、鹼礦比1：1、焙燒溫度450℃、焙燒時間30 min、水浸漬溫度25℃、水浸漬液固比200 ml/g，尤其是使用HCl以調整pH值。通常，原始焙燒產物之水浸漬液之pH值是大約介於11至12之間，且玻璃粉去除率為0%，而隨著水浸漬pH值的降低，玻璃粉去除率亦隨之增加，且當水浸漬液pH 5時，玻璃粉去除率已達到90.7%，而當水浸漬液pH 4以下時，玻璃粉去除率已達100%，所以最佳的水浸漬pH值是小於或等於pH 4。The effect and change of pH value of water immersion on the removal rate of glass powder are shown in Figure 6, where the operating conditions are 1 g of cerium oxide glass polishing waste, alkali-ore ratio 1:1, roasting temperature 450℃, roasting time 30 min , Water immersion temperature 25℃, water immersion liquid solid ratio 200 ml/g, especially use HCl to adjust pH value. Generally, the pH value of the water immersion liquid of the original roasted product is approximately between 11 and 12, and the glass frit removal rate is 0%. As the water immersion pH value decreases, the glass frit removal rate also increases. And when the pH of the water immersion solution is 5, the glass frit removal rate has reached 90.7%, and when the pH of the water immersion solution is below 4, the glass frit removal rate has reached 100%, so the best water immersion pH is less than or equal to pH 4.

第七圖顯示浸漬溫度對玻璃粉去除率的影響及變化，其中操作條件是玻璃拋光廢棄物1 g、鹼礦比1：1、焙燒溫度450℃、焙燒時間30 min、水浸漬液固比200 ml/g，且水浸漬液的pH值為pH3、pH7、pH12。如第七圖所示，水浸漬液pH 3於各浸漬溫度之玻璃粉去除率皆比pH 7及pH 12為高，而在水浸漬液pH 3時，如果浸漬溫度為25℃，則玻璃粉去除率已達100%，但是浸漬溫度為80℃時，玻璃粉去除率反而降低至74.5%，其原因為當浸漬溫度80℃以上時，矽酸鈉溶液呈膠著狀，會使得玻璃粉去除率降低。因此，最佳的水浸漬溫度是25℃，亦即保持於室溫，而不需加熱。The seventh figure shows the influence and change of immersion temperature on the removal rate of glass powder. The operating conditions are 1 g of glass polishing waste, 1:1 ratio of alkali to ore, roasting temperature of 450℃, roasting time of 30 min, and water-immersion liquid-solid ratio of 200 ml/g, and the pH value of the water immersion liquid is pH3, pH7, and pH12. As shown in Figure 7, the glass frit removal rate of the water immersion solution pH 3 at each immersion temperature is higher than that of pH 7 and pH 12. When the water immersion solution pH 3, if the immersion temperature is 25°C, the glass frit The removal rate has reached 100%, but when the immersion temperature is 80°C, the glass frit removal rate decreases to 74.5%. The reason is that when the immersion temperature is above 80°C, the sodium silicate solution is gelatinous, which will make the glass frit removal rate reduce. Therefore, the optimal water immersion temperature is 25°C, that is, kept at room temperature without heating.

關於浸漬液固比對玻璃粉去除率的影響及變化，如第八圖所示，是以礦鹼比為1：1、焙燒溫度450℃、焙燒時間30 min的焙燒條件進行鹼焙燒後，將所獲得之焙燒產物，經添加去離子水，再以水浸漬液pH 3、浸漬溫度25℃進行水浸漬。結果顯示，當液固比在25 ml/g以上時，玻璃粉去除率可達100%，所以最佳的浸漬液固比是大於或等於25 ml/g。Regarding the influence and change of the immersion liquid-solid ratio on the removal rate of glass powder, as shown in the eighth figure, the ore-alkali ratio is 1:1, the calcination temperature is 450℃, and the calcination time is 30 min. After adding deionized water, the obtained calcined product is immersed in water at pH 3 of the water immersion solution and at an immersion temperature of 25°C. The results show that when the liquid-to-solid ratio is above 25 ml/g, the glass frit removal rate can reach 100%, so the best impregnating liquid-to-solid ratio is greater than or equal to 25 ml/g.

