TW201341313A - Recovery method for hydrofluoric acid waste liquid - Google Patents
Recovery method for hydrofluoric acid waste liquid Download PDFInfo
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本發明係一種回收方法，尤指一種在工業製程時回收所產生的氫氟酸廢液之方法。
The invention is a recycling method, in particular a method for recovering a hydrofluoric acid waste liquid produced in an industrial process.
氫氟酸（HF）常被用來當作半導體製程蝕刻及清洗的溶劑，其本身具有極毒性及強腐蝕性，在室溫下為無色略帶刺激味的液體，加上氫氟酸對皮膚刺激性弱，因此常導致患者不自覺中毒，一般中毒原因皆因工作上意外暴露所致。另外，由於氫氟酸的除銹功能良好，且刺激性較鹽酸、硫酸為低；因此氫氟酸也常被應用於家庭或一般的清潔除銹用途。
而其使用後所形成的廢液目前最普遍的處理方式為添加氫氧化鈣（Ca(OH)2）或氯化鈣（CaCl2）等鈣鹽，形成氟化鈣（CaF2）沉澱。然而，處理後所形成之氟化鈣汙泥的回收再利用價值非常低，大部分被視為一般廢棄物處理。因此，若所處理之氫氟酸廢液濃度較高、容量較大，則將會生成大量的氟化鈣汙泥，成為清運處理時的一大負擔，也不環保。
對於氫氟酸廢液的處理，國內外尚有其他方式，試圖將廢液以較具再利用價值的方式做回收，例如添加矽藻土或非結晶型二氧化矽，形成氟矽酸（H2SiF6）後，再將該氟矽酸加入鈉鹽，形成氟矽酸鈉（Na2SiF6）回收。
6HF + SiO2→ H2SiF6+ 2H2O （式一）
H2SiF6+ 2Na+→ Na2SiF6+ 2H+（式二）
氟矽酸鈉目前是一種矽晶製程的主要原料，以氟矽酸鈉為原料之下，所產生的矽晶可進一步製成多晶矽，已被廣為用於半導體、光電產業、平面顯示器與太陽能電池的製造。太陽能電池產業就曾面臨多晶矽短缺問題；目前市場上以氟矽酸鈉為主要的多晶矽製造原料之供應商包括矽旭綠能公司、元晶能源科技、山陽科技、旭晶能源科技等。
然而，於過去將氫氟酸回收為氟矽酸鈉的製程中，其需要設置兩個反應槽。以投入非結晶型二氧化矽為例，於第一反應槽投入非結晶型二氧化矽而得到氟矽酸後，再將之注入第二反應槽，接著投入氟化鈉以形成氟矽酸鈉。每一道步驟皆要透過適當的控制才能讓反應完成，是為一種需要大量資金投入設備及人力的回收方法。且不僅如此，在此方法中，第一反應槽需要一段數小時的時間來溶解二氧化矽，因此需要足夠的容積來提供反應時間；第二反應槽也僅能除去一部分的氫氟酸，另一部分的氫氟酸則需要進一步靠後續其他方式進行處理。在效率和效益上都不盡理想。
是以，在上述方法皆未能確實達成高效率和高效益處理氫氟酸廢液的環保目標之下，本發明針對先前技術做出改良增進，提供一種氫氟酸廢液之回收方法，並可搭配工業製程，減少氫氟酸廢液的排放，同時也達到節省原物料的效果。
Hydrofluoric acid (HF) is often used as a solvent for etching and cleaning semiconductor processes. It is extremely toxic and highly corrosive. It is a colorless, slightly irritating liquid at room temperature, plus hydrofluoric acid for the skin. The irritating is weak, so often the patient is not consciously poisoned. The general cause of poisoning is caused by accidental exposure at work. In addition, since hydrofluoric acid has a good rust-removing function and is less irritating than hydrochloric acid and sulfuric acid; hydrofluoric acid is also often used for household or general cleaning and descaling purposes.
The most common treatment method for the waste liquid formed after use is to add calcium salt such as calcium hydroxide (Ca(OH) 2 ) or calcium chloride (CaCl 2 ) to form calcium fluoride (CaF 2 ) precipitate. However, the recovery and reuse value of the calcium fluoride sludge formed after the treatment is very low, and most of it is treated as general waste. Therefore, if the concentration of the hydrofluoric acid waste liquid to be treated is high and the capacity is large, a large amount of calcium fluoride sludge will be generated, which becomes a big burden during the transportation and transportation process, and is not environmentally friendly.
