TW202222696A - Method for processing waste sulfuric acid and calcium-containing byproduct - Google Patents
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本揭露是有關於一種硫酸廢液與含鈣副產物的處理方法，且特別是有關於一種硫酸廢液與轉爐石渣的處理方法。The present disclosure relates to a method for treating sulfuric acid waste liquid and calcium-containing by-products, and more particularly, to a method for treating sulfuric acid waste liquid and converter gravel.
硫酸是工業上一種重要的化學品，其用途相當廣泛，如製造肥料、非鹼性清潔劑、護膚品、以及油漆添加劑與炸藥等。近年來，硫酸也被運用於晶圓製造業。舉例而言，硫酸可被運用於晶圓清洗。由於晶圓製造業的蓬勃發展，硫酸廢液的產量變得相當可觀，硫酸廢液的處理方法也成為相關領域的重要課題之一。Sulfuric acid is an important chemical in industry with a wide range of uses, such as the manufacture of fertilizers, non-alkaline cleaners, skin care products, as well as paint additives and explosives. In recent years, sulfuric acid has also been used in wafer manufacturing. For example, sulfuric acid can be used for wafer cleaning. Due to the vigorous development of the wafer manufacturing industry, the output of sulfuric acid waste liquid has become considerable, and the treatment method of sulfuric acid waste liquid has also become one of the important topics in related fields.
另一方面，含鈣副產物例如是利用轉爐冶煉法煉鋼所排出的轉爐石（basic oxygen furnace slag）。轉爐石的主要成分為氧化鈣與氧化鐵，且可包括其他例如是矽、鎂、鋁、錳等元素的氧化物。轉爐石經加工後可作為水泥、塗料、瀝青、油漆等的填料。然而，作為填料的轉爐石具有易吸水膨脹而造成破損、粉化等問題，且機械性質與耐高溫性也有待改善。On the other hand, the calcium-containing by-product is, for example, a basic oxygen furnace slag discharged from steelmaking by a converter smelting method. The main components of converter stone are calcium oxide and iron oxide, and may include oxides of other elements such as silicon, magnesium, aluminum, manganese, etc. After processing, converter stone can be used as filler for cement, paint, asphalt, paint, etc. However, the converter stone used as a filler has problems such as being easily swelled by water absorption, resulting in breakage and pulverization, and the mechanical properties and high temperature resistance also need to be improved.
本揭露提供一種硫酸廢液與含鈣副產物的處理方法，其能夠一併處理硫酸廢液與含鈣副產物，並能夠產出具有強化機械性質與良好高溫特性的含鈣填料。The present disclosure provides a method for treating sulfuric acid waste liquid and calcium-containing by-products, which can treat sulfuric acid waste liquid and calcium-containing by-products together, and can produce calcium-containing fillers with enhanced mechanical properties and good high temperature characteristics.
根據本揭露的一些實施例，硫酸廢液與含鈣副產物的處理方法包括：進行混合步驟，以混合硫酸廢液與含鈣副產物，其中所述硫酸廢液包括硫酸，所述含鈣副產物包括氧化鈣，且所述硫酸與所述氧化鈣在所述混合步驟期間反應生成硫酸鈣固體；對所述硫酸廢液與所述含鈣副產物的混合液進行固液分離步驟，以分離出包括所述硫酸鈣固體的第一固態產物；以及進行水熱法長晶步驟，而藉由水熱法使所述硫酸鈣固體進行長晶，以形成硫酸鈣晶鬚。According to some embodiments of the present disclosure, a method for treating waste sulfuric acid and calcium-containing by-products includes: performing a mixing step to mix sulfuric acid waste liquid and calcium-containing by-products, wherein the sulfuric acid waste liquid includes sulfuric acid, and the calcium-containing by-product The product includes calcium oxide, and the sulfuric acid and the calcium oxide react to form calcium sulfate solid during the mixing step; the solid-liquid separation step is performed on the mixed liquid of the sulfuric acid waste liquid and the calcium-containing by-product to separate producing a first solid product including the calcium sulfate solid; and performing a hydrothermal crystallization step, and the calcium sulfate solid is crystallized by the hydrothermal method to form calcium sulfate whiskers.
在一些實施例中，所述硫酸廢液更包括過氧化氫。In some embodiments, the sulfuric acid waste liquid further includes hydrogen peroxide.
