TWI418520B - Recycling Method of Waste Dust Ash Containing High Amount of Inorganic - Google Patents
Recycling Method of Waste Dust Ash Containing High Amount of Inorganic Download PDFInfo
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本發明係關於工業上廢棄物再生利用的製造方法，尤關於一種含有高量無機鹼之廢集塵灰的再生利用方法。The present invention relates to a method for producing industrial waste recycling, and more particularly to a method for recycling waste dust containing a high amount of inorganic alkali.
依據96年7月行政院環保署公告再生資源及廢棄物代碼查核，液晶玻璃熔解製造程序空氣汙染防制設備產出集塵灰，其廢棄物分類名稱為非有害事業集塵灰D-10，廢棄物代碼為D-1099，廢棄物名稱：非有害廢集塵灰或其混合物。According to the announcement of renewable resources and waste code by the Environmental Protection Agency of the Executive Yuan in July 1996, the liquid crystal glass melting and manufacturing process produces dust ash from the air pollution control equipment. The waste classification name is non-harmful business dust ash D-10. The waste code is D-1099, waste name: non-hazardous waste dust or a mixture thereof.
目前一般有害或無害的廢集塵灰的先前處理技術均以添加溶液乾燥固化再加以掩埋，或者作為水泥添加劑使用。Previous treatment techniques for waste dust that are generally hazardous or harmless are dried by solidification with an additive solution and then buried or used as a cement additive.
然而部分液晶玻璃熔解製造程序或某些液晶玻璃製造廠商之空氣汙染防制設備產出之高鹼性廢集塵灰含有諸如氧化鈉(Na2 O)等高量的無機鹼成分，經由離子層析法檢測，其諸如氧化鈉等高量的無機鹼成分高達94%以上。若經由前述既有固化掩埋方式處理，則透過雨水長期接觸，容易滲透高鹼性之無機鹼成分汙染土壤與地下水，嚴重影響其大自然生態生長環境。可知以掩埋方式處理該含有高量無機鹼成分之廢集塵灰未盡環境保護之責任。However, some of the liquid crystal glass melting manufacturing processes or the high-alkaline waste dust collected by the air pollution control equipment of some liquid crystal glass manufacturers contain high amounts of inorganic alkali components such as sodium oxide (Na 2 O), via the ion layer. According to the analytical method, a high amount of inorganic alkali components such as sodium oxide is as high as 94% or more. If it is treated by the above-mentioned existing solidification and burying method, it will easily penetrate the highly alkaline inorganic alkali component to contaminate the soil and groundwater through long-term contact with rainwater, which seriously affects its natural ecological environment. It can be seen that the disposal of the waste dust ash containing a high amount of inorganic alkali components in a buried manner is not responsible for environmental protection.
若以該諸如氧化鈉等無機鹼成分高達94%以上之廢集塵灰依既有處理方式作為水泥添加劑使用，不僅成份中含有高量的無機鹼卻無法有效回收利用，且由於其具高鹼性，因此作為水泥添加劑用途效果不佳。If the waste dust ash with an inorganic alkali component such as sodium oxide is as high as 94% or more, it is used as a cement additive according to the existing treatment method, and not only the component contains a high amount of inorganic alkali but cannot be effectively recycled, and since it has a high alkali content Sex, so it is not effective as a cement additive.
此外，經化驗可知該含有高量無機鹼之廢集塵灰，含有氟化物、硫酸鹽及硝酸鹽等有毒物質。若採用既有之固化掩埋或作為水泥添加劑等處理方法，上述有毒物質將造成嚴重的有害汙染。In addition, it has been found that the waste dust containing high amount of inorganic alkali contains toxic substances such as fluoride, sulfate and nitrate. If the existing curing burial or treatment as a cement additive is used, the above toxic substances will cause serious harmful pollution.
前述諸如行政院環保署公告液晶玻璃熔解製造程序空氣汙染防制設備產出集塵灰等既有技術無法對於含有高量無機鹼之廢集塵灰進行有效再生利用或防汙染處理，實為目前改善的主要重點。The aforementioned technologies such as the Environmental Protection Agency of the Executive Yuan have announced that the liquid crystal glass melting and manufacturing equipment produces dust ash and other existing technologies cannot effectively recycle or prevent pollution of waste dust containing high amounts of inorganic alkali. The main focus of improvement.
有鑒於既有廢集塵灰之處理方法大多以掩埋法處理或作為水泥添加劑使用，既有方法無法有效回收利用含有高量無機鹼之廢集塵灰，且將造成大自然生態環境的污染問題，本發明之目的在於提供一種含有高量無機鹼之廢集塵灰的再生利用方法，其係將含有無機鹼的廢集塵灰與水經過混合並形成含有無機鹼的上層水溶液及非水溶性固體，該上層水溶液透過後續不同加工程序，可以成功轉換可再生利用物質，有效回收再利用，促進產業經濟發展。In view of the fact that most of the treatment methods for waste dust collection are treated by landfill or as cement additives, existing methods cannot effectively recycle waste dust containing high amounts of inorganic alkali, and will cause pollution problems of natural ecological environment. The object of the present invention is to provide a method for recycling waste dust containing high amount of inorganic alkali, which is obtained by mixing waste dust containing inorganic alkali with water to form an aqueous solution containing inorganic alkali and water-insoluble. The solid, the upper aqueous solution can successfully convert the recyclable materials through subsequent different processing procedures, effectively recover and reuse, and promote industrial economic development.
本發明係提供一種含有高量無機鹼之廢集塵灰的再生利用方法，包括有：將含有無機鹼的廢集塵灰與水混合並形成上層水溶液及下層非水溶性固體，該上層水溶液之pH值大於9以及該上層水溶液中含有水溶性無機鹼；將前述上層水溶液及下層非水溶性固體分離，通入二氧化碳氣體於該上層水溶液並調整氣體之流量，用以調整該上層水溶液之pH值介於9至11之間，以獲取無機鹼產物。The present invention provides a method for recycling waste dust containing high amount of inorganic alkali, comprising: mixing waste dust containing inorganic base with water to form an upper aqueous solution and a lower water-insoluble solid, the upper aqueous solution The pH value is greater than 9 and the upper aqueous solution contains a water-soluble inorganic base; the upper aqueous solution and the lower water-insoluble solid are separated, carbon dioxide gas is introduced into the upper aqueous solution, and the flow rate of the gas is adjusted to adjust the pH of the upper aqueous solution. Between 9 and 11 to obtain an inorganic base product.