For the treatment of hydrofluoric acid waste liquid, there are other ways at home and abroad to try to recycle the waste liquid in a way that is more reusable, such as adding diatomaceous earth or non-crystalline cerium oxide to form fluoroantimonic acid (H). After 2 SiF 6 ), the fluoroantimonic acid was added to the sodium salt to form sodium fluorophthalate (Na 2 SiF 6 ).
6HF + SiO 2 → H 2 SiF 6 + 2H 2 O (Formula 1)
H 2 SiF 6 + 2Na + → Na 2 SiF 6 + 2H + (Formula 2)
Sodium fluoroantimonate is currently the main raw material for the twinning process. With sodium fluoroantimonate as the raw material, the resulting twin crystal can be further made into polycrystalline germanium, which has been widely used in semiconductor, photovoltaic industry, flat panel display and solar energy. Battery manufacturing. The solar cell industry has faced the shortage of polycrystalline germanium; currently, suppliers of raw materials for polycrystalline germanium, which are mainly sodium fluoroantimonate, include Yanxu Green Energy, Yuanjing Energy Technology, Shanyang Technology, and Xujing Energy Technology.
However, in the past process of recovering hydrofluoric acid to sodium fluoroantimonate, it was necessary to provide two reaction tanks. Taking amorphous non-crystalline cerium oxide as an example, the amorphous cerium oxide is introduced into the first reaction tank to obtain fluorononanoic acid, and then injected into the second reaction tank, followed by sodium fluoride to form sodium fluorophthalate. . Every step must be properly controlled to get the reaction done. It is a recycling method that requires a lot of money to invest in equipment and manpower. Moreover, in this method, the first reaction tank requires a period of several hours to dissolve the cerium oxide, so a sufficient volume is required to provide the reaction time; the second reaction tank can only remove a part of the hydrofluoric acid, and the other A portion of the hydrofluoric acid needs to be further processed by other means. Not ideal in terms of efficiency and effectiveness.
Therefore, under the environmental protection goal that the above methods fail to achieve high efficiency and high efficiency in treating hydrofluoric acid waste liquid, the present invention provides an improvement and improvement of the prior art, and provides a method for recovering hydrofluoric acid waste liquid, and It can be combined with industrial processes to reduce the discharge of hydrofluoric acid waste liquid, and at the same time achieve the effect of saving raw materials.
本發明之目的，係提供一種回收氫氟酸廢液之方法，其係以回收取代排放的方式處理副產物氫氟酸，可降低排放處理設備及清運廢棄物的製造成本。
本發明之另一目的，係提供一種回收氫氟酸廢液之方法，其係以投入矽酸鈉（Na2SiO3）與氫氟酸反應，以形成氟矽酸鈉進行回收再利用。
為了達到上述之目的，本發明揭示了一種回收氫氟酸廢液之方法，其步驟包含：經由一進料口注入一氫氟酸廢液於一反應槽；投入一矽酸鈉於該反應槽，並調整該反應槽內溶液pH值為2~4，產生一氟矽酸鈉。
It is an object of the present invention to provide a method for recovering a hydrofluoric acid waste liquid which is a by-product of hydrofluoric acid by means of recovery and discharge, thereby reducing the manufacturing cost of the discharge treatment equipment and the transportation waste.
Another object of the present invention is to provide a method for recovering a waste liquid of hydrofluoric acid by reacting sodium citrate (Na 2 SiO 3 ) with hydrofluoric acid to form sodium fluoroantimonate for recycling.
In order to achieve the above object, the present invention discloses a method for recovering a hydrofluoric acid waste liquid, the method comprising: injecting a hydrofluoric acid waste liquid into a reaction tank through a feed port; and inputting sodium citrate in the reaction tank And adjusting the pH of the solution in the reaction tank to 2 to 4 to produce sodium fluorophthalate.