在一些實施例中，所述氧化鈣在所述混合步驟期間與所述過氧化氫反應生成氫氧化鈣，且所述氫氧化鈣在所述混合步驟期間與所述硫酸反應生成所述硫酸鈣固體。In some embodiments, the calcium oxide reacts with the hydrogen peroxide during the mixing step to form calcium hydroxide, and the calcium hydroxide reacts with the sulfuric acid during the mixing step to form the calcium sulfate solid.
在一些實施例中，所述含鈣副產物更包括氧化鐵。In some embodiments, the calcium-containing by-product further comprises iron oxide.
在一些實施例中，所述氧化鐵在所述混合步驟期間與所述硫酸反應生成硫酸鐵溶液。In some embodiments, the iron oxide reacts with the sulfuric acid during the mixing step to form an iron sulfate solution.
在一些實施例中，所述固液分離步驟更分離出包括所述硫酸鐵溶液的第一液態產物。In some embodiments, the solid-liquid separation step further separates a first liquid product comprising the ferric sulfate solution.
在一些實施例中，在所述固液分離步驟之後且在所述水熱法長晶步驟之前，更包括：進行水洗純化步驟，以對所述第一固態產物進行水洗。In some embodiments, after the solid-liquid separation step and before the hydrothermal crystallization step, further comprising: performing a water washing and purification step to wash the first solid product with water.
在一些實施例中，在所述水洗純化步驟之後且在所述水熱法長晶步驟之前，更包括：進行額外固液分離步驟，以將所述水洗純化步驟得到的混合液分離出包括所述硫酸鈣固體的第二固態產物以及包括水的第二液態產物。In some embodiments, after the water washing and purifying step and before the hydrothermal crystallization step, further comprising: performing an additional solid-liquid separation step, so as to separate the mixed solution obtained in the water washing and purification step into the A second solid product of the calcium sulfate solid and a second liquid product comprising water.
在一些實施例中，所述第二液態產物更包括硫酸鐵溶液。In some embodiments, the second liquid product further comprises a ferric sulfate solution.
在一些實施例中，更包括：對所述第一液態產物與所述第二液態產物的混合液進行提濃步驟，以至少部分地去除包括所述第一液態產物與所述第二液態產物的所述混合液中的水。In some embodiments, the method further includes: performing a concentration step on the mixed solution of the first liquid product and the second liquid product, so as to at least partially remove the mixture including the first liquid product and the second liquid product of the water in the mixture.
基於上述，本揭露的硫酸廢液與轉爐石的處理流程能夠一併處理硫酸廢液與轉爐石。不但如此，更可將硫酸廢液與轉爐石轉變為具有高經濟價值的塗層填料以及工業廢水的絮凝劑。特別來說，此塗層填料包括硫酸鈣晶鬚。相較於含有氧化鈣的轉爐石，硫酸鈣晶鬚不易與水汽反應，故不易產生吸水膨脹而造成破損、粉化等問題。因此，可延長塗層的使用壽命。再者，基於硫酸鈣晶鬚錯綜排列而形成網狀結構，可大幅加強塗層的機械強度。除此之外，相較於顆粒狀的硫酸鈣晶體，硫酸鈣晶鬚的一維形狀使得其比表面積（specific surface area）大幅降低。因此，相較於顆粒狀的硫酸鈣晶體，硫酸鈣晶鬚可具有更高的熔點。據此，硫酸鈣晶鬚可具有較佳的熱穩定性以及防火性。Based on the above, the processing flow of the sulfuric acid waste liquid and the converter stone of the present disclosure can treat the sulfuric acid waste liquid and the converter stone together. Not only that, it can also convert sulfuric acid waste liquid and converter stone into coating fillers with high economic value and flocculants for industrial wastewater. In particular, the coating filler includes calcium sulfate whiskers. Compared with the converter stone containing calcium oxide, the calcium sulfate whisker is not easy to react with water vapor, so it is not easy to cause problems such as damage and pulverization due to water absorption and expansion. Therefore, the service life of the coating can be extended. Furthermore, the network structure formed by the intricate arrangement of calcium sulfate whiskers can greatly enhance the mechanical strength of the coating. In addition, the one-dimensional shape of calcium sulfate whiskers results in a significantly lower specific surface area compared to granular calcium sulfate crystals. Therefore, calcium sulfate whiskers may have a higher melting point than granular calcium sulfate crystals. Accordingly, the calcium sulfate whiskers can have better thermal stability and fire resistance.
