TWI803757B - System for separation of phosphoric acid from mixed acid waste - Google Patents

System for separation of phosphoric acid from mixed acid waste Download PDF

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TWI803757B
TWI803757B TW109120096A TW109120096A TWI803757B TW I803757 B TWI803757 B TW I803757B TW 109120096 A TW109120096 A TW 109120096A TW 109120096 A TW109120096 A TW 109120096A TW I803757 B TWI803757 B TW I803757B
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magnesium
ammonium
ions
mixed acid
acid waste
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TW109120096A
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TW202200509A (en
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謝奇旭
申季剛
楊東昱
譚發祥
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崇越科技股份有限公司
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Abstract

A system and method for recycling magnesium ammonium phosphate solid from mixed acid waste solution are provided. The method includes: collecting a mixed acid waste solution, wherein the solution contains at least phosphate ion and sulfate ion; adding a magnesium ion source and an ammonium ions to the mixed acid waste solution, such that the magnesium ions and the ammonium ions react with phosphate ions to yield a magnesium ammonium phosphate solid; and separating magnesium ammonium phosphate solid from the mixed acid waste solutions. The phosphate recycle rate of the present disclosure can reach more than 99%.

Description

從混酸廢液中分離出磷酸的系統 A system for separating phosphoric acid from mixed acid waste

本發明涉及一種處理酸性廢液的系統及方法，特別是涉及一種從含硫酸和磷酸的混酸廢液中回收磷酸銨鎂固體的系統及方法。 The invention relates to a system and method for treating acidic waste liquid, in particular to a system and method for recovering ammonium magnesium phosphate solid from mixed acid waste liquid containing sulfuric acid and phosphoric acid.

磷(Phosphorus,P)屬於一種無法製造或合成的有限資源，而在半導體或面板製程下產生的大量混酸廢液中含有硫酸與磷酸，因此業界無不致力於從混酸廢液中分離出磷酸再重新利用。現有技術中的硫酸與磷酸分離處理方法，主要以自混酸廢液中移除硫酸為主，舉例而言，將選定的去除硫酸藥劑(如鈣鹽、鋇鹽、鎂鹽等)輸送至反應桶槽內，將混酸廢液中的硫酸轉變成不溶性固體的硫酸化合物(如硫酸鈣鹽、硫酸鋇、硫酸鎂等)，再進一步去除此硫酸化合物。然而，此方法去除混酸廢液中的硫酸化合物，一般也會同時捕捉混酸廢液中的磷酸鹽，兩者分離的效果差。 Phosphorus (Phosphorus, P) is a limited resource that cannot be manufactured or synthesized, and a large amount of mixed acid waste liquid produced in the semiconductor or panel process contains sulfuric acid and phosphoric acid, so the industry is committed to separating phosphoric acid from the mixed acid waste liquid and then reuse. The separation and treatment method of sulfuric acid and phosphoric acid in the prior art is mainly to remove sulfuric acid from the mixed acid waste liquid. For example, the selected sulfuric acid removal agent (such as calcium salt, barium salt, magnesium salt, etc.) is transported to the reaction tank In the tank, the sulfuric acid in the mixed acid waste liquid is converted into an insoluble solid sulfuric acid compound (such as calcium sulfate, barium sulfate, magnesium sulfate, etc.), and the sulfuric acid compound is further removed. However, this method removes sulfuric acid compounds in the mixed acid waste liquid, and generally captures the phosphate in the mixed acid waste liquid at the same time, and the separation effect of the two is poor.