本發明所提供的一種含有高量無機鹼之廢集塵灰的再生利用方法，其提供的優點：The invention provides a method for recycling waste dust containing high amount of inorganic alkali, which provides the advantages:
1、本發明將該廢集塵灰溶於水中，產生該上層水溶液的pH值大於9並通入二氧化碳氣體用以調整前述該上層水溶液的pH值介於9至11之間，可生產氫氧化鈉、碳酸鈉或碳酸氫鈉，有效將廢集塵灰回收再利用，成功轉換可再生利用物質。1. The waste dust of the present invention is dissolved in water, and the pH of the upper aqueous solution is greater than 9 and carbon dioxide gas is introduced to adjust the pH of the upper aqueous solution to be between 9 and 11, thereby producing hydrogen peroxide. Sodium, sodium carbonate or sodium bicarbonate effectively recycles and recycles waste dust and successfully converts renewable materials.
2、本發明以水溶解廢集塵灰，得到含有水溶性無機鹼的上層水溶液，控制該水溶液的pH值介於5至6之間，再添加鋇離子用以除去該上層水溶液中的陰離子(F- )，可生產出硫酸鋇(BaSO4 )，有效利用可回收物質。2. The present invention dissolves waste dust ash in water to obtain an upper aqueous solution containing a water-soluble inorganic base, and controls the pH of the aqueous solution to be between 5 and 6, and further adds cerium ions to remove anions in the upper aqueous solution ( F - ), which produces barium sulfate (BaSO 4 ) and makes efficient use of recyclable materials.
3、本發明以水溶解廢集塵灰，得到含有水溶性無機鹼的上層水溶液，添加入界面活性劑於該上層水溶液中，可以與碳酸鈉及碳酸氫鈉混合反應產生清潔劑，有效回收利用可再生物質，具有產業經濟價值。3. The invention dissolves waste dust ash in water to obtain an upper layer aqueous solution containing a water-soluble inorganic base, and adds a surfactant to the upper layer aqueous solution, which can be mixed with sodium carbonate and sodium hydrogencarbonate to produce a cleaning agent, and is effectively recycled. Renewable substances with industrial economic value.
4、本發明中所述下層非水溶性固體含有氧化鋁(Al2 O3 )或氧化鐵(Fe2 O3 )的成分可進一步加酸溶解，廣泛加工應用於助凝劑產品，具有產業利用生產價值。4. The composition of the lower layer water-insoluble solid containing alumina (Al 2 O 3 ) or iron oxide (Fe 2 O 3 ) in the present invention can be further dissolved by acid, and is widely processed into a coagulant product, and has industrial utilization. Production value.
為能詳細瞭解本發明的技術特徵和實用功效，並可依照說明書的內容來實施，玆進一步以如圖1至圖4之較佳實施例，詳細說明如后：本發明係提供一種含有高量無機鹼之廢集塵灰的再生利用方法，其係將含有無機鹼的廢集塵灰與水經過充分混合並形成水溶性無機鹼上層水溶液及非水溶性固體，透過後續不同種類的加工生產方法，可以將廢集塵灰再利用；本發明所使用的廢集塵灰為旭硝子顯示玻璃股份有限公司所生產，經過採樣送樣至元智大學環境科技研究中心，全量分析及有害特性認定，前述之廢集塵灰檢驗結果，如表1所示：In order to understand the technical features and practical effects of the present invention in detail, and in accordance with the contents of the specification, the following is further described in detail with reference to the preferred embodiments of FIG. 1 to FIG. 4 as follows: the present invention provides a high amount. A method for recycling waste dust collected from an inorganic base, which is characterized in that a waste dust containing an inorganic base is thoroughly mixed with water to form an aqueous solution of a water-soluble inorganic base and a water-insoluble solid, and the subsequent different types of processing methods are produced. The waste dust collection ash can be reused; the waste dust collected by the invention is produced by Asahi Glass Display Glass Co., Ltd., and sampled and sent to the Environmental Science and Technology Research Center of Yuanzhi University for full analysis and identification of harmful characteristics. The results of the waste dust collection test are shown in Table 1:
1. 非有害廢集塵灰全量分析報告結果，依液晶玻璃基板熔融玻璃製程及空間污染防治設備之特性，其主要原料為以氧化矽(SiO2 )為主逸散粉塵，而空氣污染防治設備主要加入料為氫氧化鈉(NaOH)及碳酸氫鈉(NaHCO3 )因受廢氣熱氣而反應或氧化，故其中富含氧化鈉(Na2 O)為主。1. The results of the non-hazardous waste dust collection analysis report, according to the characteristics of the liquid crystal glass substrate molten glass process and space pollution prevention equipment, the main raw material is yttrium oxide (SiO 2 ) as the main fugitive dust, and the air pollution prevention equipment The main additives are sodium hydroxide (NaOH) and sodium hydrogencarbonate (NaHCO 3 ) which are mainly reacted or oxidized by the hot gas of the exhaust gas, so they are rich in sodium oxide (Na 2 O).