圖1是依照本揭露一些實施例的硫酸廢液與含鈣副產物的處理方法的流程圖。以下將以轉爐石作為含鈣副產物的範例來說明上述處理方法的各個步驟。FIG. 1 is a flow chart of a method for treating sulfuric acid waste liquid and calcium-containing by-products according to some embodiments of the present disclosure. Hereinafter, each step of the above-mentioned treatment method will be explained by taking converter stone as an example of calcium-containing by-product.
請參照圖1，進行步驟S100，以提供轉爐石。轉爐石為生產鋼鐵之鐵礦原料所含有的黏土雜質與石灰石助熔劑在高溫熔爐中反應所產生的熔渣。具體而言，一般煉鋼製程所產出的爐石可包括高爐石（blast furnace slag）與轉爐石（basic oxygen furnace slag）。由高爐產生的鐵水運送至轉爐，以進行轉爐吹煉。藉由轉爐吹煉形成鋼液時，須加入石灰石等助熔劑，以去除鐵水中的雜質。此過程中的熱熔渣經冷卻後形成轉爐石。轉爐石的主要成分為氧化鈣與氧化鐵，且可包括其他例如是矽、鎂、鋁、錳等元素的氧化物。在一些實施例中，可先將塊狀的轉爐石敲碎至顆粒狀，之後進行粗篩與研磨，而得到轉爐石粉。在其他實施例中，也可使用顆粒狀的轉爐石進行後續處理步驟。Referring to FIG. 1 , step S100 is performed to provide converter stones. Converter stone is the slag produced by the reaction of clay impurities contained in iron ore raw materials for steel production and limestone flux in a high-temperature furnace. Specifically, the hearthstones produced by the general steelmaking process can include blast furnace slag and basic oxygen furnace slag. The molten iron produced by the blast furnace is transported to the converter for converter blowing. When molten steel is formed by converter blowing, fluxes such as limestone must be added to remove impurities in molten iron. The hot molten slag in this process is cooled to form converter stones. The main components of converter stone are calcium oxide and iron oxide, and may include oxides of other elements such as silicon, magnesium, aluminum, manganese, etc. In some embodiments, the massive converter stone may be crushed into particles first, and then coarsely screened and ground to obtain converter stone powder. In other embodiments, granular converter stones may also be used for subsequent processing steps.
進行步驟S102，以提供硫酸廢液。在一些實施例中，硫酸廢液為晶圓製造過程中所產生的硫酸廢液。在晶圓製造過程中，硫酸可被運用於晶圓清洗。在此些實施例中，硫酸廢液含有硫酸以及過氧化氫，且可能包括微量的其他金屬與酸根離子。舉例而言，硫酸廢液中的硫酸佔約50 wt%；過氧化氫佔約4 wt%；其他金屬與酸根離子約佔0.1 wt%。Step S102 is performed to provide sulfuric acid waste liquid. In some embodiments, the sulfuric acid waste liquid is the sulfuric acid waste liquid generated during the wafer fabrication process. During wafer fabrication, sulfuric acid can be used for wafer cleaning. In these embodiments, the sulfuric acid waste contains sulfuric acid and hydrogen peroxide, and may include traces of other metals and acid ions. For example, sulfuric acid in the sulfuric acid waste liquid accounts for about 50 wt%; hydrogen peroxide accounts for about 4 wt%; other metals and acid ions account for about 0.1 wt%.