為使 貴審查委員對本發明之特徵及所達成之功效有更進一步之瞭解與認識，謹佐以較佳之實施例及配合詳細之說明，說明如後：
於先前技術之氫氟酸回收方法，其係設置兩個反應槽做處理，而本發明則在矽酸鈉為添加物之下，僅以一反應槽即達成高效率及高效益的回收成果。
首先，為實施本發明之回收氫氟酸廢液之方法，請參考第一圖，其基本製程架構包含：一進料口1；一反應槽2；一沉澱槽3；一脫水設備4；以及一乾燥設備5。
其中，該進料口1與該反應槽2相連接；該沉澱槽3與該反應槽2相連接；該脫水設備4與該沉澱槽3相連接；而該乾燥設備5，則是與該脫水設備4相連接。此外，上述該些元件之連接係透過化學管線或機械輸送。
而在供反應物進入的管線上，於本發明中，進料口1可供工業界諸如蝕刻等製程所產生的氫氟酸廢液進入，而反應槽2則也具有管線可讓矽酸鈉投入。
在此製程架構之下，本發明之回收氫氟酸廢液之方法，其關鍵步驟為投入矽酸鈉於含氫氟酸廢液之反應槽2，以形成氟矽酸鈉。在投入此添加物之下，反應槽2內的總反應為式三：
Na2SiO3+ 6HF → Na2SiF6+ 3H2O （式三）
於本反應中，在反應槽2所投入的矽酸鈉會與氫氟酸反應，形成氟矽酸鈉及水，也就是獲得了可資利用於例如矽晶生產的有價原料，並且免除了處理氫氟酸廢液所需要的清運費用。
而在總反應式三當中，其包含了五個細部反應，分別為式四至式八：
Na2SiO3+ 2HF + H2O → Si(OH)4+ NaF （式四）
Si(OH)4+ 4HF → SiF4+ 4H2O （式五）
SiF4+ 4H2O → SiO2+ 4HF + 2H2O （式六）
SiO2+ 6HF → H2SiF6+ 2H2O （式七）
H2SiF6+ NaF → Na2SiF6+ 4HF （式八）
由於在本發明之回收氫氟酸廢液之方法的反應過程中，若pH值過高，則式七當中的中間產物氟矽酸將會水解為正矽酸（Si(OH)4），而使氟矽酸鈉的產量降低。因此將反應過程中的酸鹼環境控制在pH值為2~4，特別是pH值為3乃較佳的狀態。同時，為了避免矽酸鈉在投入反應槽2與氫氟酸廢液反應時，因為矽酸鈉在局部性的濃度過高而導致膠態固體狀的偏矽酸（H2SiO3）及矽膠（SiO2）形成，因此較佳的投入模式為先將矽酸鈉處理為極小顆粒的粉體，或是先行溶解，以在粉體或是溶液狀態下達到較佳混合效果，較有利於矽酸鈉與氫氟酸進行反應。
另外，於前述將反應過程中的酸鹼環境控制在pH值為2~4的調整上，由於矽酸鈉溶液為一種鹼液，pH值較高，而氫氟酸為強酸，因此調整pH值的方式為緩慢加入適量之矽酸鈉於反應槽4當中以中和氫氟酸，若鹼量不足以中和至反應槽4中的酸鹼環境達到pH值為3，則以氫氧化鈉或其他鹼調整pH至約3。若反應槽4中的pH值過高，例如達到pH值為6的水準，如前所述，氟矽酸將水解為正矽酸或矽膠，使氟矽酸鈉的產量降低，因此將pH值控制調整為3是較佳的操作，使式三的總反應在30分鐘即可完成。
在本發明可搭配工業界各種會產生氫氟酸廢液的製程之下，該些製程中的副產物氫氟酸可以被順利回收，請參考第二圖，本發明回收氫氟酸廢液之方法的步驟包含：
步驟S10：經由一進料口注入一氫氟酸廢液於一反應槽；
步驟S20：投入一矽酸鈉於該反應槽，並調整該反應槽內溶液pH值為2~4，產生一氟矽酸鈉；
步驟S30：脫水及乾燥該氟矽酸鈉，獲得一氟矽酸鈉回收物
於本發明之回收氫氟酸廢液之方法中，首先係於進料口1將諸多製程中產生的氫氟酸廢液注入反應槽2當中，並且可在注入之前，請參考第三圖，進一步執行一步驟S101：沉澱該氫氟酸廢液於一廢液沉澱槽6。此廢液沉澱槽6係設置於進料口1及反應槽2之間的傳輸路徑上，且具有投入污泥脫水劑聚丙烯醯胺（Polyacrylamide，PAM）的功能，以將氫氟酸廢液中的雜質沉澱，以汙泥的形式分離出，避免被一併注入反應槽2而影響降低反應的效率或是縮短反應槽2的運轉壽命。
待沉澱處理後的氫氟酸廢液注入反應槽2之後，接著，將矽酸鈉投入反應槽2以和當中的氫氟酸進行反應（如式三），並且將反應槽2的酸鹼環境調整為內溶液pH值為2~4，產生氟矽酸鈉。
所得到之氟矽酸鈉，經過脫水設備4與乾燥設備5進行脫水乾燥後，可獲得具經濟價值的氟矽酸鈉回收物，循環使用於相關工業製程。
而除上述步驟之外，在反應槽2產生氟矽酸鈉之後，請參考第四圖，可進一步包含一步驟S201：沉澱濃縮該氟矽酸鈉。此時係透過沉澱槽3將經反應槽2內部反應所得的氟矽酸鈉沉澱物，導入沉澱槽3後進行固液分離的處理，以提高固體物的含量。
於脫水及乾燥過程中，脫水設備4係以機械力去除大部分的含水量，可採用包括帶濾式、壓濾式、離心式等脫水方法，並且可視情況加入適當之混凝劑或助凝劑以提升脫水效果。除此之外，由於反應槽2當中的產物會摻雜一些不純物、未完全反應的氫氟酸，或是未完全反應的中間產物氟矽酸、矽酸及鈉鹽等物質，因此可配和清水淋洗的設計，請參考第五圖，在脫水設備4之後方再設置一淋洗器7，將雜質以清水淋洗的方式去除，以提高氟矽酸鈉的純度。
乾燥設備5則係將脫水後的泥餅狀氟矽酸鈉進一步做乾燥，而乾燥的方式包括迴轉式乾燥機、烘乾機、瞬間乾燥機、震動乾燥機、氣流式乾燥機或是未經脫水進行噴霧乾燥等方法。
另，脫水設備4、乾燥設備5以及淋洗器7所不可避免產生的廢氣或廢水，則循其附屬之管道進一步做處理以及排放。
透過此回收氫氟酸廢液之方法，氫氟酸可以在矽酸鈉的投入下被成功回收，並且回收反應的速度相當快，進而可促使輔助整體矽晶的製造流程達到快速且高效率、節省原物料投入及減少廢棄物排放的目標。