進一步，針對水浸漬液之水玻璃或矽酸鈣回收以舉例說明。以鹼焙燒暨水浸漬所得之水浸漬液(矽酸鈉水溶液)，將水份蒸發後，可回收矽酸鈉(水玻璃)。或將其調整pH值後，添加氯化鈣，再進行水洗處理，去除氯化鈉，可回收矽酸鈣，其化學反應式為：Na 2SiO 3+ CaCl 2→ CaSiO 3+ 2NaCl。 Furthermore, the recovery of water glass or calcium silicate in the water immersion liquid will be illustrated as an example. The water immersion liquid (sodium silicate aqueous solution) obtained by alkali roasting and water immersion can recover sodium silicate (water glass) after the water is evaporated. Or after adjusting the pH value, adding calcium chloride and then washing with water to remove sodium chloride, calcium silicate can be recovered. The chemical reaction formula is: Na 2 SiO 3 + CaCl 2 → CaSiO 3 + 2NaCl.

此外，在水浸漬液之原始pH值為pH 3時，於200 ml之pH 3水浸漬液中添加1.5 g氯化鈣進行攪拌後，產生無矽酸鈣。當pH值調整至pH 5以上，再添加1.5 g氯化鈣進行攪拌後，有明顯懸浮微粒產生，再以離心機進行固液分離，而將固體物於105℃、24 hr烘乾後秤重，第九圖顯示不同矽酸鈉水溶液pH值所獲得之固體物重量。隨著矽酸鈉水溶液之pH值提高，所獲得之固體物重量亦隨之增加。調整至pH 11時雖可獲得之固體物最多，然而須添加大量之鹼劑，所以選定於中性範圍之pH 7當作較佳的操作條件。In addition, when the original pH of the water immersion solution was pH 3, 1.5 g of calcium chloride was added to 200 ml of the pH 3 water immersion solution and stirred to produce calcium silicate-free. When the pH value is adjusted to above pH 5, and 1.5 g of calcium chloride is added for stirring, obvious suspended particles are generated, and then solid-liquid separation is carried out with a centrifuge, and the solids are dried at 105°C for 24 hr and weighed , The ninth figure shows the weight of solids obtained with different pH values of sodium silicate aqueous solution. As the pH value of the sodium silicate aqueous solution increases, the weight of the solids obtained also increases. Although the maximum amount of solids can be obtained when the pH is adjusted to 11, a large amount of alkaline agent must be added, so the pH 7 in the neutral range is selected as the better operating condition.

在200 m l之矽酸鈉水溶液pH值為中性範圍之pH 7的操作條件下，氯化鈣添加量對所獲得之固體物重量之影響是如第十圖所示，其中氯化鈣添加量越多時，固體物重量亦隨之增加，而當添加至2.5g以上時，固體物重量無明顯變化。因此，當氯化鈣添加3 g以上時，矽酸鈣已反應完全。因此，較佳的氯化鈣添加量為大於或等於3 g。Under the operating condition that the pH value of 200 ml of sodium silicate aqueous solution is pH 7 in the neutral range, the effect of calcium chloride addition on the weight of the solids obtained is shown in Figure 10, where calcium chloride addition When the amount is higher, the weight of the solids will increase, and when added to more than 2.5g, the weight of the solids will not change significantly. Therefore, when calcium chloride is added more than 3 g, calcium silicate has reacted completely. Therefore, the preferred calcium chloride addition amount is greater than or equal to 3 g.

於pH 7之矽酸鈉水溶液，添加1.5 g氯化鈣後所獲得之固體物，經XRD分析結果如第十一圖所示，其中出現氯化鈉(NaCl)以及矽酸鈣(CaSiO 3)之特徵峰，與上述矽酸鈣的化學反應式相符。為去除氯化鈉以獲得矽酸鈣，對固體物反覆水洗10次，經XRD分析後，其結果如第十二圖所示，而與第十一圖相比，NaCl之特徵峰較小，表示NaCl可經由水洗過後，溶解於水中，其剩餘固體物為CaSiO 3。 The solid material obtained by adding 1.5 g of calcium chloride to the aqueous solution of sodium silicate at pH 7. The result of XRD analysis is shown in Figure 11. Sodium chloride (NaCl) and calcium silicate (CaSiO 3 ) are present. The characteristic peaks are consistent with the above-mentioned chemical reaction formula of calcium silicate. In order to remove sodium chloride to obtain calcium silicate, the solid was repeatedly washed with water 10 times. After XRD analysis, the result is shown in Figure 12. Compared with Figure 11, the characteristic peak of NaCl is smaller. It means that NaCl can be washed with water and then dissolved in water, and the remaining solid is CaSiO 3 .