現有技術的另一方法則是使用可再生的硫酸鹽吸附材料(如陰離子交換樹脂)，當硫酸鹽吸附材料達到飽和後，可使用的再生藥劑進行再生，進一步重複作為硫酸鹽吸附使用，然而，此方法去除混酸廢液中的硫酸鹽化合物，使用的硫酸鹽吸附材料往往也會吸附混酸廢液中的磷酸鹽，因此，分離效果也並不理想，此外，硫酸鹽吸附材料所使用的再生藥劑亦會產生額外的廢液，需要再另外清運。 Another method in the prior art is to use a reproducible sulfate adsorption material (such as anion exchange resin). When the sulfate adsorption material reaches saturation, the regeneration agent that can be used is regenerated and further used as sulfate adsorption. However, this method to remove sulfate compounds in mixed acid waste liquid, the used sulfate adsorption material often also adsorbs phosphate in mixed acid waste liquid, therefore, the separation effect is not ideal, in addition, the regeneration agent used in the sulfate adsorption material Additional waste liquid will be generated and will need to be removed separately.

故，如何有效針對混酸廢液回收再利用，將磷成為循環利用之資源，來克服上述的缺陷，已成為該項事業所欲解決的重要課題之一。 Therefore, how to effectively recycle and reuse the mixed acid waste liquid and turn phosphorus into a recycled resource to overcome the above-mentioned defects has become one of the important issues that this enterprise wants to solve.

本發明所要解決的技術問題在於，針對現有技術的不足提供一種從混酸廢液中回收磷酸銨鎂固體的系統及方法，其能夠確實將磷酸與硫酸分離，並且回收再利用。 The technical problem to be solved by the present invention is to provide a system and method for recovering ammonium magnesium phosphate solids from mixed acid waste liquid in view of the deficiencies of the prior art, which can surely separate phosphoric acid from sulfuric acid and recycle them for reuse.

為了解決上述的技術問題，本發明所採用的其中一技術方案是提供一種從混酸廢液中回收磷酸銨鎂固體的方法，其包括：收集一混酸廢液，所述混酸廢液至少含有磷酸根離子以及硫酸根離子；加入一鎂離子源與一銨離子源於所述混酸廢液中，以提供鎂離子和銨離子與磷酸根離子發生反應，從而生成磷酸銨鎂固體；以及將所述磷酸銨鎂固體從所述混酸廢液中分離。 In order to solve the above-mentioned technical problems, one of the technical solutions adopted by the present invention is to provide a method for recovering ammonium magnesium phosphate solids from mixed acid waste liquid, which includes: collecting a mixed acid waste liquid, which contains at least phosphate Ions and sulfate ions; adding a source of magnesium ions and an ammonium ion originates from the mixed acid waste liquid to provide magnesium ions and ammonium ions to react with phosphate ions, thereby generating magnesium ammonium phosphate solid; and the phosphoric acid Ammonium magnesium solids are separated from the mixed acid waste liquid.

在本發明的一實施例中，在收集所述混酸廢液的步驟中，還包括分析磷酸根離子的濃度；在生成所述磷酸銨鎂固體的步驟中，所加入的所述鎂離子源與所述銨離子源的濃度是根據分析得到的磷酸根離子的濃度來決定的。 In an embodiment of the present invention, in the step of collecting the mixed acid waste liquid, it also includes analyzing the concentration of phosphate ions; in the step of generating the magnesium ammonium phosphate solid, the added magnesium ion source and The concentration of the ammonium ion source is determined according to the concentration of the phosphate ion obtained by analysis.

在本發明的一實施例中，在生成所述磷酸銨鎂固體的步驟中，還包括將所述混酸廢液的pH值調整至8至8.5；並且，鎂離子、銨離子與磷酸根離子是在20℃至40℃的溫度下反應。 In one embodiment of the present invention, in the step of generating the magnesium ammonium phosphate solid, it also includes adjusting the pH value of the mixed acid waste liquid to 8 to 8.5; and, magnesium ions, ammonium ions and phosphate ions are React at a temperature of 20°C to 40°C.

在本發明的一實施例中，反應時間為30分鐘。 In one embodiment of the present invention, the reaction time is 30 minutes.