惟以上所述者，僅為本發明之較佳實施例而已，並非用來限定本發明實施之範圍，舉凡依本發明申請專利範圍所述之形狀、構造、特徵及精神所為之均等變化與修飾，均應包括於本發明之申請專利範圍內。
本發明係實為一具有新穎性、進步性及可供產業利用者，應符合我國專利法所規定之專利申請要件無疑，爰依法提出發明專利申請，祈 鈞局早日賜准專利，至感為禱。
In order to provide a better understanding and understanding of the features of the present invention and the efficacies achieved, the preferred embodiments and detailed descriptions are provided as follows:
In the prior art hydrofluoric acid recovery method, two reaction tanks are provided for treatment, and in the present invention, under the action of sodium citrate as an additive, high-efficiency and high-efficiency recovery results are achieved by only one reaction tank.
First, in order to carry out the method for recovering the hydrofluoric acid waste liquid of the present invention, please refer to the first drawing, wherein the basic process architecture comprises: a feed port 1; a reaction tank 2; a sedimentation tank 3; a dewatering device 4; A drying device 5.
Wherein, the feed port 1 is connected to the reaction tank 2; the precipitation tank 3 is connected to the reaction tank 2; the dewatering device 4 is connected to the sedimentation tank 3; and the drying device 5 is dehydrated The devices 4 are connected. In addition, the connections of the above components are transmitted through chemical lines or mechanical means.
In the pipeline for the reactants to enter, in the present invention, the feed port 1 can be used to enter the hydrofluoric acid waste liquid produced by the industrial process such as etching, and the reaction tank 2 also has a pipeline for the sodium citrate. Invest.
Under the process architecture, the method for recovering the hydrofluoric acid waste liquid of the present invention has the key step of introducing sodium citrate into the reaction tank 2 containing the hydrofluoric acid waste liquid to form sodium fluoroantimonate. Under the input of this additive, the total reaction in the reaction tank 2 is Equation 3:
Na 2 SiO 3 + 6HF → Na 2 SiF 6 + 3H 2 O (Formula 3)
In the present reaction, sodium citrate charged in the reaction tank 2 reacts with hydrofluoric acid to form sodium fluoroantimonate and water, that is, a valuable raw material which can be utilized for, for example, twin production, and is free from treatment. The shipping cost required for the hydrofluoric acid waste liquid.
