TW201305064A - Processing method for collecting waste liquid containing fluorine and apparatus thereof - Google Patents

Processing method for collecting waste liquid containing fluorine and apparatus thereof Download PDF

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TW201305064A
TW201305064A TW100126434A TW100126434A TW201305064A TW 201305064 A TW201305064 A TW 201305064A TW 100126434 A TW100126434 A TW 100126434A TW 100126434 A TW100126434 A TW 100126434A TW 201305064 A TW201305064 A TW 201305064A
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waste liquid
containing waste
fluorine
alkaline
tank
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TW100126434A
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Chinese (zh)
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Kuo-Yi Chen
I-Chang Tsao
Ching-Lien Chen
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Mega Union Technology Inc
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Abstract

A processing method for collecting waste liquid containing fluorine comprises adding an alkaline solvent into a waste liquid containing fluorine to form an alkaline waste liquid, separating the alkaline waste liquid into a high and a low concentration waste liquids by a reverse osmosis membrane, and separating the high concentration waste liquid into waste liquids respectively containing anions and cations, so as to collect the waste liquid containing anions. The present invention further provides a processing apparatus for collecting waste liquid containing fluorine. After the alkaline waste liquid formed in a pH adjusting tank is separated into the high and the low concentration waste liquids by the reverse osmosis membrane, the high concentration waste liquid is further separated into the waste liquids respectively containing anions and cations in an ionization tank, so as to collect the waste liquid containing anions in a collecting tank.

Description

含氟廢液的回收處理方法及其設備Fluorine waste liquid recycling treatment method and equipment thereof

本發明是有關於一種廢液(waste liquid)的回收處理方法及其設備,且特別是有關於一種含氟(fluorine)廢液的回收處理方法及其設備。The present invention relates to a method for recycling waste liquid and an apparatus therefor, and more particularly to a method for recovering fluorine liquid and a device therefor.

隨著氣候變遷日益劇烈,全球各地發生澇災與旱災的機率也逐漸昇高,進而導致越來越不容易有效地保存與利用人類生存所不可或缺的乾淨水資源。更重要的是,全球人口數量急速成長與工業科技的迅速發展,導致人類對於環境污染日益嚴重,更使得水資源的保存與利用問題越來越惡化。因此,如何能夠有效地回收工業廢水(industrial waste water)中的污染物質,以降低污染物質對於環境的污染,已逐漸成為世界各國政府亟待解決的問題之一。With the gradual increase of climate, the chances of disasters and droughts in the world have gradually increased, which has made it increasingly difficult to effectively preserve and utilize the clean water resources that are indispensable for human survival. More importantly, the rapid growth of the global population and the rapid development of industrial technology have led to the increasing environmental pollution of human beings and the worsening of the problem of water conservation and utilization. Therefore, how to effectively recover pollutants in industrial waste water to reduce the pollution of pollutants to the environment has gradually become one of the problems that governments around the world need to solve urgently.

舉例來說,在半導體產業中,氟化氫(hydrofluoric acid,化學式為HF,俗稱氫氟酸)因具有能夠溶解矽晶圓(silicon wafer)的特性,因此經常會被用來對矽晶圓進行浸蝕、清洗與刻劃標記等製程。然而,若未能有效回收上述製程廢水中的氟化物,則排放至環境中的製程廢水將會對環境造成污染。特別是製程廢水中的氟化物若是在動植物體內持續累積,不僅可能會使植物生長受阻與農作物產量減少,更可能會影響動物體內對於鈣質的代謝,進而導致骨頭與牙齒發生異常性的鈣化。因此,部分國家已經立法,或者是傾向於立法,來限制廢水中的氟化物含量。For example, in the semiconductor industry, hydrogen fluoride (chemical formula HF, commonly known as hydrofluoric acid) is often used to etch wafers because it has the property of dissolving silicon wafers. Cleaning and scoring marks and other processes. However, if the fluoride in the process wastewater is not effectively recovered, the process wastewater discharged into the environment will pollute the environment. In particular, if fluoride in process wastewater continues to accumulate in plants and animals, it may not only hinder plant growth and reduce crop yield, but may also affect the metabolism of calcium in animals, leading to abnormal calcification of bones and teeth. Therefore, some countries have already enacted legislation or are inclined to legislate to limit the fluoride content in wastewater.

目前市場上通常是直接利用電透析(electro-deionization,EDI)法來回收廢水中的氟化物。然而,這種做法必須使用到數量較多的電透析模組才能有效處理大量的廢水,因此不僅回收成本會較高,回收效率也會較低。Currently, on the market, the electro-deionization (EDI) method is directly used to recover fluoride in wastewater. However, this method must use a large number of electrodialysis modules to effectively treat a large amount of wastewater, so not only the recovery cost will be higher, but also the recovery efficiency will be lower.

為了解決上述問題,本發明提供了一種含氟廢液的回收處理方法,以提高含氟廢液的回收效率。In order to solve the above problems, the present invention provides a method for recycling fluorine-containing waste liquid to improve the recovery efficiency of the fluorine-containing waste liquid.

為了解決上述問題,本發明更提供了一種含氟廢液的回收處理設備,以降低含氟廢液的回收成本。In order to solve the above problems, the present invention further provides a recycling treatment device for fluorine-containing waste liquid to reduce the recovery cost of the fluorine-containing waste liquid.