在本發明的一實施例中，鎂離子、銨離子與磷酸根離子的莫耳比例為1：1：1。 In an embodiment of the present invention, the molar ratio of magnesium ions, ammonium ions and phosphate ions is 1:1:1.

在本發明的一實施例中，所述鎂離子源包含至少一種鎂鹽，且所述銨離子源至少一種銨鹽。 In one embodiment of the invention, said source of magnesium ions comprises at least one magnesium salt, and said source of ammonium ions is at least one ammonium salt.

在本發明的一實施例中，所述鎂鹽選自於氯化鎂、硫酸鎂、碳酸鎂、氧化鎂以及氫氧化鎂，且所述銨鹽選自於氨水、氯化銨、硫酸銨、硝酸銨以及碳酸氫銨。 In one embodiment of the present invention, the magnesium salt is selected from magnesium chloride, magnesium sulfate, magnesium carbonate, magnesium oxide and magnesium hydroxide, and the ammonium salt is selected from ammonia water, ammonium chloride, ammonium sulfate, ammonium nitrate and ammonium bicarbonate.

為了解決上述的技術問題，本發明所採用的其中一技術方案是提供一種從混酸廢液中回收磷酸銨鎂固體的系統，其包括一反應單元、一第一儲存單元、一第二儲存單元以及一固液分離單元，所述第一儲存單元、所述第二儲存單元與所述固液分離單元都與所述反應單元流體連通。所述反應單元用於處理一混酸廢液，其中所述混酸廢液至少含有磷酸根離子以及硫酸根離子，所述第一儲存單元用於提供一鎂離子源至所述反應單元，所述第二儲存單元用於提供一銨離子源至所述反應單元，所述固液分離單元與所述反應單元流體連通。當所述反應單元中收集有所述混酸廢液時，所述鎂離子源所提供的鎂離子和所述銨離子源所提供的銨離子能與磷酸根離子發生反應，以生成磷酸銨鎂固體，且所述固液分離單元能將所述磷酸銨鎂固體從所述混酸廢液中分離。 In order to solve the above technical problems, one of the technical solutions adopted in the present invention is to provide a system for reclaiming magnesium ammonium phosphate solids from mixed acid waste liquid, which includes a reaction unit, a first storage unit, a second storage unit and A solid-liquid separation unit, the first storage unit, the second storage unit and the solid-liquid separation unit are all in fluid communication with the reaction unit. The reaction unit is used to treat a mixed acid waste liquid, wherein the mixed acid waste liquid contains at least phosphate ions and sulfate ions, the first storage unit is used to provide a source of magnesium ions to the reaction unit, and the second The second storage unit is used to provide an ammonium ion source to the reaction unit, and the solid-liquid separation unit is in fluid communication with the reaction unit. When the mixed acid waste liquid is collected in the reaction unit, the magnesium ions provided by the magnesium ion source and the ammonium ions provided by the ammonium ion source can react with phosphate ions to generate magnesium ammonium phosphate solid , and the solid-liquid separation unit can separate the magnesium ammonium phosphate solid from the mixed acid waste liquid.

在本發明的一實施例中，所述鎂離子源包含至少一種鎂鹽，且所述銨離子源至少一種銨鹽。 In one embodiment of the invention, said source of magnesium ions comprises at least one magnesium salt, and said source of ammonium ions is at least one ammonium salt.

在本發明的一實施例中，所述鎂鹽選自於氯化鎂、硫酸鎂、碳酸鎂、氧化鎂以及氫氧化鎂，且所述銨鹽選自於氨水、氯化銨、硫酸銨、硝酸銨以及碳酸氫銨。 In one embodiment of the present invention, the magnesium salt is selected from magnesium chloride, magnesium sulfate, magnesium carbonate, magnesium oxide and magnesium hydroxide, and the ammonium salt is selected from ammonia water, ammonium chloride, ammonium sulfate, ammonium nitrate and ammonium bicarbonate.