隨後，進行步驟S104，以混合轉爐石與硫酸廢液。在一些實施例中，可在常溫常壓下於攪拌器中進行攪拌。如式（1）所示，硫酸廢液中的硫酸會與轉爐石中的氧化鈣反應，而生成硫酸鈣與水。硫酸鈣在常溫常壓下幾乎不溶於水。舉例而言，在攝氏20度、1大氣壓下，硫酸鈣在水中的溶解度約為0.24 g/100 mL。 CaO (s)+ H 2SO 4(aq)→ CaSO 4(s)+ H 2O (l)（1） Then, step S104 is performed to mix the converter stone and the sulfuric acid waste liquid. In some embodiments, stirring can be performed in a mixer at normal temperature and pressure. As shown in formula (1), the sulfuric acid in the sulfuric acid waste liquid will react with the calcium oxide in the converter stone to generate calcium sulfate and water. Calcium sulfate is almost insoluble in water at normal temperature and pressure. For example, at 20°C and 1 atmosphere, the solubility of calcium sulfate in water is approximately 0.24 g/100 mL. CaO (s) + H 2 SO 4(aq) → CaSO 4(s) + H 2 O (l) (1)
如式（2）所示，在硫酸廢液中含有過氧化氫的實施例中，硫酸廢液中的過氧化氫可能會與轉爐石中的氧化鈣反應而生成固態的氫氧化鈣。如式（3）所示，氫氧化鈣可與硫酸反應生成硫酸鈣與水。在此些實施例中，基於過氧化氫作為強氧化劑的作用，可顯著地加速由氧化鈣轉變為硫酸鈣的反應速度。 2CaO (s)+ 2H 2O 2(aq)→ 2Ca(OH) 2(s)+ O 2(g)（2） Ca(OH) 2(s)+ H 2SO 4(aq)→ CaSO 4(s)+ 2H 2O (l)（3） As shown in formula (2), in the embodiment in which the sulfuric acid waste liquid contains hydrogen peroxide, the hydrogen peroxide in the sulfuric acid waste liquid may react with calcium oxide in the converter stone to generate solid calcium hydroxide. As shown in formula (3), calcium hydroxide can react with sulfuric acid to form calcium sulfate and water. In these embodiments, the reaction rate of the conversion from calcium oxide to calcium sulfate can be significantly accelerated based on the role of hydrogen peroxide as a strong oxidant. 2CaO (s) + 2H 2 O 2(aq) → 2Ca(OH) 2(s) + O 2(g) (2) Ca(OH) 2(s) + H 2 SO 4(aq) → CaSO 4( s) + 2H 2 O (l) (3)
另一方面，如式（4）所示，硫酸廢液中的硫酸會與轉爐石中的氧化鐵反應，而生成硫酸鐵與水。在常溫常壓下，硫酸鐵可溶於水，故以水溶液的型態作為反應生成物。 Fe 2O 3(s)+ 3H 2SO 4(aq)→ Fe 2(SO 4) 3(aq)+ 3H 2O (l)（4） On the other hand, as shown in formula (4), the sulfuric acid in the sulfuric acid waste liquid reacts with the iron oxide in the converter stone to generate iron sulfate and water. At normal temperature and pressure, ferric sulfate is soluble in water, so the form of an aqueous solution is used as the reaction product. Fe 2 O 3(s) + 3H 2 SO 4(aq) → Fe 2 (SO 4 ) 3(aq) + 3H 2 O (l) (4)
在硫酸廢液中含有過氧化氫的實施例中，硫酸廢液中的過氧化氫會加速與轉爐石中的氧化鐵之反應，而生成溶於水的硫酸鐵。在此些實施例中，基於過氧化氫作為強氧化劑的作用，可顯著地加速由氧化鐵轉變為硫酸鐵的反應速度。In the embodiment in which the sulfuric acid waste liquid contains hydrogen peroxide, the hydrogen peroxide in the sulfuric acid waste liquid will accelerate the reaction with the iron oxide in the converter stone to generate water-soluble iron sulfate. In these embodiments, the reaction rate of conversion from iron oxide to iron sulfate can be significantly accelerated based on the role of hydrogen peroxide as a strong oxidant.
進行步驟S106，以對混合液進行固液分離。前一步驟所形成的包括硫酸鈣固體與硫酸鐵溶液的混合液可在此步驟中進行固液分離。在一些實施例中，藉由離心分離法、板框過濾法或其類似者對上述的混合液進行固液分離。所分離出的固態產物SL可包括硫酸鈣，而所分離出的液態產物AQ可包括硫酸鐵溶液。在一些實施例中，分離出的固態產物SL更可包括轉爐石中未與硫酸反應的固態雜質，例如是包括矽、鋁、鎂、錳或其氧化物。Step S106 is performed to perform solid-liquid separation on the mixed liquid. The mixed solution including calcium sulfate solid and ferric sulfate solution formed in the previous step can be subjected to solid-liquid separation in this step. In some embodiments, the solid-liquid separation of the above-mentioned mixed liquid is performed by centrifugation, plate and frame filtration, or the like. The separated solid product SL may include calcium sulfate, and the separated liquid product AQ may include a ferric sulfate solution. In some embodiments, the separated solid product SL may further include solid impurities not reacted with sulfuric acid in the converter stone, such as silicon, aluminum, magnesium, manganese or oxides thereof.