2. 如表1所示，元智大學環境科技研究中心的廢棄物樣品檢驗報告，呈現具有高含量的氧化鈉，及部份的氟化物、硫酸鹽、硝酸鹽，及其他的金屬氧化物；其中所含的氟離子(F- )含量約0.3%與硫酸根離子(SO4 2- )含量約5.24%，可利用本發明方法中通入二氧化碳氣體並調整其氣體流量，藉此調整該上層水溶液的pH值介於5至6之間，再添加鋇離子(Ba2+ )用以去除陰離子(F- )，進一步產生BaSO4(s) 。2. As shown in Table 1, the waste sample inspection report of the Environmental Science and Technology Research Center of Yuanzhi University presents high levels of sodium oxide, and some fluorides, sulfates, nitrates, and other metal oxides; The fluorine ion (F - ) content is about 0.3% and the sulfate ion (SO 4 2- ) content is about 5.24%, and the upper layer can be adjusted by introducing carbon dioxide gas into the method of the present invention and adjusting the gas flow rate thereof. The pH of the aqueous solution is between 5 and 6, and cesium ions (Ba 2+ ) are added to remove the anion (F - ) to further produce BaSO 4 (s) .
如圖1所示，本發明提供一種含有高量無機鹼之廢集塵灰的再生利用方法：生產工業級碳酸鈉或碳酸氫鈉，結合下列第一步驟及第二步驟，詳細敘述如下；本發明係提供一種含有高量無機鹼之廢集塵灰的再生利用方法，包括有下列步驟：將含有無機鹼的廢集塵灰與純水經過充分混合並形成上層水溶液及下層非水溶性固體，該上層水溶液之pH值大於9以及該上層水溶液中含有水溶性無機鹼(第一步驟)；將前述上層水溶液及下層非水溶性固體分離，進一步添加氫氧化鈉於該上層水溶液中，用以調整該上層水溶液之pH值大於14，藉此將上述無機鹼產物溶解；再於該上層水溶液中通入二氧化碳氣體並調整其氣體流量，二氧化碳與水反應產生H2 CO3(aq) ，調整該上層水溶液之pH介於10至11之間，生產出碳酸鈉或碳酸氫鈉等無機鹼產物(第二步驟)。As shown in FIG. 1 , the present invention provides a method for recycling waste dust containing high amount of inorganic alkali: producing industrial grade sodium carbonate or sodium hydrogencarbonate, in combination with the following first step and second step, which are described in detail below; The invention provides a method for recycling waste dust containing ash with a high amount of inorganic alkali, comprising the steps of: thoroughly mixing waste dust containing inorganic alkali with pure water to form an upper aqueous solution and a lower water-insoluble solid, The upper layer aqueous solution has a pH greater than 9 and the upper aqueous solution contains a water-soluble inorganic base (first step); the upper aqueous solution and the lower layer of water-insoluble solid are separated, and further sodium hydroxide is added to the upper aqueous solution for adjustment The pH of the upper aqueous solution is greater than 14, thereby dissolving the inorganic base product; then carbon dioxide gas is introduced into the upper aqueous solution and the gas flow rate is adjusted, and carbon dioxide reacts with water to produce H 2 CO 3 (aq) , and the upper layer is adjusted. The pH of the aqueous solution is between 10 and 11, and an inorganic base product such as sodium carbonate or sodium hydrogencarbonate is produced (second step).
將含有無機鹼的廢集塵灰之成份分析結果發現，除少量非水溶性氧化物，如氧化矽(0.0223%)、氧化鋁(0.0409%)、氧化鐵(0.0078%)外，亦含有水溶性鹼金屬氧化鈉(94.2%)、氧化鉀(0.0285%)及碳酸鈉與碳酸氫鈉。前述之水溶性無機鹼，為工業上常用的重要化學品。本發明透過以純水溶解出水溶性無機鹽，通入二氧化碳氣體用以調控整體水溶液的pH值，再經後續回收製程，有效回收再利用上述水溶液中的氫氧化鈉、碳酸鈉或碳酸氫鈉。The analysis of the components of the waste dust containing inorganic base found that, in addition to a small amount of water-insoluble oxides such as cerium oxide (0.0223%), alumina (0.0409%), iron oxide (0.0078%), it also contained water-soluble Alkali metal oxide (94.2%), potassium oxide (0.0285%), and sodium carbonate and sodium hydrogencarbonate. The aforementioned water-soluble inorganic base is an important chemical commonly used in the industry. The invention dissolves the water-soluble inorganic salt in pure water, introduces carbon dioxide gas to regulate the pH value of the whole aqueous solution, and then recovers and reuses the sodium hydroxide, sodium carbonate or sodium hydrogencarbonate in the aqueous solution through a subsequent recovery process.
如圖6所示，將集塵灰儲槽21內部儲存的廢集塵灰經由流量控制器22控制前述廢集塵灰之流量並通入攪拌槽28中，同時透過管線24通入純水於攪拌槽28中，並經由流量控制器25控制前述純水之流量，將前述廢塵灰與純水於攪拌槽28進行混合，形成水溶性無機鹼，並利用pH控制器26調控攪拌槽28內水溶性無機鹼的pH值，攪拌槽28反應如下：As shown in FIG. 6, the waste dust collected in the dust collecting ash storage tank 21 is controlled by the flow controller 22 to flow the waste dust ash into the stirring tank 28, and the pure water is introduced through the pipeline 24. In the agitation tank 28, the flow rate of the pure water is controlled by the flow rate controller 25, and the waste dust and the pure water are mixed in the agitation tank 28 to form a water-soluble inorganic base, and the pH controller 26 is used to regulate the inside of the agitation tank 28. The pH of the water-soluble inorganic base, the stirring tank 28 reacts as follows:
攪拌槽反應：Stirring tank reaction:
Na2 O(s) +H2 O→2NaOH(aq) Na 2 O (s) +H 2 O→2NaOH (aq)
Na2 CO3(s) +H2 O→Na2 CO3(aq) Na 2 CO 3(s) +H 2 O→Na 2 CO 3(aq)
NaHCO3(s) +H2 O→NaHCO3(aq) NaHCO 3(s) +H 2 O→NaHCO 3(aq)
NaHCO3(aq) +NaOH→Na2 CO3(aq) +H2 ONaHCO 3(aq) +NaOH→Na 2 CO 3(aq) +H 2 O
因此，由攪拌槽28出來之水溶液為氫氧化鈉與碳酸鈉與碳氫酸鈉。Therefore, the aqueous solution from the agitation tank 28 is sodium hydroxide and sodium carbonate and sodium hydrogencarbonate.