本發明提供一種含氟廢液的回收處理方法,其包括下列步驟。首先,在一含氟廢液中加入一鹼性溶劑(alkaline solvent),以形成一鹼性廢液(alkaline waste liquid)。接著,利用一逆滲透膜(reverse osmosis membrane,RO membrane)將鹼性廢液分離為一高濃度廢液以及一低濃度廢液。然後,再將高濃度廢液分離為一含陰離子(anions)廢液以及一含陽離子(cations)廢液,以回收含陰離子廢液。The invention provides a method for recycling fluorine-containing waste liquid, which comprises the following steps. First, an alkaline solvent is added to a fluorine-containing waste liquid to form an alkaline waste liquid. Next, the alkaline waste liquid is separated into a high-concentration waste liquid and a low-concentration waste liquid by using a reverse osmosis membrane (RO membrane). Then, the high-concentration waste liquid is separated into an anions-containing waste liquid and a cation-containing waste liquid to recover the anion-containing waste liquid.

在本發明的一實施例中,上述的含氟廢液的成分更包含過氧化氫(hydrogen peroxide,化學式為H2O2,俗稱雙氧水),並且在將鹼性廢液分離為高濃度廢液以及低濃度廢液之前,更包括利用一觸媒(catalyst)去除鹼性廢液中的過氧化氫。其中,觸媒可為活性碳(activated carbon fibers,ACF)、二氧化錳(manganese dioxide,化學式為MnO2)或者是鐵錳砂(manganese ore)。In an embodiment of the present invention, the fluorine-containing waste liquid component further comprises hydrogen peroxide (hydrogen peroxide, chemical formula is H 2 O 2 , commonly known as hydrogen peroxide), and the alkaline waste liquid is separated into a high-concentration waste liquid. And the low concentration of waste liquid, including the use of a catalyst to remove hydrogen peroxide in the alkaline waste liquid. The catalyst may be activated carbon fibers (ACF), manganese dioxide (manufactured by MnO 2 ) or manganese ore (manganese ore).

在本發明的一實施例中,上述的高濃度廢液是利用一電透析模組或者是一離子交換樹脂(ion exchange resin)分離為含陰離子廢液以及含陽離子廢液。In an embodiment of the invention, the high-concentration waste liquid is separated into an anion-containing waste liquid and a cation-containing waste liquid by using an electrodialysis module or an ion exchange resin.

本發明更提供一種含氟廢液的回收處理設備,其包括一酸鹼值調整槽(pH adjusting tank)、一逆滲透膜、一解離槽(ionization tank)以及一回收槽(collecting tank),其中逆滲透膜配置於酸鹼值調整槽與解離槽之間,並且回收槽連通於解離槽。酸鹼值調整槽用以容納一含氟廢液,並且適於注入一鹼性溶劑,以使含氟廢液形成一鹼性廢液。逆滲透膜用以將鹼性廢液分離為一高濃度廢液以及一低濃度廢液。解離槽用以將高濃度廢液分離為一含陰離子廢液以及一含陽離子廢液。回收槽用以回收含陰離子廢液。The present invention further provides a fluorine-containing waste liquid recovery processing apparatus, comprising a pH adjusting tank, a reverse osmosis membrane, an ionization tank, and a collecting tank, wherein The reverse osmosis membrane is disposed between the pH adjustment tank and the dissociation tank, and the recovery tank is in communication with the dissociation tank. The pH adjusting tank is for containing a fluorine-containing waste liquid, and is suitable for injecting an alkaline solvent to form the fluorine-containing waste liquid into an alkaline waste liquid. The reverse osmosis membrane is used to separate the alkaline waste liquid into a high concentration waste liquid and a low concentration waste liquid. The dissociation tank is used to separate the high concentration waste liquid into an anion-containing waste liquid and a cation-containing waste liquid. The recovery tank is used to recover the anion-containing waste liquid.

在本發明的一實施例中,上述的含氟廢液的回收處理設備更包括一觸媒,而含氟廢液的成分更包含過氧化氫,並且觸媒配置於酸鹼值調整槽與逆滲透膜之間,用以去除鹼性廢液中的過氧化氫。其中,觸媒為活性碳、二氧化錳或者是鐵錳砂。In an embodiment of the present invention, the fluorine-containing waste liquid recovery processing device further includes a catalyst, and the fluorine-containing waste liquid component further contains hydrogen peroxide, and the catalyst is disposed in the acid-base adjusting tank and the reverse Between the permeable membranes to remove hydrogen peroxide from the alkaline waste liquid. Among them, the catalyst is activated carbon, manganese dioxide or iron manganese sand.

在本發明的一實施例中,上述的解離槽中具有一電透析模組或者是一離子交換樹脂,並且高濃度廢液利用電透析模組或者是離子交換樹脂分離為含陰離子廢液以及含陽離子廢液。In an embodiment of the invention, the dissociation tank has an electrodialysis module or an ion exchange resin, and the high concentration waste liquid is separated into an anion-containing waste liquid by using an electrodialysis module or an ion exchange resin, and Cationic waste liquid.

在本發明的一實施例中,上述的解離槽連通於酸鹼值調整槽,用以將含陽離子廢液當作鹼性溶劑注入酸鹼值調整槽中。In an embodiment of the invention, the dissociation tank is connected to the pH adjustment tank for injecting the cation-containing waste liquid into the pH adjustment tank as an alkaline solvent.