本發明的其中一有益效果在於，本發明的從混酸廢液中回收磷酸銨鎂固體的系統及方法，其能利用鎂離子源(鎂鹽)與銨離子源(銨鹽)從混酸廢液中專一性地捕捉磷酸根離子並生成磷酸銨鎂固體，以大幅提高磷酸根的回收率(回收率可達99%以上)，從而實現磷資源的循環利用。 One of the beneficial effects of the present invention is that the system and method for reclaiming ammonium magnesium phosphate solids from mixed acid waste liquid of the present invention can utilize magnesium ion source (magnesium salt) and ammonium ion source (ammonium salt) to extract from mixed acid waste liquid Specifically capture phosphate ions and generate magnesium ammonium phosphate solids to greatly increase the recovery rate of phosphate (the recovery rate can reach more than 99%), thereby realizing the recycling of phosphorus resources.

為使能更進一步瞭解本發明的特徵及技術內容，請參閱以下有 關本發明的詳細說明與圖式，然而所提供的圖式僅用於提供參考與說明，並非用來對本發明加以限制。 For enabling a further understanding of the features and technical content of the present invention, please refer to the following The detailed description and drawings related to the present invention, however, the provided drawings are only for reference and illustration, and are not intended to limit the present invention.

10:反應單元 10: Reaction unit

20:第一儲存單元 20: The first storage unit

30:第二儲存單元 30: Second storage unit

40:固液分離單元 40: Solid-liquid separation unit

S100至S300:方法步驟 S100 to S300: method steps

圖1為本發明從混酸廢液中回收磷酸銨鎂固體的方法的流程圖。 Fig. 1 is the flow chart of the present invention reclaims the method for ammonium magnesium phosphate solid from mixed acid waste liquid.

圖2為從混酸廢液中回收磷酸銨鎂固體的系統的示意圖。 Figure 2 is a schematic diagram of a system for recovering magnesium ammonium phosphate solids from mixed acid waste liquid.

以下是通過特定的具體實施例來說明本發明所公開有關“從混酸廢液中回收磷酸銨鎂固體的系統及方法”的實施方式，本領域技術人員可由本說明書所公開的內容瞭解本發明的優點與效果。本發明可通過其他不同的具體實施例加以施行或應用，本說明書中的各項細節也可基於不同觀點與應用，在不背離本發明的構思下進行各種修改與變更。另外，本發明的附圖僅為簡單示意說明，並非依實際尺寸的描繪，事先聲明。以下的實施方式將進一步詳細說明本發明的相關技術內容，但所公開的內容並非用以限制本發明的保護範圍。另外，本文中所使用的術語“或”，應視實際情況可能包括相關聯的列出項目中的任一個或者多個的組合。 The following is to illustrate the implementation of the "system and method for reclaiming magnesium ammonium phosphate solids from mixed acid waste liquid" disclosed by the present invention through specific specific examples. Those skilled in the art can understand the present invention from the content disclosed in this specification Advantages and effects. The present invention can be implemented or applied through other different specific embodiments, and various modifications and changes can be made to the details in this specification based on different viewpoints and applications without departing from the concept of the present invention. In addition, the drawings of the present invention are only for simple illustration, and are not drawn according to the actual size, which is stated in advance. The following embodiments will further describe the relevant technical content of the present invention in detail, but the disclosed content is not intended to limit the protection scope of the present invention. In addition, the term "or" used herein may include any one or a combination of more of the associated listed items depending on the actual situation.