如圖2所示，第二種含有高量無機鹼之廢集塵灰的再生利用方法，結合第一步驟及第二步驟-1：添加介面活性劑，生產清潔劑，前述之製程敘述如下；將含有無機鹼的廢集塵灰與純水經過充分混合並形成上層水溶液及下層非水溶性固體，該上層水溶液之pH值大於9以及該上層水溶液中含有水溶性無機鹼(第一步驟)；將前述上層水溶液及下層非水溶性固體分離，與前述之第一種方法相同，先通入二氧化碳氣體於該上層水溶液中，所通入的CO2 氣體與水反應產生H2 CO3(aq) ，藉由調整CO2 氣體之流量，用以調整該上層水溶液的pH值介於9至11之間；之後於該上層水溶液中加入約重量百分濃度介於10至15%的界面活性劑與該上層水溶液中的碳酸鈉及碳酸氫鈉混合反應產生清潔劑(第二步驟-1)。As shown in FIG. 2, a second method for recycling waste dust containing high amount of inorganic alkali, combined with the first step and the second step-1: adding a surfactant to produce a cleaning agent, the foregoing process is described as follows; The waste dust containing the inorganic base is thoroughly mixed with the pure water to form an upper aqueous solution and a lower water-insoluble solid, the upper aqueous solution having a pH greater than 9 and the upper aqueous solution containing a water-soluble inorganic base (first step); Separating the upper aqueous solution and the lower water-insoluble solid, and in the same manner as the first method described above, first introducing carbon dioxide gas into the upper aqueous solution, and the introduced CO 2 gas reacts with water to generate H 2 CO 3 (aq). Adjusting the flow rate of the CO 2 gas to adjust the pH of the upper aqueous solution to be between 9 and 11; then adding about 10 to 15% of the surfactant to the upper aqueous solution. The sodium carbonate and sodium hydrogencarbonate in the upper aqueous solution are mixed to produce a detergent (second step-1).
如圖6所示，前述之攪拌槽內部反應如前所述相同，經固液分離後，於該上層水溶液中加入界面活性劑，調配生產清潔劑；因溶液中主要以Na2 CO3 及NaHCO3 為主，加入重量百分濃度介於10至15%的的界面活性劑(可為十二烷基硫酸鈉(Sodium dodecyl sulfate，SDS))可生產常用的家庭用清潔劑。一般洗衣粉含：界面活性劑約15%、Na2 CO3 約10%、Na2 SO4 18至20%、矽酸鈉14至15%以及磷酸鈉約30%。As shown in Fig. 6, the internal reaction of the agitation tank is the same as described above. After solid-liquid separation, a surfactant is added to the upper aqueous solution to prepare a cleaning agent; the solution mainly contains Na 2 CO 3 and NaHCO. 3 is mainly based on adding 10% to 15% by weight of a surfactant (sodium dodecyl sulfate (SDS)) to produce a commonly used household cleaner. Typical laundry detergents contain about 15% surfactant, about 10% Na 2 CO 3 , 18 to 20% Na 2 SO 4 , 14 to 15% sodium citrate, and about 30% sodium phosphate.
一般的洗衣粉配方例子：界面活性劑：15%、肥皂：3%、磷酸鈉鹽或沸石：30%以及矽酸鈉：14%。Examples of general detergent formulations: surfactant: 15%, soap: 3%, sodium phosphate or zeolite: 30%, and sodium citrate: 14%.
如圖3所示，第三種含有高量無機鹼之廢集塵灰的再生利用方法，結合第一步驟和第三步驟：利用通入二氧化碳氣體，用以調整前述水溶性無機鹼的pH值並添加鋇離子(Ba2+ )，產生白色之硫酸鋇(BaSO4 )沉澱，前述之製程詳細敘述如下；將含有無機鹼的廢集塵灰與水經過充分混合(第一步驟)，形成上層水溶液及下層非水溶性固體，該上層水溶液之pH值大於9以及該上層水溶液中含有水溶性無機鹼(第三步驟)；將前述上層水溶液及下層非水溶性固體分離，通入二氧化碳氣體於該上層水溶液，所通入的CO2 氣體與水反應產生H2 CO3(ag) ，藉由通入CO2 氣體並調整其氣體流量，用以調整該上層水溶液的pH值介於5至6之間，並添加鋇離子(Ba2+ )於該上層水溶液中(第三步驟)，產生下層沉澱物硫酸鋇(BaSO4(s) )及上層含有無機鹼水溶液(第三步驟)。As shown in FIG. 3, a third method for recycling waste dust containing high amount of inorganic alkali is combined with the first step and the third step: using carbon dioxide gas to adjust the pH of the water-soluble inorganic base. And adding barium ions (Ba 2+ ) to produce white barium sulfate (BaSO 4 ) precipitate, the above process is described in detail below; the waste dust containing inorganic base is thoroughly mixed with water (first step) to form the upper layer An aqueous solution and a lower layer of water-insoluble solid, wherein the pH of the upper aqueous solution is greater than 9 and the aqueous solution of the upper layer contains a water-soluble inorganic base (third step); separating the aqueous solution of the upper layer and the lower layer of water-insoluble solid, and introducing carbon dioxide gas thereto The upper aqueous solution, the introduced CO 2 gas reacts with water to generate H 2 CO 3 (ag) , and the pH of the upper aqueous solution is adjusted to be 5 to 6 by introducing CO 2 gas and adjusting the gas flow rate thereof. Meanwhile, cerium ions (Ba 2+ ) are added to the upper aqueous solution (third step) to produce a lower precipitate of barium sulfate (BaSO 4 (s) ) and an upper layer containing an aqueous solution of an inorganic alkali (third step).