進行步驟S108，以對於前一步驟所分離出的固態產物SL進行水洗純化。如上所述，前一步驟（亦即步驟S106）所分離出的固態產物SL主要包括硫酸鈣。然而，此些固態產物SL更可能附著有一些硫酸鐵溶液。在當前步驟（亦即步驟S108）中，以水洗製程將可能附著於這些固態產物SL上的硫酸鐵溶液洗除。如此一來，可純化此些主要包括硫酸鈣的固態產物SL。Step S108 is performed to wash and purify the solid product SL separated in the previous step. As mentioned above, the solid product SL separated in the previous step (ie, step S106 ) mainly includes calcium sulfate. However, these solid products SL are more likely to have some ferric sulfate solution attached. In the current step (ie, step S108 ), the ferric sulfate solution possibly adhering to the solid products SL is washed away by a water washing process. In this way, these solid products SL, which mainly comprise calcium sulfate, can be purified.
進行步驟S110，以再次進行固液分離。前一步驟（亦即步驟S108）將水與固態產物SL混合，以使可能附著於固態產物SL上的硫酸鐵溶液溶於水中。在當前步驟中（亦即步驟S110），將可能含有硫酸鐵的水溶液與前述的固態產物SL分離，以得到液態產物AQ與固態產物SL。需注意的是，此步驟（亦即步驟S110）分離出的液態產物AQ的硫酸鐵濃度可能低於步驟S106所分離出的液態產物AQ的硫酸鐵濃度。然而，以簡潔起見，兩步驟所得的液態產物均標示為液態產物AQ。在一些實施例中，藉由離心分離法、板框過濾法或其類似者進行固液分離處理。Step S110 is performed to perform solid-liquid separation again. The previous step (ie, step S108 ) mixes water with the solid product SL, so that the iron sulfate solution that may be attached to the solid product SL is dissolved in the water. In the current step (ie, step S110 ), the aqueous solution possibly containing ferric sulfate is separated from the aforementioned solid product SL to obtain a liquid product AQ and a solid product SL. It should be noted that the ferric sulfate concentration of the liquid product AQ separated in this step (ie, step S110 ) may be lower than the ferric sulfate concentration of the liquid product AQ separated in step S106 . However, for the sake of brevity, the liquid product obtained in both steps is designated as liquid product AQ. In some embodiments, the solid-liquid separation process is performed by centrifugation, plate and frame filtration, or the like.
選擇性地進行步驟S112，以對於經水洗純化的固態產物SL進行材料分析。材料分析可包括成分分析以及結晶相分析。在一些實施例中，成分分析的方法包括X光螢光（X-ray fluorescence，XRF）分析以及感應耦合電漿質譜儀（inductively coupled plasma optical emission spectrometry，ICP-OES）分析。藉由進行成分分析，可確認附著於這些固態產物SL上的包含硫酸鐵的溶液是否低於預設標準。若是，則可對這些固態產物SL進行後續步驟。若否，則可再次進行步驟S108的水洗純化處理以及步驟S110的固液分離處理。另一方面，結晶相分析可例如是X光繞射（X-ray diffraction，XRD）分析。藉由進行此結晶相分析，可取得上述固態產物SL進行後續的長晶處理之前的起始結晶狀態。Step S112 is selectively performed to perform material analysis on the solid product SL purified by water washing. Material analysis may include compositional analysis as well as crystalline phase analysis. In some embodiments, the method of compositional analysis includes X-ray fluorescence (XRF) analysis and inductively coupled plasma optical emission spectrometry (ICP-OES) analysis. By performing composition analysis, it can be confirmed whether or not the iron sulfate-containing solution attached to these solid products SL is lower than a predetermined standard. If so, subsequent steps can be performed on these solid products SL. If not, the water washing purification process in step S108 and the solid-liquid separation process in step S110 can be performed again. On the other hand, the crystalline phase analysis may be, for example, X-ray diffraction (XRD) analysis. By carrying out this crystalline phase analysis, the initial crystalline state of the above-mentioned solid product SL before the subsequent crystallization treatment can be obtained.