綜合而言，本發明的特點主要在於針對玻璃拋光廢棄物，添加鹼劑，進行低溫焙燒的熱處理以及水洗處理，藉以完全去除其中的玻璃碎屑粉而回收高純度的氧化鈰拋光粉，並接著對水洗後的水浸漬液進行蒸發以回收水玻璃或矽酸鉀，或添加含鈣物質以回收矽酸鈣，因此，可達成氧化鈰拋光粉的循環再利用，以及玻璃拋光廢棄物的完全回收及資源化，進而減少玻璃拋光廢棄物的最終處理量。In summary, the feature of the present invention is mainly for glass polishing waste, adding an alkali agent, performing low-temperature roasting heat treatment and water washing treatment, so as to completely remove the glass shards and recover high-purity cerium oxide polishing powder, and then Evaporate the washed water immersion liquid to recover water glass or potassium silicate, or add calcium-containing substances to recover calcium silicate. Therefore, recycling of cerium oxide polishing powder and complete recovery of glass polishing waste can be achieved And resource utilization, thereby reducing the final treatment volume of glass polishing waste.

以上所述者僅為用以解釋本發明之較佳實施例，並非企圖據以對本發明做任何形式上之限制，是以，凡有在相同之發明精神下所作有關本發明之任何修飾或變更，皆仍應包括在本發明意圖保護之範疇。The above descriptions are only used to explain the preferred embodiments of the present invention, and are not intended to restrict the present invention in any form. Therefore, any modification or change related to the present invention is made under the same spirit of the invention. , Should still be included in the scope of the present invention's intended protection.

S10、S20、S30 、S40:步驟S10, S20, S30, S40: steps

第一圖顯示依據本發明實施例玻璃拋光廢棄物的回收再利用方法的操作流程示意圖。 第二圖顯示依據本發明方法中鹼礦比對玻璃粉去除率的影響及變化。 第三圖顯示依據本發明方法中焙燒溫度對玻璃粉去除率的影響及變化。 第四圖顯示依據本發明方法中鹼焙燒暨水浸漬後之氧化鈰玻璃拋光廢棄物之XRD分析結果。 第五圖顯示依據本發明方法中焙燒時間對玻璃粉去除率的影響及變化。 第六圖顯示依據本發明方法中水浸漬pH值對玻璃粉去除率的影響及變化。 第七圖顯示依據本發明方法中浸漬溫度對玻璃粉去除率的影響及變化。 第八圖顯示依據本發明方法中浸漬液固比對玻璃粉去除率的影響及變化。 第九圖顯示依據本發明方法中不同矽酸鈉水溶液pH值所獲得之固體物重量的變化。 第十圖顯示依據本發明方法中氯化鈣添加量對所獲得之固體物重量之影響。 第十一圖顯示依據本發明方法中添加1.5 g氯化鈣後所獲得之固體物的XRD分析結果。 第十二圖顯示依據本發明方法中添加1.5 g氯化鈣後所獲得之固體物經反覆水洗10次後的XRD分析結果。 The first figure shows a schematic diagram of the operation flow of the method for recycling and reusing glass polishing waste according to an embodiment of the present invention. The second figure shows the influence and change of the alkali-ore ratio on the removal rate of glass powder in the method according to the present invention. The third figure shows the influence and change of the firing temperature on the glass frit removal rate in the method according to the present invention. The fourth figure shows the XRD analysis result of the cerium oxide glass polishing waste after alkali roasting and water immersion in the method of the present invention. The fifth figure shows the influence and change of the firing time on the glass frit removal rate in the method according to the present invention. The sixth figure shows the influence and change of the pH value of water immersion in the method of the present invention on the removal rate of glass frit. The seventh figure shows the influence and change of the immersion temperature on the glass frit removal rate in the method according to the present invention. The eighth figure shows the influence and change of the immersion liquid-solid ratio on the glass frit removal rate in the method according to the present invention. The ninth graph shows the changes in the weight of solids obtained with different pH values of the aqueous sodium silicate solution according to the method of the present invention. The tenth graph shows the influence of the added amount of calcium chloride on the weight of the solids obtained in the method according to the present invention. The eleventh figure shows the XRD analysis result of the solid obtained after adding 1.5 g of calcium chloride according to the method of the present invention. The twelfth figure shows the XRD analysis result of the solid obtained after adding 1.5 g of calcium chloride in the method of the present invention after repeated washing with water for 10 times.