如圖6所示，前述之攪拌槽內部反應如前所述相同，經固液分離後，前述之充分混合反應後的水溶性無機鹼，經由管線27通入下一攪拌槽35中，並透過流量控制器29控制前述水溶性無機鹼進入攪拌槽35中的流量，將高壓氣體儲槽32內部的二氧化碳高壓氣體，通入前述攪拌槽35中，並與水溶性無機鹼充分反應，藉由通入二氧化碳氣體並調整其氣體流量，用以調整前述水溶性無機鹼的pH值，並利用pH控制器33調控攪拌槽35內水溶性無機鹼的pH值，反應如下：As shown in Fig. 6, the internal reaction of the agitation tank described above is the same as described above, and after the solid-liquid separation, the water-soluble inorganic base which has been sufficiently mixed as described above is introduced into the next agitation tank 35 via the line 27, and is permeated. The flow controller 29 controls the flow rate of the water-soluble inorganic base into the agitation tank 35, and passes the high-pressure carbon dioxide gas inside the high-pressure gas storage tank 32 into the agitation tank 35, and fully reacts with the water-soluble inorganic base. The carbon dioxide gas is adjusted and the gas flow rate is adjusted to adjust the pH value of the water-soluble inorganic base, and the pH controller 33 is used to adjust the pH value of the water-soluble inorganic base in the stirring tank 35. The reaction is as follows:
PH調整槽：PH adjustment slot:
NaOH(aq) +H2 CO3(aq) →Na2 CO3(aq) +H2 ONaOH (aq) + H 2 CO 3 (aq) → Na 2 CO 3 (aq) + H 2 O
Na2 CO3(aq) +H2 CO3(aq) →2NaHCO3(aq) Na 2 CO 3(aq) +H 2 CO 3(aq) →2NaHCO 3(aq)
利用CO2 調整溶液之pH值，可產生Na2 CO3 與NaHCO3 ，因使用CO2 不致有其他陰離子加入。(CO2 之用量，依所需溶液pH而定。)By adjusting the pH of the solution with CO 2 , Na 2 CO 3 and NaHCO 3 can be produced, and no other anions are added due to the use of CO 2 . (The amount of CO 2 depends on the pH of the desired solution.)
前述之攪拌槽35內水溶性無機鹼利用通入CO2 並調整其氣體流量，用以調整溶液之pH值，同時結合添加劑泵39、管線38與添加劑加入控制器37，於攪拌槽35中通入含有鋇離子(Ba2+ )的添加劑，充分反應，產生下層白色之硫酸鋇(BaSO4 )沉澱，製作過程如下：生產BaSO4 ，於攪拌槽35內水溶性無機鹼中測定SO4 2- 含量時，以CO2 調整溶液於不同的pH範圍之間，以Ba2+ 與SO4 2- 反應生產BaSO4 ；溶液通入CO2 以調整溶液之pH在5至6之間，依測定之SO4 2- 含量，加Ba2+ ，產生白色之BaSO4 沉澱物。The water-soluble inorganic base in the agitation tank 35 is used to adjust the pH of the solution by introducing CO 2 and adjusting the gas flow rate thereof, and is combined with the additive pump 39, the line 38 and the additive to the controller 37, and is passed through the agitation tank 35. The additive containing barium ions (Ba 2+ ) is sufficiently reacted to produce a white precipitate of barium sulfate (BaSO 4 ), which is produced as follows: BaSO 4 is produced, and SO 4 2- is determined in a water-soluble inorganic base in a stirred tank 35. When the content is adjusted, the solution is adjusted to a different pH range with CO 2 , and Ba 2+ is reacted with SO 4 2- to produce BaSO 4 ; the solution is passed through CO 2 to adjust the pH of the solution between 5 and 6, according to the determination. The content of SO 4 2- was added with Ba 2+ to produce a white BaSO 4 precipitate.
將前述之含有NaOH與Na2 CO3 與NaHCO3 的上層水溶性無機鹼透過管線34通入純化處理槽41中，並經由流量控制器40控制前述上層水溶性無機鹼之流量，製造出工業級Na2 CO3 或NaHCO3 ，其產量比率依進料廢棄物之成份與市場需求而定。The upper water-soluble inorganic base containing the NaOH and Na 2 CO 3 and NaHCO 3 is passed through the purification treatment tank 41 through the line 34, and the flow rate of the upper water-soluble inorganic base is controlled by the flow controller 40 to produce an industrial grade. Na 2 CO 3 or NaHCO 3 , the yield ratio depends on the composition of the feed waste and market demand.
如圖4所示，第四種含有高量無機鹼之廢集塵灰的再生利用方法，結合第一步驟及第四步驟：另有小部分(約10%)固體不溶解，經固液分離後，形成下層非水溶性固體且其含有氧化鋁(Al2 O3 )或氧化鐵(Fe2 O3 )的成分，可以進行廢集塵灰再利用回收技術；非水溶性固體可再進一步加酸溶解產生混凝劑產品，其中酸可為鹽酸或硝酸或硫酸等，廣泛加工應用於助凝劑產品，具有經濟回收利用價值。As shown in FIG. 4, the fourth method for recycling waste dust containing high amount of inorganic alkali combines the first step and the fourth step: another small portion (about 10%) of the solid is insoluble, and is separated by solid-liquid separation. After that, a lower layer of water-insoluble solid is formed and contains a component of aluminum oxide (Al 2 O 3 ) or iron oxide (Fe 2 O 3 ), which can be used for recycling waste dust collection; the water-insoluble solid can be further added The acid dissolves to produce a coagulant product, wherein the acid can be hydrochloric acid or nitric acid or sulfuric acid, etc., and is widely processed into a coagulant product, and has economic recycling value.
其餘非水溶性固體物Al2 O3 及Fe2 O3 可再加酸溶解：The remaining water-insoluble solids, Al 2 O 3 and Fe 2 O 3 , can be dissolved by acid addition:
Al2 O3(s) +HCl(aq) →AlCl3(aq) Al 2 O 3(s) +HCl (aq) →AlCl 3(aq)
Fe2 O3(s) +HCl(aq) →FeCl3(aq) Fe 2 O 3(s) +HCl (aq) →FeCl 3(aq)
AlCl3(aq) 與FeCl3(aq) 再純化濃縮，可做為廢水處理之混凝劑。AlCl 3 (aq) and FeCl 3 (aq) are re-purified and concentrated to be used as a coagulant for wastewater treatment.