參閱圖1所示，本發明一較佳實施例提供一種從混酸廢液中回收磷酸銨鎂固體的方法，其包括：步驟S100，收集一混酸廢液，其至少含有磷酸根離子以及硫酸根離子；步驟S200，加入一鎂離子源與一銨離子源於混酸廢液中，以提供鎂離子和銨離子與磷酸根離子發生反應，從而生成磷酸銨鎂固體；以及步驟S300，將磷酸銨鎂固體從混酸廢液中分離。 Referring to Fig. 1, a preferred embodiment of the present invention provides a method for recovering ammonium magnesium phosphate solids from mixed acid waste liquid, which includes: step S100, collecting a mixed acid waste liquid, which contains at least phosphate ions and sulfate ions ; Step S200, adding a source of magnesium ions and an ammonium ion from the mixed acid waste liquid to provide magnesium ions and ammonium ions to react with phosphate ions, thereby generating magnesium ammonium phosphate solid; and step S300, adding magnesium ammonium phosphate solid Separation from mixed acid waste liquid.

配合參閱圖2所示，在步驟S100中，可使用一反應單元10來收集 混酸廢液，混酸廢液可為半導體或面板製造工藝大量產生的廢液，但不限於此。實際應用時，反應單元10可為一耐腐蝕性的反應槽，且反應槽內部可設有擾流器及檢測器(如液位、溫度、酸鹼值及離子濃度的檢測器)，其中擾流器可以適當的方式在混酸廢液中產生穩定的流場。進一步而言，當反應單元10中收集有混酸廢液時，可以先分析混酸廢液中磷酸根離子的濃度，據以計量添加鎂離子源與銨離子源。然而，以上所述只是可行的實施方式，而並非用以限定本發明。 With reference to Fig. 2, in step S100, a reaction unit 10 can be used to collect Mixed acid waste liquid, the mixed acid waste liquid may be waste liquid produced in large quantities in the semiconductor or panel manufacturing process, but is not limited thereto. In actual application, the reaction unit 10 can be a corrosion-resistant reaction tank, and the inside of the reaction tank can be provided with a spoiler and a detector (such as a detector of liquid level, temperature, pH value and ion concentration), wherein the disturbance The flow device can generate a stable flow field in the mixed acid waste liquid in an appropriate manner. Furthermore, when the mixed acid waste liquid is collected in the reaction unit 10, the concentration of phosphate ions in the mixed acid waste liquid can be analyzed first, and the magnesium ion source and the ammonium ion source can be metered accordingly. However, the above descriptions are only feasible implementation manners, and are not intended to limit the present invention.

在步驟S200中，鎂離子源與銨離子源可以液體的形式加入於混酸廢液，而所加入的鎂離子源與銨離子源的濃度是根據分析得到的磷酸根離子的濃度來決定的。在本實施例中，鎂離子源可包含選自於氯化鎂、硫酸鎂、碳酸鎂、氧化鎂及氫氧化鎂中的至少一種鎂鹽，優選的鎂鹽為氧化鎂；銨離子源可包含選自於氨水、氯化銨、硫酸銨、硝酸銨及碳酸氫銨中的至少一種銨鹽，優選的銨鹽為氨水。值得說明的是，鎂離子源所提供的鎂離子可與銨離子源所提供的銨離子配合，以從混酸廢液中專一性地捕捉磷酸根離子並生成磷酸銨鎂固體(磷酸銨鎂結晶)沉澱，其反應式如下，以確實將磷酸與硫酸分離。 In step S200, the source of magnesium ions and the source of ammonium ions can be added to the mixed acid waste liquid in the form of liquid, and the concentration of the added source of magnesium ions and ammonium ions is determined according to the concentration of phosphate ions obtained through analysis. In this embodiment, the source of magnesium ions may comprise at least one magnesium salt selected from magnesium chloride, magnesium sulfate, magnesium carbonate, magnesium oxide and magnesium hydroxide, the preferred magnesium salt is magnesium oxide; the source of ammonium ions may comprise At least one ammonium salt in ammonia water, ammonium chloride, ammonium sulfate, ammonium nitrate and ammonium bicarbonate, the preferred ammonium salt is ammonia water. It is worth noting that the magnesium ions provided by the magnesium ion source can cooperate with the ammonium ions provided by the ammonium ion source to specifically capture phosphate ions from the mixed acid waste liquid and generate ammonium magnesium phosphate solid (magnesium ammonium phosphate crystallization) Precipitation, whose reaction formula is as follows, to separate phosphoric acid from sulfuric acid.