在本發明的一實施例中,上述的含氟廢液的回收處理設備更包括一貯存槽(storage tank)。貯存槽連通於酸鹼值調整槽,用以貯存鹼性溶劑,並且適於將鹼性溶劑注入酸鹼值調整槽中。In an embodiment of the invention, the fluorine-containing waste liquid recovery processing apparatus further includes a storage tank. The storage tank is connected to the pH adjustment tank for storing the alkaline solvent, and is suitable for injecting the alkaline solvent into the pH adjustment tank.

在本發明的一實施例中,上述的鹼性廢液的酸鹼值約為9.5。In an embodiment of the invention, the alkaline waste liquid has a pH of about 9.5.

在本發明的一實施例中,上述的含氟廢液、鹼性溶劑與含陽離子廢液的成分皆包含鈉離子(sodium ion,化學式為Na+)與鉀離子(potassium ion,化學式為K+)至少其中之一。In an embodiment of the invention, the fluorine-containing waste liquid, the alkaline solvent and the cation-containing waste liquid component all contain sodium ions (sodium ion, chemical formula is Na + ) and potassium ions (potassium ion, chemical formula is K + ) at least one of them.

在本發明的一實施例中,上述的含氟廢液的成分更包含硫酸根離子(sulfate ion,化學式為SO4 2-)與磷酸根離子(phosphate ion,化學式為PO4 3-)至少其中之一。In an embodiment of the present invention, the fluorine-containing waste liquid component further comprises at least a sulfate ion (chemical formula: SO 4 2- ) and a phosphate ion (chemical formula: PO 4 3- ). one.

相較於先前技術,本發明不僅對於廢液中氟化物(fluoride)的回收效率會較高,對於氟化物的回收成本也會因為可不需要使用到多個電透析模組而較低。Compared with the prior art, the present invention not only has a higher recovery efficiency for fluoride in the waste liquid, but also a lower recovery cost for the fluoride because it is not necessary to use a plurality of electrodialysis modules.

為讓本發明的上述特徵和優點能更明顯易懂,下文特舉多個實施例,並配合所附圖式,作詳細說明如下。The above described features and advantages of the invention will be apparent from the following description.

圖1繪示出根據本發明一個實施例的一種含氟廢液的回收處理方法的流程圖。請參考圖1所示,含氟廢液的回收處理方法包括下列步驟。首先,如步驟S100所示,在一含氟廢液中加入一鹼性溶劑,以將原來呈酸性的含氟廢液的酸鹼值調整至9.5左右,進而形成一鹼性廢液。接著,如步驟S110所示,再利用逆滲透膜將鹼性廢液分離為一高濃度廢液以及一低濃度廢液。然後,如步驟S120所示,再對高濃度廢液進行解離處理,以將高濃度廢液分離為含有氟離子的一含陰離子廢液以及一含陽離子廢液。如此一來,如步驟S130所示,便能回收含有氟化物的含陰離子廢液。1 is a flow chart showing a method of recycling a fluorine-containing waste liquid according to an embodiment of the present invention. Referring to FIG. 1, the recycling treatment method of the fluorine-containing waste liquid includes the following steps. First, as shown in step S100, an alkaline solvent is added to a fluorine-containing waste liquid to adjust the pH value of the originally acidic fluorine-containing waste liquid to about 9.5 to form an alkaline waste liquid. Next, as shown in step S110, the alkaline waste liquid is separated into a high concentration waste liquid and a low concentration waste liquid by using a reverse osmosis membrane. Then, as shown in step S120, the high-concentration waste liquid is subjected to dissociation treatment to separate the high-concentration waste liquid into an anion-containing waste liquid containing fluorine ions and a cation-containing waste liquid. As a result, as shown in step S130, the fluoride-containing anion-containing waste liquid can be recovered.

更詳細而言,由於鹼性液體會使逆滲透膜帶負電,因而會有利於逆滲透膜排斥同樣是帶負電的氟離子(fluorine ion,化學式為F-),進而在高濃度廢液中保留更多的氟離子。因此,於此實施例中會先進行步驟S100,以藉由鹼性溶劑將原來呈酸性的含氟廢液調整為鹼性廢液。接著,在進行步驟S110,以利用逆滲透膜將鹼性廢液分離為高濃度廢液以及低濃度廢液時,便能夠提高高濃度廢液中的氟離子含量。此時,氟離子含量極低的低濃度廢液便能夠回收再利用,或者是排放至廢水處理廠進行後續的一般廢水處理製程。In more detail, since the alkaline liquid negatively charges the reverse osmosis membrane, it is advantageous for the reverse osmosis membrane to repel the negatively charged fluoride ion (chemical formula F - ), thereby retaining it in the high concentration waste liquid. More fluoride ions. Therefore, in this embodiment, step S100 is first performed to adjust the originally acidic fluorine-containing waste liquid to an alkaline waste liquid by an alkaline solvent. Next, in step S110, when the alkaline waste liquid is separated into the high-concentration waste liquid and the low-concentration waste liquid by the reverse osmosis membrane, the fluorine ion content in the high-concentration waste liquid can be increased. At this time, the low-concentration waste liquid having a very low fluorine ion content can be recycled or reused, or discharged to a wastewater treatment plant for subsequent general wastewater treatment processes.