其中固體物可能含有之SO4 2- 或F- 等離子，通入二氧化碳氣體以控制該水溶液之pH介於5至6之間，於HCO3 - 存在條件下，添加Ba2+ 用以除去陰離子(F- )並沉澱產生BaF2(s) 再去除，而所生產出的BaSO4(s) 可再純化使用，。The solid matter may contain SO 4 2- or F - plasma, and carbon dioxide gas is introduced to control the pH of the aqueous solution to be between 5 and 6. In the presence of HCO 3 - , Ba 2+ is added to remove the anion ( F - ) and precipitation produce BaF 2 (s) and then removed, and the produced BaSO 4 (s) can be used for further purification.
SO4 2- +Ba2+ →BaSO4(s) SO 4 2- +Ba 2+ →BaSO 4(s)
F- +Ba2+ →BaF2(s) F - +Ba 2+ →BaF 2(s)
前述之所回收利用的沉澱產物硫酸鋇(BaSO4 )可作顏料用途，其係是第一個低折光係數的顏料，成功的作為油漆組份，這是作為立德粉的組成份的直接結果，立德粉的複合白色顏料，含有28至30%重量的硫化鋅和70至72%重量的硫酸鋇的共同沈澱物。同樣，硫酸鋇也是第一個二氧化鈦與鋇複合顏料的組成分子，當白鉛作為室外房屋油漆的主要顏料時，硫酸鋇有時作為滲合劑，因為此滲合劑有較高比重，此類用重量出售，如同在歐洲，好的顏料硫酸鋇或重晶石顏料(bayte)含有至少96%硫酸鋇，前述之回收利用的產物硫酸鋇可以廣泛應用於產業上，具有更高的產業利用價值。The above-mentioned recovered precipitated product barium sulfate (BaSO 4 ) can be used as a pigment, which is the first low refractive index pigment, which is successfully used as a paint component, which is a direct result of the composition of the lithopone. A composite white pigment of Lithopone containing a coprecipitate of 28 to 30% by weight of zinc sulfide and 70 to 72% by weight of barium sulfate. Similarly, barium sulphate is also the first component of titanium dioxide and cerium composite pigments. When white lead is used as the main pigment in outdoor house paints, barium sulphate is sometimes used as an osmotic agent because of the higher specific gravity of this osmotic agent. For sale, as in Europe, good pigment barium sulfate or barite contains at least 96% barium sulfate, and the above-mentioned recycled product barium sulfate can be widely used in the industry and has higher industrial utilization value.
如圖5所示，前述之本發明含有高量無機鹼之廢集塵灰的再生利用方法中所述的第一步驟與第二步驟至第四步驟中任一步驟可相組合實施，如圖1至圖4所示及其前述說明，本發明中所述的再生利用方法之步驟，可相組合成一套完整的廢集塵灰可再生利用物質之再生利用方法，透過後續不同種類的加工生產方法，可以有效回收再利用廢集塵灰中的可再生利用物質。As shown in FIG. 5, the first step and the second step to the fourth step described in the foregoing method for recycling waste dust containing high amount of inorganic alkali of the present invention may be combined and implemented. 1 to 4 and the foregoing description, the steps of the recycling method described in the present invention can be combined into a complete recycling method of waste dust collection materials, which can be produced through subsequent processing of different types. The method can effectively recycle and recycle the recyclable materials in the waste dust.
【實施例】[Examples]
本實施例選取旭硝子顯示玻璃股份有限公司所生產的廢集塵灰，有效回收利用廢集塵灰；選取重量100g的廢集塵灰固體廢棄物加入160g的水混合，形成重量250 g的NaOH與Na2 CO3 飽和混合液及可能的與其他物質(如Na2 SO4 )[中間產物A(液體)]，以及10 g的非溶解性固體[中間產物B(固體)]。In this embodiment, waste dust ash produced by Asahi Glass Display Glass Co., Ltd. is selected, and waste dust ash is effectively recycled; 100 g of waste dust ash solid waste is added and 160 g of water is mixed to form 250 g of NaOH and Saturated Na 2 CO 3 mixture and possibly with other substances (such as Na 2 SO 4 ) [intermediate A (liquid)], and 10 g of insoluble solid [intermediate B (solid)].
160g的水中有18g的水與Na2 O反應生成NaOH(g) ，其餘用於溶解NaOH與Na2 CO3 ；非溶解性固體主要為Al2 O3 、Fe2 O3 與SiO2 為主，可經過後續再研發再利用製程，請參見圖7所示，流程圖說明如下：In 160g of water, 18g of water reacts with Na 2 O to form NaOH (g) , and the rest is used to dissolve NaOH and Na 2 CO 3 ; the non-soluble solids are mainly Al 2 O 3 , Fe 2 O 3 and SiO 2 . After further development and reuse of the process, please refer to Figure 7, the flow chart is as follows:
(1) 固體廢棄物：依元智大學分析報告指出含有下列成分Na2 O(94.2%)、K2 O(0.0285%)、Na2 CO3 與NaHCO3 (5.1%)、SiO2 (0.0223%)、Al2 O3 (0.0409%)、Fe2 O3 (0.0078%)。(1) Solid waste: According to the analysis report of Yuanzhi University, the following ingredients are included: Na 2 O (94.2%), K 2 O (0.0285%), Na 2 CO 3 and NaHCO 3 (5.1%), SiO 2 (0.0223%) ), Al 2 O 3 (0.0409%), Fe 2 O 3 (0.0078%).