Mg2++NH4 ++PO4 3-+6H2O→Mg(NH4)PO4．6H2O↓上述生成磷酸銨鎂固體的反應優選在pH值為8至8.5及溫度為20℃至40℃的條件下進行，其中鎂離子、銨離子與磷酸根離子的莫耳比例優選為1：1：1，且反應時間優選為30分鐘，但本發明並不限制於此。 Mg 2+ +NH 4 + +PO 4 3- +6H 2 O→Mg(NH 4 )PO 4 . 6H 2 O ↓ The above reaction to form magnesium ammonium phosphate solid is preferably carried out at a pH value of 8 to 8.5 and a temperature of 20°C to 40°C, wherein the molar ratio of magnesium ions, ammonium ions, and phosphate ions is preferably 1 :1:1, and the reaction time is preferably 30 minutes, but the present invention is not limited thereto.

進一步而言，鎂離子源可先儲存於一第一儲存單元20中，當反應單元10中收集有混酸廢液時，再從第一儲存單元20提供至反應單元10；另外，銨離子源可先儲存於一第二儲存單元30中，當反應單元10中收集有混酸廢液時，再從第二儲存單元30提供至反應單元10。鎂離子源和銨離子源可同 時以適當的濃度被提供至反應單元10，或者可先提供適當濃度的銨離子源至反應單元10，然後再提供適當濃度的鎂離子源至反應單元10，以避免非必要的反應發生影響到磷酸銨鎂固體的回收效率。實際應用時，第一儲存單元20可為鎂離子源的儲存槽，且第一儲存單元20可通過一輸送管線與反應單元10流體連通，第二儲存單元30可為銨離子源的儲存槽，且第二儲存單元30也可通過一輸送管線與反應單元10流體連通。然而，以上所述只是可行的實施方式，而並非用以限定本發明。 Further, the magnesium ion source can be stored in a first storage unit 20 first, and when mixed acid waste liquid is collected in the reaction unit 10, it can be provided to the reaction unit 10 from the first storage unit 20; in addition, the ammonium ion source can be It is first stored in a second storage unit 30 , and then provided to the reaction unit 10 from the second storage unit 30 when the mixed acid waste liquid is collected in the reaction unit 10 . Magnesium ion source and ammonium ion source can be the same is provided to the reaction unit 10 at an appropriate concentration, or the ammonium ion source of an appropriate concentration can be provided to the reaction unit 10 first, and then the magnesium ion source of an appropriate concentration can be provided to the reaction unit 10, so as to avoid unnecessary reactions affecting the Recovery efficiency of magnesium ammonium phosphate solids. In actual application, the first storage unit 20 can be a storage tank of the magnesium ion source, and the first storage unit 20 can be in fluid communication with the reaction unit 10 through a delivery pipeline, and the second storage unit 30 can be a storage tank of the ammonium ion source, And the second storage unit 30 can also be in fluid communication with the reaction unit 10 through a delivery line. However, the above descriptions are only feasible implementation manners, and are not intended to limit the present invention.

在步驟S300中，可使用一固液分離單元40將磷酸銨鎂固體從混酸廢液中分離出來，固液分離單元40可為一沉降式固液分離裝置或一過濾式固液分離裝置，但不限於此。實際應用時，固液分離單元40可通過一輸送管線與反應單元10流體連通，或者固液分離單元40可與反應單元10整合成一體。然而，以上所述只是可行的實施方式，而並非用以限定本發明。 In step S300, a solid-liquid separation unit 40 can be used to separate the magnesium ammonium phosphate solid from the mixed acid waste liquid. The solid-liquid separation unit 40 can be a sedimentation type solid-liquid separation device or a filter type solid-liquid separation device, but Not limited to this. In practical application, the solid-liquid separation unit 40 may be in fluid communication with the reaction unit 10 through a delivery pipeline, or the solid-liquid separation unit 40 may be integrated with the reaction unit 10 . However, the above descriptions are only feasible implementation manners, and are not intended to limit the present invention.