然後,如步驟S120所示,再利用一電透析模組或者是一離子交換樹脂來對高濃度廢液進行解離處理,以將高濃度廢液分離為含陰離子廢液以及含陽離子廢液。相較於先前技術,由於此實施例已先在步驟S110中將濃度較低的含氟廢液濃縮為高濃度廢液,因此電透析模組或者是離子交換樹脂便能夠更有效率地將高濃度廢液解離為含陰離子廢液以及含陽離子廢液。換句話說,相較於先前技術,此實施例能夠以數量較少的電透析模組或者是離子交換樹脂來處理相同體積的含氟廢液。因此,相較之下,此實施例不僅具有較高的氟化物回收效率,也具有較低的回收成本。Then, as shown in step S120, an electrodialysis module or an ion exchange resin is used to dissociate the high-concentration waste liquid to separate the high-concentration waste liquid into an anion-containing waste liquid and a cation-containing waste liquid. Compared with the prior art, since this embodiment first concentrates the fluorine-containing waste liquid having a lower concentration into a high-concentration waste liquid in step S110, the electrodialysis module or the ion exchange resin can be more efficiently performed. The concentration waste liquid is dissociated into an anion-containing waste liquid and a cation-containing waste liquid. In other words, this embodiment is capable of treating the same volume of fluorine-containing waste liquid with a smaller number of electrodialysis modules or ion exchange resins than prior art. Therefore, in comparison, this embodiment not only has a higher fluoride recovery efficiency but also a lower recovery cost.

值得注意的是,為了簡化上述製程中的低濃度廢液、含陰離子廢液以及含陽離子廢液等副產物的後續處理作業,鹼性溶劑中所含有的陽離子成分最好是與含氟廢液中所含有的主要陽離子成分相同,以避免上述副產物中的主要成分太過複雜。It is worth noting that in order to simplify the subsequent processing of low-concentration waste liquid, anion-containing waste liquid, and by-products including cationic waste liquid in the above process, the cationic component contained in the alkaline solvent is preferably a fluorine-containing waste liquid. The main cationic components contained in the same are the same to avoid the complexity of the main components in the above-mentioned by-products.

更詳細而言,來自於半導體產業或者是其他產業的含氟廢液的主要成分通常不會只包含有氟離子,可能還會包含有鈉離子或者是鉀離子等陽離子。舉例來說,含氟廢液的主要成分可為氟化鈉(sodium fluoride,化學式為NaF)廢液或者是氟化鉀(potassium fluoride,化學式為KF)廢液。此時,鹼性溶劑的主要成分便可為氫氧化鈉(sodium hydroxide,化學式為NaOH,俗稱苛性鈉,caustic soda)溶液或者是氫氧化鉀(potassium hydroxide,化學式為KOH,俗稱苛性鉀,potassium soda)。More specifically, the main component of the fluorine-containing waste liquid from the semiconductor industry or other industries usually does not contain only fluorine ions, and may contain cations such as sodium ions or potassium ions. For example, the main component of the fluorine-containing waste liquid may be a sodium fluoride (chemical formula: NaF) waste liquid or a potassium fluoride (chemical formula KF) waste liquid. At this time, the main component of the alkaline solvent may be sodium hydroxide (chemical formula NaOH, commonly known as caustic soda, caustic soda) solution or potassium hydroxide (potassium hydroxide, chemical formula KOH, commonly known as caustic potash, potassium soda ).

另外,當含氟廢液的主要成分包含有鈉離子或者是鉀離子時,在步驟S120中所產生的含陽離子廢液的主要成分中,亦會包含有鈉離子與鉀離子至少其中之一。此時,含陽離子廢液便可被當作用來調整含氟廢液酸鹼值的鹼性溶劑,以進行重複利用。Further, when the main component of the fluorine-containing waste liquid contains sodium ions or potassium ions, at least one of sodium ions and potassium ions may be contained in the main component of the cation-containing waste liquid generated in step S120. At this time, the cation-containing waste liquid can be regarded as an alkaline solvent for adjusting the pH value of the fluorine-containing waste liquid for reuse.

除此之外,於此實施例中,含氟廢液的成分更可包含硫酸根離子(SO4 2-)與磷酸根離子(PO4 3-)至少其中之一。因此,在回收含陰離子廢液時,除了可回收到氟化物之外,更可一併回收到硫酸根化合物與磷酸根化合物至少其中之一。In addition, in this embodiment, the composition of the fluorine-containing waste liquid may further contain at least one of a sulfate ion (SO 4 2- ) and a phosphate ion (PO 4 3- ). Therefore, in recovering the anion-containing waste liquid, at least one of the sulfate compound and the phosphate compound can be recovered in addition to the fluoride.

圖2繪示出根據本發明另一個實施例的一種含氟廢液的回收處理方法的流程圖。請參考圖2所示,此實施例中的含氟廢液的回收處理方法與前一實施例中的含氟廢液的回收處理方法相似,二者不同之處在於此實施例中的含氟廢液的主要成分更包含過氧化氫。因此,在進行步驟S110,以將鹼性廢液分離為高濃度廢液以及低濃度廢液之前,更包括進行步驟S105,以利用一觸媒去除鹼性廢液中的過氧化氫。其中,觸媒可為活性碳、二氧化錳或者是鐵錳砂。其他步驟與前一實施例相同,於此不再贅述。2 is a flow chart showing a method of recycling fluorine-containing waste liquid according to another embodiment of the present invention. Referring to FIG. 2, the method for recovering the fluorine-containing waste liquid in this embodiment is similar to the method for recovering the fluorine-containing waste liquid in the previous embodiment, and the difference is the fluorine-containing in this embodiment. The main component of the waste liquid further contains hydrogen peroxide. Therefore, before the step S110 is performed to separate the alkaline waste liquid into the high-concentration waste liquid and the low-concentration waste liquid, the step S105 is further included to remove the hydrogen peroxide in the alkaline waste liquid by using a catalyst. Among them, the catalyst may be activated carbon, manganese dioxide or iron manganese sand. The other steps are the same as in the previous embodiment, and are not described herein again.