(2) 攪拌槽反應：(2) Stirring tank reaction:
Na2 O(s) +H2 O→2NaOH(aq) Na 2 O (s) +H 2 O→2NaOH (aq)
Na2 CO3(s) +H2 O→Na2 CO3(aq) Na 2 CO 3(s) +H 2 O→Na 2 CO 3(aq)
NaHCO3(s) +H2 O→NaHCO3(aq) NaHCO 3(s) +H 2 O→NaHCO 3(aq)
NaHCO3(aq) +NaOH→Na2 CO3(aq) +H2 ONaHCO 3(aq) +NaOH→Na 2 CO 3(aq) +H 2 O
請參見圖7所示，前述之重量100g的廢集塵灰固體廢棄物加入160g的水混合，由攪拌槽分離出來的水溶液約250g，含有NaOH、Na2 CO3 與NaHCO3 ，另有小部分約10%不溶解固體約10g(SiO2 、Al2 O3 、Fe2 O3 等)，將該上述水溶液250g進行後續有效再回收分離。從而可知本實施例所呈現之方法可以於水溶液中分離出90%之諸如碳酸鈉等水溶性成分，具有相當高的回收率。Referring to Figure 7, the above-mentioned 100g of waste dust ash solid waste is mixed with 160g of water, and the aqueous solution separated by the stirring tank is about 250g, containing NaOH, Na 2 CO 3 and NaHCO 3 , and a small part. About 10% of the solids were dissolved in about 10 g (SiO 2 , Al 2 O 3 , Fe 2 O 3 , etc.), and 250 g of the above aqueous solution was subjected to subsequent effective recovery and separation. Thus, it can be seen that the method presented in this example can separate 90% of water-soluble components such as sodium carbonate in an aqueous solution, and has a relatively high recovery rate.
(3) pH調整槽：(3) pH adjustment tank:
CO2(g) +H2 O(aq) →H2 CO3 (aq)CO 2(g) +H 2 O (aq) →H 2 CO 3 (aq)
NaOH(aq) +H2 CO3(aq )→Na2 CO3(aq) +H2 ONaOH (aq) + H 2 CO 3 (aq ) → Na 2 CO 3 (aq) + H 2 O
Na2 CO3(aq) +H2 CO3(aq) →2 NaHCO3(aq) Na 2 CO 3(aq) +H 2 CO 3(aq) →2 NaHCO 3(aq)
通入CO2 氣體於水中形成H2 CO3(aq) ，所形成的H2 CO3(aq) 與NaOH(aq) 及Na2 CO3(aq) 反應，利用通入CO2 調整溶液之pH值，可產生Na2 CO3 與NaHCO3 ，因使用CO2 不致有其他陰離子加入，CO2 之用量，依所需溶液pH而定。H 2 CO 3 (aq) is formed by introducing CO 2 gas into water, and the formed H 2 CO 3 (aq) is reacted with NaOH (aq) and Na 2 CO 3 (aq) , and the pH of the solution is adjusted by using CO 2 . The value can produce Na 2 CO 3 and NaHCO 3 . Since CO 2 is not used, other anions are added, and the amount of CO 2 depends on the pH of the desired solution.
再利用製程：將含有NaOH、Na2 CO3 與NaHCO3 的上層水溶液再利用生產NaHCO3 與Na2 CO3 ：首先測定SO4 2- 含量時，通入CO2 用以調整水溶液pH，介於5至6之間，依測定之SO4 2- 含量，添加入Ba2+ ，產生白色之BaSO4 沉澱，經固液分離後，上層水溶液含有NaOH、Na2 CO3 與NaHCO3 ，可直接生產NaHCO3 或加NaOH，調整pH在10至11之間生產Na2 CO3 。Recycling process: Reusing the upper aqueous solution containing NaOH, Na 2 CO 3 and NaHCO 3 to produce NaHCO 3 and Na 2 CO 3 : When the SO 4 2- content is first determined, CO 2 is introduced to adjust the pH of the aqueous solution. Between 5 and 6, according to the measured SO 4 2- content, Ba 2+ is added to produce a white BaSO 4 precipitate. After solid-liquid separation, the upper aqueous solution contains NaOH, Na 2 CO 3 and NaHCO 3 , which can be directly produced. NaHCO 3 or NaOH was added to adjust the pH between 10 and 11 to produce Na 2 CO 3 .
藉由上述方法再利用生產出的NaOH、Na2 CO3 及NaHCO3 產物，後續以實驗室所習用的溶解度測定方法，於20℃時分別對NaOH、Na2 CO3 及NaHCO3 進行溶解度測定，獲得在水中之溶解度分別為111 g/100mlH2 O、22 g/100mlH2 O與10 g/100ml H2 O。The NaOH, Na 2 CO 3 and NaHCO 3 products produced by the above method were reused, and the solubility of NaOH, Na 2 CO 3 and NaHCO 3 was measured at 20 ° C by the solubility measurement method conventionally used in the laboratory. the solubility in water were 111 g / 100mlH 2 O, 22 g / 100mlH 2 O and 10 g / 100ml H 2 O.
所生產出的NaOH、Na2 CO3 及NaHCO3 產量比率依進料廢棄物之成份與市場需求而定而定。The ratio of production of NaOH, Na 2 CO 3 and NaHCO 3 produced depends on the composition of the feed waste and market demand.
回收再利用性的產品開發：Recycling product development:
(1)加入界面活性劑，參配生產清潔劑：因該上層水溶液中主要以NaOH、Na2 CO3 及NaHCO3 為主，加入約重量百分濃度介於10至15%的的界面活性劑可生產常用的家庭用清潔劑。一般洗衣粉含界面活性劑約15%、Na2 CO3 約10%、Na2 SO4 約18至20%、矽酸鈉約14至15%、磷酸鈉約30%(逐年降低中)，另有其他芳香劑等。生產者可依市場需求，長期開發配方。(1) Adding a surfactant, and preparing a detergent: as the main solution is mainly composed of NaOH, Na 2 CO 3 and NaHCO 3 , and adding about 10 to 15% by weight of the surfactant. It can produce commonly used household cleaners. The general washing powder contains about 15% of surfactant, about 10% of Na 2 CO 3 , about 18 to 20% of Na 2 SO 4 , about 14 to 15% of sodium citrate, about 30% of sodium phosphate (reduced year by year), and There are other fragrances and the like. Producers can develop formulas for a long time according to market demand.