In the total reaction formula 3, it contains five detailed reactions, which are four to eight:
Na 2 SiO 3 + 2HF + H 2 O → Si(OH) 4 + NaF (Formula 4)
Si(OH) 4 + 4HF → SiF 4 + 4H 2 O (Equation 5)
SiF 4 + 4H2O → SiO 2 + 4HF + 2H 2 O (Equation 6)
SiO 2 + 6HF → H 2 SiF 6 + 2H 2 O (Equation 7)
H 2 SiF 6 + NaF → Na 2 SiF 6 + 4HF (Equation 8)
In the reaction process of the method for recovering hydrofluoric acid waste liquid of the present invention, if the pH value is too high, the intermediate product fluoroantimonic acid in the formula VII will be hydrolyzed to n-decanoic acid (Si(OH) 4 ), and The yield of sodium fluorophthalate is lowered. Therefore, the acid-base environment during the reaction is controlled to a pH of 2 to 4, particularly a pH of 3 is preferred. At the same time, in order to avoid the reaction of sodium citrate in the reaction tank 2 and the hydrofluoric acid waste liquid, the sodium citrate is too high in local concentration, resulting in a colloidal solid of bismuthic acid (H 2 SiO 3 ) and tannin (SiO 2 ) is formed, so the preferred mode of input is to first treat sodium citrate as a powder of very small particles, or to dissolve first, in order to achieve better mixing effect in powder or solution state, which is more favorable for 矽Sodium is reacted with hydrofluoric acid.
In addition, in the foregoing, the acid-base environment in the reaction process is controlled at a pH of 2 to 4, since the sodium citrate solution is a lye, the pH is high, and the hydrofluoric acid is a strong acid, so the pH is adjusted. The method is to slowly add an appropriate amount of sodium citrate in the reaction tank 4 to neutralize the hydrofluoric acid. If the amount of the base is insufficient to neutralize to the pH in the acid-base environment in the reaction tank 4, the sodium hydroxide or The other base adjusts the pH to about 3. If the pH in the reaction tank 4 is too high, for example, to a level of pH 6, as described above, the fluoroantimonic acid will be hydrolyzed to n-decanoic acid or tannin, so that the yield of sodium fluorophthalate is lowered, so the pH is lowered. A control adjustment of 3 is a preferred operation, and the total reaction of Formula 3 can be completed in 30 minutes.
In the process of the invention, the hydrofluoric acid as a by-product in the processes can be smoothly recovered under the process of producing various hydrofluoric acid waste liquids in the industry. Please refer to the second figure, the recycling of the hydrofluoric acid waste liquid of the present invention. The steps of the method include:
Step S10: injecting a hydrofluoric acid waste liquid into a reaction tank through a feed port;
Step S20: input sodium citrate in the reaction tank, and adjust the pH of the solution in the reaction tank to 2 to 4 to produce sodium fluorophthalate;
Step S30: dehydrating and drying the sodium fluoroantimonate to obtain a sodium fluorocarbonate recovery product in the method for recovering the hydrofluoric acid waste liquid of the present invention, firstly, the hydrofluoric acid produced in a plurality of processes in the feed port 1 The waste liquid is injected into the reaction tank 2, and before the injection, please refer to the third figure, and further performing a step S101: precipitating the hydrofluoric acid waste liquid in a waste liquid sedimentation tank 6. The waste liquid sedimentation tank 6 is disposed on a transport path between the feed port 1 and the reaction tank 2, and has a function of loading a sludge dehydrating agent, polyacrylamide (PAM), to hydrofluoric acid waste liquid. The impurities in the precipitate are separated in the form of sludge, and are prevented from being injected into the reaction tank 2 together to affect the efficiency of reducing the reaction or shorten the operating life of the reaction tank 2.
After the hydrofluoric acid waste liquid to be precipitated is injected into the reaction tank 2, sodium citrate is then introduced into the reaction tank 2 to react with the hydrofluoric acid therein (as in the third formula), and the acid-base environment of the reaction tank 2 is Adjusted to the internal solution pH value of 2 ~ 4, resulting in sodium fluorophthalate.
The obtained sodium fluoroantimonate is dehydrated and dried by the dehydration device 4 and the drying device 5, and the recovered sodium fluorocarbonate having economic value can be obtained and recycled for use in a related industrial process.
In addition to the above steps, after the sodium fluorophthalate is produced in the reaction tank 2, please refer to the fourth figure, which may further comprise a step S201: precipitating and concentrating the sodium fluoroantimonate. At this time, the sodium fluoroantimonate precipitate obtained by the reaction inside the reaction tank 2 is introduced into the precipitation tank 3 through the precipitation tank 3, and then subjected to solid-liquid separation treatment to increase the solid content.