為了讓本技術領域中具有通常知識者能夠更容易理解上述含氟廢液的回收處理方法。以下將以具體實施例進一步揭露一種含氟廢液的回收處理設備。然而,上述含氟廢液的回收處理方法並非只能利用下述含氟廢液的回收處理設備才能進行。The recycling treatment method of the above-mentioned fluorine-containing waste liquid can be more easily understood by those skilled in the art. A recycling treatment apparatus for a fluorine-containing waste liquid will be further disclosed below by way of specific examples. However, the above-described method for recovering the fluorine-containing waste liquid can be carried out only by using the following fluorine-containing waste liquid recovery processing equipment.

圖3繪示出根據本發明一個實施例的一種含氟廢液的回收處理設備的結構示意圖。請參考圖3所示,含氟廢液的回收處理設備100a包括一個酸鹼值調整槽110、一個逆滲透膜120、一個解離槽130以及一個回收槽140。其中,逆滲透膜120配置於酸鹼值調整槽110與解離槽130之間,並且回收槽140連通於解離槽130。3 is a schematic view showing the structure of a recycling processing apparatus for a fluorine-containing waste liquid according to an embodiment of the present invention. Referring to FIG. 3, the fluorine-containing waste liquid recovery processing apparatus 100a includes a pH adjustment tank 110, a reverse osmosis membrane 120, a dissociation tank 130, and a recovery tank 140. The reverse osmosis membrane 120 is disposed between the pH adjustment tank 110 and the dissociation tank 130 , and the recovery tank 140 is in communication with the dissociation tank 130 .

酸鹼值調整槽110用以容納含氟廢液,並且適於注入鹼性溶劑,以將原來呈酸性的含氟廢液調整為鹼性廢液。然後,再利用逆滲透膜120將鹼性廢液分離為高濃度廢液以及低濃度廢液。其中,氟離子含量極低的低濃度廢液能夠回收再利用,或者是排放至廢水處理廠進行後續的一般廢水處理製程,而氟離子含量極高的高濃度廢液則會注入解離槽130中,以利用解離槽130中的電透析模組或者是離子交換樹脂進一步分離為含陰離子廢液以及含陽離子廢液。之後,再將含陰離子廢液注入回收槽140進行回收。The pH adjusting tank 110 is for accommodating the fluorine-containing waste liquid, and is suitable for injecting an alkaline solvent to adjust the originally acidic fluorine-containing waste liquid to an alkaline waste liquid. Then, the alkaline waste liquid is separated into a high-concentration waste liquid and a low-concentration waste liquid by using the reverse osmosis membrane 120. Among them, the low-concentration waste liquid with extremely low fluoride ion content can be recycled or reused, or discharged to a wastewater treatment plant for subsequent general wastewater treatment process, and the high-concentration waste liquid with extremely high fluoride ion content is injected into the dissociation tank 130. Further separating into an anion-containing waste liquid and a cation-containing waste liquid by using an electrodialysis module in the dissociation tank 130 or an ion exchange resin. Thereafter, the anion-containing waste liquid is injected into the recovery tank 140 for recovery.

相同地,相較於先前技術,由於此實施例會先將濃度較低的含氟廢液濃縮為高濃度廢液,因此電透析模組或者是離子交換樹脂便能夠更有效率地將高濃度廢液解離為含陰離子廢液以及含陽離子廢液。也因此,相較之下,此實施例不僅具有較高的回收效率,也具有較低的回收成本。Similarly, compared with the prior art, since this embodiment first concentrates the fluorine-containing waste liquid having a lower concentration into a high-concentration waste liquid, the electrodialysis module or the ion exchange resin can more efficiently discharge the high-concentration waste. The liquid dissociates into an anion-containing waste liquid and a cation-containing waste liquid. Therefore, in contrast, this embodiment not only has higher recovery efficiency but also lower recovery cost.

另外,當含氟廢液的主要成分還包含有鈉離子或者是鉀離子等陽離子時,可選擇上述陽離子的氫氧化物來做為鹼性溶劑的主要成分,以便簡化低濃度廢液、含陰離子廢液以及含陽離子廢液等副產物的後續處理作業。而且,於此實施例中,解離槽130亦可連通於酸鹼值調整槽110。此時,還能夠直接將含陽離子廢液當做用來調整含氟廢液酸鹼值的鹼性溶劑來注入酸鹼值調整槽110中,以進行重複利用。In addition, when the main component of the fluorine-containing waste liquid further contains a cation such as sodium ion or potassium ion, the hydroxide of the above cation can be selected as a main component of the alkaline solvent to simplify the low-concentration waste liquid and the anion. Subsequent processing of waste liquid and by-products such as cation waste liquid. Moreover, in this embodiment, the dissociation groove 130 may also communicate with the pH adjustment groove 110. At this time, it is also possible to directly inject the cation-containing waste liquid into the pH-adjusting tank 110 as an alkaline solvent for adjusting the pH value of the fluorine-containing waste liquid for reuse.