S10、S20、S30、S40:步驟 S10, S20, S30, S40: steps

Claims (6)

一種玻璃拋光廢棄物的回收再利用方法，用以對包含玻璃粉屑以及氧化鈰拋光粉的一玻璃拋光廢棄物進行回收再利用，包括：一鹼焙燒處理，係對該玻璃拋光廢棄物添加一鹼劑以及進行一熱處理，該鹼劑包含氫氧化鈉(NaOH)、碳酸鈉(Na2CO3)或氫氧化鉀(KOH)，該熱處理是將添加該鹼劑後的該玻璃拋光廢棄物加熱到一焙燒溫度，並維持一焙燒時間，且經冷卻後，形成一鹼焙燒處理混合物；一浸漬處理，係在一浸漬溫度下，對該鹼焙燒處理混合物，添加去離子水以及一pH值調整劑而混合形成一浸漬液，該浸漬液的一液固比為至少25ml/g，該浸漬液的pH值是調整至pH 4以下，且該浸漬溫度為不超過25℃；一固液分離處理，利用一固液分離裝置，對該浸漬液進行固液分離而形成固體的一固體分離物以及液體的一水浸漬液，該固體分離物即為該氧化鈰拋光粉，該水浸漬液包含該玻璃粉屑的矽酸鹽成份，該矽酸鹽是包含矽酸鈉或矽酸鉀；以及一回收矽酸鹽處理，包含先調整該水浸漬液的pH值至不低於pH 7，再利用添加氯化鈣(CaCl2)至該水浸漬液的方式以形成矽酸鈣的一沉澱物，接著經液固分離而對分離後的固體物進行水洗以去除氯化鈉，而回收獲得固態的矽酸鈣。 A method for recycling glass polishing waste is used to recycle and reuse a glass polishing waste containing glass flakes and cerium oxide polishing powder. Alkali agent and a heat treatment, the alkali agent includes sodium hydroxide (NaOH), sodium carbonate (Na 2 CO 3 ) or potassium hydroxide (KOH), the heat treatment is to heat the glass polishing waste after adding the alkali agent To a calcination temperature and maintain a calcination time, and after cooling, an alkali calcination treatment mixture is formed; an immersion treatment is to add deionized water and a pH value adjustment to the alkali calcination treatment mixture at an immersion temperature To form an immersion liquid, the liquid-solid ratio of the immersion liquid is at least 25ml/g, the pH value of the immersion liquid is adjusted to below pH 4, and the immersion temperature is not more than 25°C; a solid-liquid separation treatment , Using a solid-liquid separation device to separate the immersion liquid from solid-liquid to form a solid solid separation and a liquid water immersion liquid. The solid separation is the cerium oxide polishing powder, and the water immersion liquid contains the The silicate component of glass powder, the silicate contains sodium silicate or potassium silicate; and a recycling silicate treatment, including adjusting the pH of the water immersion liquid to not less than pH 7, and then using it Calcium chloride (CaCl 2 ) is added to the water immersion solution to form a precipitate of calcium silicate, and then the separated solids are washed with water to remove sodium chloride through liquid-solid separation to obtain a solid Calcium silicate. 如請求項1所述之玻璃拋光廢棄物的回收再利用方法，其中該鹼劑對該玻璃拋光廢棄物的一重量比例為一鹼礦比，而該鹼礦比為至少1：1。 The method for recycling glass polishing waste according to claim 1, wherein a weight ratio of the alkali agent to the glass polishing waste is an alkali-ore ratio, and the alkali-ore ratio is at least 1:1. 如請求項1所述之玻璃拋光廢棄物的回收再利用方法，其中該焙燒溫度是至少400℃，而該焙燒時間是至少30分鐘。 The method for recycling glass polishing waste according to claim 1, wherein the firing temperature is at least 400°C, and the firing time is at least 30 minutes. 如請求項1所述之玻璃拋光廢棄物的回收再利用方法，其中該pH值調整劑包含氯化氫(HCl)。 The method for recycling glass polishing waste according to claim 1, wherein the pH adjusting agent contains hydrogen chloride (HCl). 如請求項1所述之玻璃拋光廢棄物的回收再利用方法，其中該固液分離裝置包含一離心機。 The method for recycling glass polishing waste according to claim 1, wherein the solid-liquid separation device includes a centrifuge. 如請求項1所述之玻璃拋光廢棄物的回收再利用方法，其中該水浸漬液以及氯化鈣的液固比為至多80ml/g。The method for recycling glass polishing waste according to claim 1, wherein the liquid-to-solid ratio of the water immersion liquid and calcium chloride is at most 80 ml/g.
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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103103361A (en) * 2013-02-28 2013-05-15 包头稀土研究院 Method for preparing rare earth oxide from rare earth polishing powder waste
CN104087757A (en) * 2014-07-12 2014-10-08 连云港健发磁性材料有限公司 Simplified method for recovering rare earth elements from waste residues of rare earth polishing powder

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103103361A (en) * 2013-02-28 2013-05-15 包头稀土研究院 Method for preparing rare earth oxide from rare earth polishing powder waste
CN104087757A (en) * 2014-07-12 2014-10-08 连云港健发磁性材料有限公司 Simplified method for recovering rare earth elements from waste residues of rare earth polishing powder

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