In the process of dehydration and drying, the dewatering equipment 4 removes most of the water content by mechanical force, and may adopt a dewatering method including a filter type, a pressure filter type, a centrifugal type, and the like, and may optionally add a suitable coagulant or coagulant. To enhance the dehydration effect. In addition, since the product in the reaction tank 2 is doped with some impurities, incompletely reacted hydrofluoric acid, or an incompletely reacted intermediate such as fluoroantimonic acid, citric acid or sodium salt, it can be blended. For the design of clean water rinsing, please refer to the fifth figure. After the dewatering equipment 4, a rinsing device 7 is arranged to remove impurities in the form of water to improve the purity of sodium fluoroantimonate.
The drying device 5 further dries the dehydrated mud cake-like sodium fluoroantimonate, and the drying method includes a rotary dryer, a dryer, an instant dryer, a vibration dryer, a gas flow dryer or not. Dehydration is carried out by a method such as spray drying.
In addition, the exhaust gas or waste water which is inevitably generated by the dewatering device 4, the drying device 5, and the rinser 7 is further processed and discharged according to the attached pipeline.
Through the method of recovering the hydrofluoric acid waste liquid, the hydrofluoric acid can be successfully recovered by the input of sodium citrate, and the recovery reaction speed is relatively fast, thereby facilitating the rapid and high-efficiency manufacturing process of assisting the overall twin crystal. Save on raw materials and reduce waste emissions.
The above is only the preferred embodiment of the present invention, and is not intended to limit the scope of the present invention, and the variations, modifications, and modifications of the shapes, structures, features, and spirits described in the claims of the present invention. All should be included in the scope of the patent application of the present invention.
The invention is a novelty, progressive and available for industrial use, and should meet the requirements of the patent application stipulated in the Patent Law of China, and the invention patent application is filed according to law, and the prayer bureau will grant the patent as soon as possible. prayer.
1．．．進料口1. . . Inlet
2．．．反應槽2. . . Reaction tank
3．．．沉澱槽3. . . Precipitation tank
4．．．脫水設備4. . . Dewatering equipment
5．．．乾燥設備5. . . Drying equipment
6．．．廢液沉澱槽6. . . Waste liquid sedimentation tank
7．．．淋洗器7. . . Rinse
第一圖：其係為本發明之一較佳實施例之製程架構圖；
第二圖：其係為本發明之一較佳實施例之流程示意圖；
第三圖：其係為本發明之一較佳實施例之流程示意圖；
第四圖：其係為本發明之一較佳實施例之流程示意圖；及
第五圖：其係為本發明之一較佳實施例之製程架構圖。
The first figure is a process architecture diagram of a preferred embodiment of the present invention;
Second: it is a schematic flow chart of a preferred embodiment of the present invention;
Third: it is a schematic flowchart of a preferred embodiment of the present invention;
FIG. 4 is a schematic flow chart of a preferred embodiment of the present invention; and FIG. 5 is a process architecture diagram of a preferred embodiment of the present invention.
無
no
Claims (5)
經由一進料口注入一氫氟酸廢液於一反應槽；
投入一矽酸鈉於該反應槽，並調整該反應槽內溶液pH值為2~4，產生一氟矽酸鈉。A method for recovering a hydrofluoric acid waste liquid, the steps comprising:
Injecting a hydrofluoric acid waste liquid into a reaction tank through a feed port;
Sodium citrate is added to the reaction tank, and the pH of the solution in the reaction tank is adjusted to 2 to 4 to produce sodium fluorocarbonate.
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|---|---|---|---|
| TW101113160A TW201341313A (en) | 2012-04-13 | 2012-04-13 | Recovery method for hydrofluoric acid waste liquid |
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| Application Number | Priority Date | Filing Date | Title |
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| TW101113160A TW201341313A (en) | 2012-04-13 | 2012-04-13 | Recovery method for hydrofluoric acid waste liquid |
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| TW201341313A true TW201341313A (en) | 2013-10-16 |
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| TW (1) | TW201341313A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105951102A (en) * | 2016-05-13 | 2016-09-21 | 巫协森 | Method for reclamation of waste acid in hydrofluoric acid etching process |
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2012
- 2012-04-13 TW TW101113160A patent/TW201341313A/en unknown
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105951102A (en) * | 2016-05-13 | 2016-09-21 | 巫协森 | Method for reclamation of waste acid in hydrofluoric acid etching process |
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