如前述表1所示，本發明廢集塵灰，呈現具有高含量的氧化鈉，及部份的氟化物、硫酸鹽、硝酸鹽，及其他的金屬氧化物；藉由本發明方法可以有效利用精製生產NaOH、Na2 CO3 及NaHCO3 產物，以及其他相關衍生產品應用；另外，本發明廢集塵灰所含氟化物、硫酸鹽、硝酸鹽等具有毒性物質，其中的氟離子(F- )含量約0.3%、與硫酸根離子(SO4 2- )含量約5.24%，可利用本發明通入二氧化碳氣體之方法，藉此調整該上層水溶液的pH值介於5至6之間，再添加鋇離子(Ba2+ )用以去除陰離子(F- )，產生BaF2 (s)再去除，而所生成的BaSO4 (s)將再純化使用，成功轉換並除去原本前述之廢集塵灰內所含有的毒性物質，較具環保安全性及再生利用經濟價值。As shown in Table 1 above, the waste dust ash of the present invention exhibits a high content of sodium oxide, and a part of fluoride, sulfate, nitrate, and other metal oxides; the method of the present invention can effectively utilize refining Production of NaOH, Na 2 CO 3 and NaHCO 3 products, and other related derivative products; in addition, the waste dust of the present invention contains toxic substances such as fluorides, sulfates, nitrates, etc., among which fluoride ions (F - ) The content of about 0.3% and the content of sulfate ion (SO 4 2- ) is about 5.24%, and the method of introducing carbon dioxide gas into the invention can be used, thereby adjusting the pH of the upper aqueous solution to be between 5 and 6, and then adding The cesium ion (Ba 2+ ) is used to remove the anion (F - ), and the BaF 2 (s) is removed, and the generated BaSO 4 (s) is re-purified to successfully convert and remove the previously used waste dust. The toxic substances contained in the product are more environmentally safe and have economic value for recycling.
本發明係將含有無機鹼的廢集塵灰與水經過充分混合並形成含有水溶性無機鹼的上層水溶液及非水溶性固體，透過後續不同加工程序，透過後續不同種類的加工生產方法，可以將廢集塵灰完全回收再利用，成功轉換廢集塵灰中的可再生利用物質，且亦可提供有效處理氟化物、硫酸鹽及硝酸鹽等有毒物質的效果。The invention combines waste dust ash containing inorganic alkali with water to form an upper aqueous solution containing water-soluble inorganic alkali and water-insoluble solid, and through subsequent different processing procedures, through subsequent different kinds of processing and production methods, The waste dust collection ash is completely recycled and reused, and the recyclable materials in the waste dust collection ash are successfully converted, and the effects of effectively treating toxic substances such as fluoride, sulfate and nitrate can also be provided.
21．．．集塵灰儲槽twenty one. . . Dust collecting ash storage tank
23、30．．．攪拌機23, 30. . . Mixer
28、35．．．攪拌槽28, 35. . . Stirring tank
32．．．高壓氣體儲槽32. . . High pressure gas storage tank
37．．．添加劑加入控制器37. . . Additives to the controller
39．．．添加劑泵39. . . Additive pump
41．．．純化處理槽41. . . Purification tank
26、33．．．pH控制器26, 33. . . pH controller
44．．．加壓馬達44. . . Pressurized motor
46．．．水氣回收器46. . . Water gas recovery
24、27、34、38、42、45．．．管線24, 27, 34, 38, 42, 45. . . Pipeline
22、25、29、31、36、40、43．．．流量控制器22, 25, 29, 31, 36, 40, 43. . . Flow controller
圖1係為本發明回收方法的第一步驟結合第二步驟的製作流程圖。Figure 1 is a flow chart showing the first step of the recycling method of the present invention in combination with the second step.
圖2係為本發明回收方法的第一步驟結合第二步驟-1的製作流程圖。2 is a flow chart showing the first step of the recycling method of the present invention in combination with the second step-1.
圖3係為本發明回收方法的第一步驟結合第三步驟的製作流程圖。3 is a flow chart showing the first step of the recycling method of the present invention in combination with the third step.
圖4係為本發明回收方法的第一步驟結合第四步驟的製作流程圖。4 is a flow chart showing the first step of the recycling method of the present invention in combination with the fourth step.
圖5係為本發明回收方法中所述的第一步驟與第二步驟至第四步驟中任一步驟可相組合的製作流程圖。Figure 5 is a flow chart showing the fabrication of the first step and the second step to the fourth step described in the recycling method of the present invention.
圖6係為本發明之較佳實施例示意圖。Figure 6 is a schematic illustration of a preferred embodiment of the present invention.
圖7係為本發明廢集塵灰再利用製程流程圖。FIG. 7 is a flow chart of the process for recycling waste dust collection ash according to the present invention.
Claims (9)
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| TW99145257A TWI418520B (en) | 2010-12-22 | 2010-12-22 | Recycling Method of Waste Dust Ash Containing High Amount of Inorganic |
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| TW99145257A TWI418520B (en) | 2010-12-22 | 2010-12-22 | Recycling Method of Waste Dust Ash Containing High Amount of Inorganic |
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TW209856B (en) * | 1990-01-30 | 1993-07-21 | Air Prod & Chem | |
| CN100549527C (en) * | 2002-10-01 | 2009-10-14 | 维特罗环球有限公司 | Be used for controlling the control system of the supply and the burning of glass-melting furnace dusty fuel |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TW209856B (en) * | 1990-01-30 | 1993-07-21 | Air Prod & Chem | |
| CN100549527C (en) * | 2002-10-01 | 2009-10-14 | 维特罗环球有限公司 | Be used for controlling the control system of the supply and the burning of glass-melting furnace dusty fuel |
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