進行步驟S114，以使經水洗純化的固態產物SL進行長晶。具體而言，固態產物SL中原本可能是顆粒狀或塊狀的硫酸鈣可在當前步驟中成長為硫酸鈣晶鬚WH。在一些實施例中，以水熱法進行硫酸鈣的長晶處理。在此些實施例中，上述的固態產物SL經加水後輸入至蒸汽反應釜中，以使固態產物SL中的硫酸鈣在高溫高壓環境下進行長晶。舉例而言，長晶條件可控制在約攝氏90度至約攝氏130度的範圍中，而長晶的壓力可控制在約0.1 MPa至約0.3 MPa的範圍中。在高溫高壓環境下，可迫使硫酸鈣溶於水，且結晶析出為晶體。除此之外，可將助長劑與催化劑加入蒸汽反應釜中。助長劑在水中可溶解出離子，且因此會基於同離子效應而提高硫酸鈣在水中的溶解度。再者，此些離子可能會附著於硫酸鈣晶核周圍，進而增大晶核在特定方向上的表面能，而使硫酸鈣晶體能夠單向生長而形成晶鬚。舉例而言，助長劑可包括硫酸鈉溶液與氧化鈣溶液，且更可包括氯化鎂溶液、氯化銨溶液、硫酸銅溶液或硫酸錳溶液。另一方面，催化劑可促進硫酸根離子與鈣離子在硫酸鈣晶核上結晶。舉例而言，催化劑可包括亞氯酸鈉溶液或過錳酸鉀溶液。再者，蒸汽反應釜更可連通於加酸管路。加酸管路經配置以將酸性溶液加入至蒸汽反應釜中，以調整蒸汽反應釜中的pH值。在一些實施例中，蒸汽反應釜中的pH值經控制在約3至4的範圍中。在形成硫酸鈣晶鬚WH之後，可進行脫水處理，而將硫酸鈣晶鬚WH分離出來。Step S114 is performed to crystallize the solid product SL purified by water washing. Specifically, calcium sulfate in the solid product SL, which may have been granular or agglomerated, can grow into calcium sulfate whiskers WH in the current step. In some embodiments, the crystal growth of calcium sulfate is performed hydrothermally. In these embodiments, the above-mentioned solid product SL is fed into a steam reactor after adding water, so that calcium sulfate in the solid product SL is crystallized under a high temperature and high pressure environment. For example, the crystal growth conditions may be controlled in the range of about 90 degrees Celsius to about 130 degrees Celsius, and the crystal growth pressure may be controlled in the range of about 0.1 MPa to about 0.3 MPa. In the high temperature and high pressure environment, calcium sulfate can be forced to dissolve in water, and crystallize out into crystals. In addition, promoters and catalysts can be added to the steam reactor. Promoters can dissolve ions in water and thus increase the solubility of calcium sulfate in water based on the same ion effect. Furthermore, these ions may be attached around the calcium sulfate crystal nucleus, thereby increasing the surface energy of the crystal nucleus in a specific direction, so that the calcium sulfate crystal can grow unidirectionally to form whiskers. For example, the promoter can include sodium sulfate solution and calcium oxide solution, and more can include magnesium chloride solution, ammonium chloride solution, copper sulfate solution or manganese sulfate solution. On the other hand, the catalyst can promote the crystallization of sulfate ions and calcium ions on calcium sulfate nuclei. For example, the catalyst may include sodium chlorite solution or potassium permanganate solution. Furthermore, the steam reactor can be connected to the acid adding pipeline. The acid addition line is configured to add the acidic solution to the steam reactor to adjust the pH in the steam reactor. In some embodiments, the pH in the steam reactor is controlled in the range of about 3 to 4. After the calcium sulfate whiskers WH are formed, dehydration treatment may be performed to separate the calcium sulfate whiskers WH.
圖2示出硫酸鈣晶鬚WH的掃描式電子顯微鏡影像。Figure 2 shows a scanning electron microscope image of calcium sulfate whiskers WH.