值得注意的是,部分的陽離子會在上述製程中隨著低濃度廢液被排放掉,因此含陽離子廢液中的陽離子含量可能不足以在後續製程中將含氟廢液調整至所需酸鹼值。因此,此實施例中的含氟廢液的回收處理設備100a更可包括連通於酸鹼值調整槽110,並且用以貯存鹼性溶劑的一個貯存槽150,以便根據需求量將鹼性溶劑從貯存槽150注入酸鹼值調整槽110中。It is worth noting that some of the cations will be discharged with the low-concentration waste liquid in the above process, so the cation content in the cation-containing waste liquid may not be sufficient to adjust the fluorine-containing waste liquid to the desired acid-base in the subsequent process. value. Therefore, the fluorine-containing waste liquid recovery processing apparatus 100a in this embodiment may further include a storage tank 150 connected to the pH adjustment tank 110 and used to store the alkaline solvent, so as to remove the alkaline solvent according to the demand. The storage tank 150 is injected into the pH adjustment tank 110.

此外,含氟廢液的回收處理設備100a還可包括複數個泵浦160、170以及180。其中,泵浦160可連接於酸鹼值調整槽110與逆滲透膜120之間,用以將鹼性廢液從酸鹼值調整槽110輸送至逆滲透膜120。再者,泵浦170可連接於逆滲透膜120與解離槽130之間,用以將高濃度廢液從逆滲透膜120注入解離槽130。另外,泵浦180則可連接於貯存槽150與酸鹼值調整槽110之間,用以將鹼性溶劑從貯存槽150注入至酸鹼值調整槽110。Further, the fluorine-containing waste liquid recovery processing apparatus 100a may further include a plurality of pumps 160, 170, and 180. The pump 160 may be connected between the pH adjustment tank 110 and the reverse osmosis membrane 120 for transporting the alkaline waste liquid from the pH adjustment tank 110 to the reverse osmosis membrane 120. Furthermore, the pump 170 can be connected between the reverse osmosis membrane 120 and the dissociation tank 130 for injecting a high concentration waste liquid from the reverse osmosis membrane 120 into the dissociation tank 130. In addition, the pump 180 can be connected between the storage tank 150 and the pH adjustment tank 110 for injecting the alkaline solvent from the storage tank 150 into the pH adjustment tank 110.

除此之外,於此實施例中,含氟廢液的成分更可包含硫酸根離子與磷酸根離子至少其中之一。因此,在回收含陰離子廢液時,除了可回收到氟化物之外,更可一併回收到硫酸根化合物與磷酸根化合物至少其中之一。In addition, in this embodiment, the component of the fluorine-containing waste liquid may further contain at least one of a sulfate ion and a phosphate ion. Therefore, in recovering the anion-containing waste liquid, at least one of the sulfate compound and the phosphate compound can be recovered in addition to the fluoride.

圖4繪示出根據本發明另一個實施例的一種含氟廢液的回收處理設備的結構示意圖。請參考圖4所示,此實施例中的含氟廢液的回收處理設備100b與前一實施例中的含氟廢液的回收處理設備100a相似,二者不同之處在於此實施例中的含氟廢液的主要成分更包含過氧化氫,因此含氟廢液的回收處理設備100b更可包括配置於酸鹼值調整槽110與逆滲透膜120之間的一個觸媒190。其中,觸媒190可為活性碳、二氧化錳或者是鐵錳砂,用以在將鹼性廢液分離為高濃度廢液以及低濃度廢液之前,去除鹼性廢液中的過氧化氫。此時,泵浦160可連接於酸鹼值調整槽110與觸媒190之間,用以將鹼性廢液從酸鹼值調整槽110輸送至觸媒190。其他元件的功能及連接關係與前一實施例相同,於此不再贅述。4 is a schematic view showing the structure of a fluorine-containing waste liquid recycling processing apparatus according to another embodiment of the present invention. Referring to FIG. 4, the fluorine-containing waste liquid recovery processing apparatus 100b in this embodiment is similar to the fluorine-containing waste liquid recovery processing apparatus 100a in the previous embodiment, and the difference is in this embodiment. The main component of the fluorine-containing waste liquid further contains hydrogen peroxide. Therefore, the fluorine-containing waste liquid recovery processing apparatus 100b may further include a catalyst 190 disposed between the acid-base adjusting tank 110 and the reverse osmosis membrane 120. The catalyst 190 may be activated carbon, manganese dioxide or iron manganese sand for removing hydrogen peroxide in the alkaline waste liquid before separating the alkaline waste liquid into a high concentration waste liquid and a low concentration waste liquid. . At this time, the pump 160 may be connected between the pH adjusting tank 110 and the catalyst 190 for transporting the alkaline waste liquid from the pH adjusting tank 110 to the catalyst 190. The functions and connection relationships of other components are the same as those of the previous embodiment, and will not be described herein.