請參照圖2，硫酸鈣晶體大致上朝單一方向生長，而形成硫酸鈣晶鬚WH。此外，多條沿不同方向生長的硫酸鈣晶鬚WH可錯綜堆疊而形成網狀結構。在一些實施例中，硫酸鈣晶鬚WH的直徑約1 μm至2 μm，長度可達到約100 mm。相似於轉爐石的應用，硫酸鈣晶鬚WH也可應用於水泥、塗料、瀝青、油漆等的填料。相較於含有氧化鈣的轉爐石，硫酸鈣不易與水汽反應，故不易產生吸水膨脹而造成破損、粉化等問題。因此，可延長塗層的使用壽命。再者，基於硫酸鈣晶鬚WH錯綜排列而形成網狀結構，可大幅加強塗層的機械強度。除此之外，相較於顆粒狀的硫酸鈣晶體，硫酸鈣晶鬚WH的一維形狀使得其比表面積（specific surface area）大幅降低。因此，相較於顆粒狀的硫酸鈣晶體，硫酸鈣晶鬚WH可具有更高的熔點。據此，硫酸鈣晶鬚可具有較佳的熱穩定性以及防火性。舉例而言，顆粒狀的硫酸鈣晶體的熔點約為攝氏1200度，而硫酸鈣晶鬚WH的熔點可達約攝氏1450度。此外，作為測試，硫酸鈣晶鬚WH在攝氏1800度下兩小時僅失重0.75%。Referring to FIG. 2 , calcium sulfate crystals generally grow in a single direction to form calcium sulfate whiskers WH. In addition, a plurality of calcium sulfate whiskers WH growing in different directions can be intricately stacked to form a network structure. In some embodiments, the calcium sulfate whiskers WH are about 1 μm to 2 μm in diameter and may be up to about 100 mm in length. Similar to the application of converter stone, calcium sulfate whiskers WH can also be used as fillers for cement, paint, asphalt, paint, etc. Compared with the converter stone containing calcium oxide, calcium sulfate is not easy to react with water vapor, so it is not easy to cause water expansion and cause damage, pulverization and other problems. Therefore, the service life of the coating can be extended. Furthermore, the network structure formed by the intricate arrangement of the calcium sulfate whiskers WH can greatly enhance the mechanical strength of the coating. Besides, the one-dimensional shape of the calcium sulfate whiskers WH greatly reduces its specific surface area compared to the granular calcium sulfate crystals. Therefore, calcium sulfate whiskers WH may have a higher melting point than granular calcium sulfate crystals. Accordingly, the calcium sulfate whiskers can have better thermal stability and fire resistance. For example, the melting point of granular calcium sulfate crystals is about 1200 degrees Celsius, and the melting point of calcium sulfate whiskers WH can reach about 1450 degrees Celsius. In addition, as a test, the calcium sulfate whisker WH lost only 0.75% of its weight at 1800 degrees Celsius for two hours.
另一方面，進行步驟S116，以對於步驟S106與步驟S110的固液分離處理所得到的液態產物AQ進行提濃處理。在當前步驟（亦即步驟S116）中，去除液態產物AQ中的水，以提高硫酸鐵的濃度。在一些實施例中，藉由蒸發器或多效蒸發管來進行提濃處理（亦即除水處理）。經提濃的液態產物AQ具有相對高濃度的硫酸鐵溶液，且可作為處理工業鹼性廢水的絮凝劑。On the other hand, step S116 is performed to perform concentration processing on the liquid product AQ obtained by the solid-liquid separation processing in steps S106 and S110. In the current step (ie, step S116 ), the water in the liquid product AQ is removed to increase the concentration of ferric sulfate. In some embodiments, the concentration treatment (ie, water removal treatment) is performed by an evaporator or a multi-effect evaporator. The concentrated liquid product AQ has a relatively high concentration of ferric sulfate solution, and can be used as a flocculant for the treatment of industrial alkaline wastewater.
在一些實施例中，在進行步驟S116之前，可選擇性地進行步驟S118，以對即將進行提濃處理的液態產物AQ進行檢測。在一些實施例中，檢測可包括pH值檢測與成分分析。pH值檢測可能是為了確認液態產物AQ是否符合絮凝劑的需求。另外，成分分析可用於檢測液態產物AQ中的硫酸鐵的濃度。在一些實施例中，成分分析的方法包括感應耦合電漿質譜儀（inductively coupled plasma optical emission spectrometry，ICP-OES）分析。In some embodiments, before step S116 is performed, step S118 may be selectively performed to detect the liquid product AQ to be subjected to the concentration treatment. In some embodiments, detection may include pH detection and compositional analysis. The pH value test may be to confirm whether the liquid product AQ meets the needs of the flocculant. In addition, compositional analysis can be used to detect the concentration of ferric sulfate in the liquid product AQ. In some embodiments, the method of compositional analysis includes inductively coupled plasma optical emission spectrometry (ICP-OES) analysis.
至此，已完成根據一些實施例的硫酸廢液與轉爐石的處理流程，其能夠一併處理硫酸廢液與轉爐石。不但如此，更可將硫酸廢液與轉爐石轉變為具有高經濟價值的塗層填料以及工業廢水的絮凝劑。特別來說，此塗層填料包括硫酸鈣晶鬚。相較於含有氧化鈣的轉爐石，硫酸鈣晶鬚不易與水汽反應，故不易產生吸水膨脹而造成破損、粉化等問題。因此，可延長塗層的使用壽命。再者，基於硫酸鈣晶鬚錯綜排列而形成網狀結構，可大幅加強塗層的機械強度。除此之外，相較於顆粒狀的硫酸鈣晶體，硫酸鈣晶鬚的一維形狀使得其比表面積（specific surface area）大幅降低。因此，相較於顆粒狀的硫酸鈣晶體，硫酸鈣晶鬚可具有更高的熔點。據此，硫酸鈣晶鬚可具有較佳的熱穩定性以及防火性。So far, the treatment process of sulfuric acid waste liquid and converter stone according to some embodiments has been completed, which can treat sulfuric acid waste liquid and converter stone together. Not only that, it can also convert sulfuric acid waste liquid and converter stone into coating fillers with high economic value and flocculants for industrial wastewater. In particular, the coating filler includes calcium sulfate whiskers. Compared with the converter stone containing calcium oxide, the calcium sulfate whisker is not easy to react with water vapor, so it is not easy to cause problems such as damage and pulverization due to water absorption and expansion. Therefore, the service life of the coating can be extended. Furthermore, the network structure formed by the intricate arrangement of calcium sulfate whiskers can greatly enhance the mechanical strength of the coating. In addition, the one-dimensional shape of calcium sulfate whiskers results in a significantly lower specific surface area compared to granular calcium sulfate crystals. Therefore, calcium sulfate whiskers may have a higher melting point than granular calcium sulfate crystals. Accordingly, the calcium sulfate whiskers can have better thermal stability and fire resistance.
在其他含鈣副產物並非為轉爐石的實施例中，含鈣副產物可能包括氧化鈣而並未包括氧化鐵。在此些實施例中，可省略與氧化鐵有關的步驟（例如是包括步驟S116與步驟S118），或者對應於含鈣副產物的原料而將上述步驟更改為其他步驟。In other embodiments where the calcium-containing by-product is not a converter stone, the calcium-containing by-product may include calcium oxide but not iron oxide. In these embodiments, the steps related to iron oxide (for example, including steps S116 and S118 ) may be omitted, or the above steps may be changed to other steps corresponding to the calcium-containing by-product raw material.
AQ:液態產物 SL:固態產物 S100、S102、S104、S106、S108、S110、S112、S114、S116、S118:步驟 WH:硫酸鈣晶鬚 AQ: liquid product SL: solid product S100, S102, S104, S106, S108, S110, S112, S114, S116, S118: Steps WH: calcium sulfate whiskers
圖1是依照本揭露一些實施例的硫酸廢液與含鈣副產物的處理方法的流程圖。 圖2示出硫酸鈣晶鬚的掃描式電子顯微鏡影像。 FIG. 1 is a flow chart of a method for treating sulfuric acid waste liquid and calcium-containing by-products according to some embodiments of the present disclosure. Figure 2 shows a scanning electron microscope image of calcium sulfate whiskers.
AQ:液態產物 AQ: liquid product
SL:固態產物 SL: solid product
S100、S102、S104、S106、S108、S110、S112、S114、S116、S118:步驟 S100, S102, S104, S106, S108, S110, S112, S114, S116, S118: Steps
WH:硫酸鈣晶鬚 WH: calcium sulfate whiskers
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