綜合上述,由於鹼性液體會使逆滲透膜帶負電,因而會有利於逆滲透膜排斥氟離子,以便在高濃度廢液中保留更多的氟離子。因此,本發明先將含氟廢液的酸鹼值調整為鹼性,然後在利用逆滲透膜將鹼性廢液分離為高濃度廢液以及低濃度廢液時,便能提高逆滲透膜對於氟離子的回收效率。然後,再對高濃度廢液進行處理,以將其分離為含陰離子廢液以及含陽離子廢液。之後,便能回收含有氟化物的含陰離子廢液。因此,相較於先前技術,本發明不僅對於氟化物的回收效率會較高,對於氟化物的回收成本也會因為可不需要使用到多個電透析模組而較低。In summary, since the alkaline liquid negatively charges the reverse osmosis membrane, it is advantageous for the reverse osmosis membrane to repel the fluoride ion so as to retain more fluoride ions in the high concentration waste liquid. Therefore, the present invention first adjusts the pH value of the fluorine-containing waste liquid to be alkaline, and then, when the alkaline waste liquid is separated into a high-concentration waste liquid and a low-concentration waste liquid by using a reverse osmosis membrane, the reverse osmosis membrane can be improved. Fluoride ion recovery efficiency. Then, the high-concentration waste liquid is treated to separate it into an anion-containing waste liquid and a cation-containing waste liquid. Thereafter, the fluoride-containing anion-containing waste liquid can be recovered. Therefore, compared with the prior art, the present invention not only has higher recovery efficiency for fluoride, but also lowers the recovery cost for fluoride because it does not require the use of multiple electrodialysis modules.

雖然本發明已以實施例揭露如上,然其並非用以限定本發明,任何所屬技術領域中具有通常知識者,在不脫離本發明的精神和範圍內,當可作些許的更動與潤飾,因此本發明的保護範圍當視後附的申請專利範圍所界定者為準。Although the present invention has been disclosed in the above embodiments, it is not intended to limit the present invention, and those skilled in the art can make some modifications and refinements without departing from the spirit and scope of the present invention. The scope of the invention is defined by the scope of the appended claims.

100a、100b...含氟廢液的回收處理設備100a, 100b. . . Fluorine waste liquid recycling equipment

110...酸鹼值調整槽110. . . pH adjustment tank

120...逆滲透膜120. . . Reverse osmosis membrane

130...解離槽130. . . Dissociation slot

140...回收槽140. . . Recovery tank

150...貯存槽150. . . Storage tank

160、170、180...泵浦160, 170, 180. . . Pump

190...觸媒190. . . catalyst

S100、S105、S110、S120、S130...步驟S100, S105, S110, S120, S130. . . step

圖1繪示出根據本發明一個實施例的一種含氟廢液的回收處理方法的流程圖。1 is a flow chart showing a method of recycling a fluorine-containing waste liquid according to an embodiment of the present invention.

圖2繪示出根據本發明另一個實施例的一種含氟廢液的回收處理方法的流程圖。2 is a flow chart showing a method of recycling fluorine-containing waste liquid according to another embodiment of the present invention.

圖3繪示出根據本發明一個實施例的一種含氟廢液的回收處理設備的結構示意圖。3 is a schematic view showing the structure of a recycling processing apparatus for a fluorine-containing waste liquid according to an embodiment of the present invention.

圖4繪示出根據本發明另一個實施例的一種含氟廢液的回收處理設備的結構示意圖。4 is a schematic view showing the structure of a fluorine-containing waste liquid recycling processing apparatus according to another embodiment of the present invention.

S100、S110、S120、S130...步驟S100, S110, S120, S130. . . step

Claims (16)

一種含氟廢液的回收處理方法,包括:在一含氟廢液中加入一鹼性溶劑,以形成一鹼性廢液;利用一逆滲透膜將該鹼性廢液分離為一高濃度廢液以及一低濃度廢液;以及將該高濃度廢液分離為一含陰離子廢液以及一含陽離子廢液,以回收該含陰離子廢液。A method for recycling fluorine-containing waste liquid comprises: adding an alkaline solvent to a fluorine-containing waste liquid to form an alkaline waste liquid; and separating the alkaline waste liquid into a high-concentration waste by using a reverse osmosis membrane And a low concentration waste liquid; and separating the high concentration waste liquid into an anion containing waste liquid and a cation containing waste liquid to recover the anion containing waste liquid. 如申請專利範圍第1項所述的含氟廢液的回收處理方法,其中該含氟廢液的成分更包含過氧化氫,並且在將該鹼性廢液分離為該高濃度廢液以及該低濃度廢液之前,更包括利用一觸媒去除該鹼性廢液中的該過氧化氫。The method for recovering a fluorine-containing waste liquid according to claim 1, wherein the fluorine-containing waste liquid component further comprises hydrogen peroxide, and the alkaline waste liquid is separated into the high-concentration waste liquid and the Before the low concentration waste liquid, the use of the catalyst to remove the hydrogen peroxide in the alkaline waste liquid is further included. 如申請專利範圍第2項所述的含氟廢液的回收處理方法,其中該觸媒為活性碳、二氧化錳或者是鐵錳砂。The method for recovering fluorine-containing waste liquid according to claim 2, wherein the catalyst is activated carbon, manganese dioxide or iron manganese sand. 如申請專利範圍第1項所述的含氟廢液的回收處理方法,其中該鹼性廢液的酸鹼值約為9.5。The method for recovering a fluorine-containing waste liquid according to claim 1, wherein the alkaline waste liquid has a pH of about 9.5. 如申請專利範圍第1項所述的含氟廢液的回收處理方法,其中該高濃度廢液是利用一電透析模組或者是一離子交換樹脂分離為該含陰離子廢液以及該含陽離子廢液。The method for recycling fluorine-containing waste liquid according to claim 1, wherein the high-concentration waste liquid is separated into the anion-containing waste liquid and the cation-containing waste by using an electrodialysis module or an ion exchange resin. liquid. 如申請專利範圍第1項所述的含氟廢液的回收處理方法,其中該含氟廢液、該鹼性溶劑與該含陽離子廢液的成分皆包含鈉離子與鉀離子至少其中之一。The method for recovering a fluorine-containing waste liquid according to claim 1, wherein the fluorine-containing waste liquid, the alkaline solvent, and the cation-containing waste liquid-containing component each contain at least one of sodium ions and potassium ions. 如申請專利範圍第1項所述的含氟廢液的回收處理方法,其中該含氟廢液的成分更包含硫酸根離子與磷酸根離子至少其中之一。The method for recovering a fluorine-containing waste liquid according to claim 1, wherein the fluorine-containing waste liquid component further comprises at least one of a sulfate ion and a phosphate ion. 一種含氟廢液的回收處理設備,包括:一酸鹼值調整槽,用以容納一含氟廢液,並且適於注入一鹼性溶劑,以使該含氟廢液形成一鹼性廢液;一逆滲透膜,用以將該鹼性廢液分離為一高濃度廢液以及一低濃度廢液;一解離槽,該逆滲透膜配置於該酸鹼值調整槽與該解離槽之間,並且該解離槽用以將該高濃度廢液分離為一含陰離子廢液以及一含陽離子廢液;以及一回收槽,連通於該解離槽,用以回收該含陰離子廢液。The utility model relates to a recycling treatment device for a fluorine-containing waste liquid, comprising: a pH adjustment tank for accommodating a fluorine-containing waste liquid, and suitable for injecting an alkaline solvent, so that the fluorine-containing waste liquid forms an alkaline waste liquid; a reverse osmosis membrane for separating the alkaline waste liquid into a high concentration waste liquid and a low concentration waste liquid; a dissociation membrane disposed between the pH adjustment tank and the dissociation tank And the dissociation tank is configured to separate the high concentration waste liquid into an anion-containing waste liquid and a cation-containing waste liquid; and a recovery tank connected to the dissociation tank for recovering the anion-containing waste liquid. 如申請專利範圍第8項所述的含氟廢液的回收處理設備,更包括一觸媒,並且該含氟廢液的成分更包含過氧化氫,其中該觸媒配置於該酸鹼值調整槽與該逆滲透膜之間,用以去除該鹼性廢液中的該過氧化氫。The recycling processing device for a fluorine-containing waste liquid according to claim 8, further comprising a catalyst, wherein the fluorine-containing waste liquid component further comprises hydrogen peroxide, wherein the catalyst is disposed in the pH adjustment Between the tank and the reverse osmosis membrane for removing the hydrogen peroxide in the alkaline waste liquid. 如申請專利範圍第9項所述的含氟廢液的回收處理設備,其中該觸媒為活性碳、二氧化錳或者是鐵錳砂。The recycling treatment device for a fluorine-containing waste liquid according to claim 9, wherein the catalyst is activated carbon, manganese dioxide or iron manganese sand. 如申請專利範圍第8項所述的含氟廢液的回收處理方法,其中該鹼性廢液的酸鹼值約為9.5。The method for recovering a fluorine-containing waste liquid according to claim 8, wherein the alkaline waste liquid has a pH of about 9.5. 如申請專利範圍第8項所述的含氟廢液的回收處理設備,其中該解離槽中具有一電透析模組或者是一離子交換樹脂,並且該高濃度廢液利用該電透析模組或者是該離子交換樹脂分離為該含陰離子廢液以及該含陽離子廢液。The recycling treatment device for a fluorine-containing waste liquid according to claim 8, wherein the dissociation tank has an electrodialysis module or an ion exchange resin, and the high-concentration waste liquid utilizes the electrodialysis module or The ion exchange resin is separated into the anion-containing waste liquid and the cation-containing waste liquid. 如申請專利範圍第8項所述的含氟廢液的回收處理設備,其中該解離槽連通於該酸鹼值調整槽,用以將該含陽離子廢液當作該鹼性溶劑注入該酸鹼值調整槽中。The recycling treatment device for a fluorine-containing waste liquid according to claim 8, wherein the dissociation tank is connected to the pH adjustment tank for injecting the cation-containing waste liquid as the alkaline solvent into the acid-base. The value is adjusted in the slot. 如申請專利範圍第8項所述的含氟廢液的回收處理設備,更包括一貯存槽,連通於該酸鹼值調整槽,用以貯存該鹼性溶劑,並且適於將該鹼性溶劑注入該酸鹼值調整槽中。The recycling processing device for a fluorine-containing waste liquid according to claim 8, further comprising a storage tank connected to the pH adjustment tank for storing the alkaline solvent, and suitable for the alkaline solvent Inject into the pH adjustment tank. 如申請專利範圍第8項所述的含氟廢液的回收處理設備,其中該含氟廢液、該鹼性溶劑與該含陽離子廢液的成分皆包含鈉離子與鉀離子至少其中之一。The fluorine-containing waste liquid recovery processing apparatus according to claim 8, wherein the fluorine-containing waste liquid, the alkaline solvent and the cation-containing waste liquid-containing component each contain at least one of sodium ions and potassium ions. 如申請專利範圍第8項所述的含氟廢液的回收處理設備,其中該含氟廢液的成分更包含硫酸根離子與磷酸根離子至少其中之一。The fluorine-containing waste liquid recovery processing apparatus according to claim 8, wherein the fluorine-containing waste liquid component further comprises at least one of a sulfate ion and a phosphate ion.
TW100126434A 2011-07-26 2011-07-26 Processing method for collecting waste liquid containing fluorine and apparatus thereof TW201305064A (en)

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