參閱圖2所示，本發明還提供一種從混酸廢液中回收磷酸銨鎂固體的系統，用以實現上述的步驟。本發明的系統包括一反應單元10、一第一儲存單元20、一第二儲存單元30及一固液分離單元40。反應單元10用於處理一混酸廢液，其中混酸廢液至少含有磷酸根離子以及硫酸根離子，第一儲存單元20與反應單元10流體連通，用於提供一鎂離子源至反應單元10，第二儲存單元30與反應單元流體連通，用於提供一銨離子源至反應單元10，固液分離單元40與反應單元10流體連通。當反應單元10中收集有混酸廢液時，鎂離子源所提供的鎂離子和銨離子源所提供的銨離子能與磷酸根離子發生反應，以生成磷酸銨鎂固體，且固液分離40單元能將磷酸銨鎂固體從混酸廢液中分離。關於反應單元10、第一儲存單元20、第二儲存單元30與固液分離單元40的特徵，已詳述於前面的段落中，故在此不加以贅述。 Referring to Fig. 2, the present invention also provides a system for reclaiming ammonium magnesium phosphate solids from mixed acid waste liquid, in order to realize the above steps. The system of the present invention includes a reaction unit 10 , a first storage unit 20 , a second storage unit 30 and a solid-liquid separation unit 40 . The reaction unit 10 is used to treat a mixed acid waste liquid, wherein the mixed acid waste liquid contains at least phosphate ions and sulfate ions, the first storage unit 20 is in fluid communication with the reaction unit 10, and is used to provide a source of magnesium ions to the reaction unit 10, the second The second storage unit 30 is in fluid communication with the reaction unit for providing an ammonium ion source to the reaction unit 10 , and the solid-liquid separation unit 40 is in fluid communication with the reaction unit 10 . When mixed acid waste liquid is collected in the reaction unit 10, the magnesium ions provided by the magnesium ion source and the ammonium ions provided by the ammonium ion source can react with phosphate ions to generate magnesium ammonium phosphate solids, and the solid-liquid separation 40 units It can separate solid magnesium ammonium phosphate from mixed acid waste liquid. The characteristics of the reaction unit 10 , the first storage unit 20 , the second storage unit 30 , and the solid-liquid separation unit 40 have been described in detail in the previous paragraphs, so they will not be repeated here.

[實施例1] [Example 1]

收集一面板製程產生的混酸廢液，其包括磷酸根離子以及硫酸根離子，分析得到磷酸根離子的濃度，然後按計量比添加氨水與氯化鎂至混酸廢液中，使得鎂離子、銨離子與磷酸根離子的莫耳比例為1：1：1。反應產物中有白色的磷酸銨鎂結晶析出，使用過濾式固液分離單元將磷酸銨鎂結晶固體從反應產物中分離出來。分析反應後的混酸廢液，發現磷酸根轉換為磷酸銨鎂結晶固體>99%(結晶固體中硫酸根<1%)。 Collect the mixed acid waste liquid produced by a panel process, which includes phosphate ions and sulfate ions, analyze the concentration of phosphate ions, and then add ammonia water and magnesium chloride to the mixed acid waste liquid according to the metering ratio, so that magnesium ions, ammonium ions and phosphoric acid The molar ratio of root ions is 1:1:1. In the reaction product, white ammonium magnesium phosphate crystals are precipitated, and the solid-liquid separation unit of the filter type is used to separate the ammonium magnesium phosphate crystalline solid from the reaction product. After analyzing the mixed acid waste liquid after the reaction, it was found that the phosphate group was converted into ammonium magnesium phosphate crystalline solid>99% (sulfate group<1% in the crystalline solid).

[比較例1至4] [Comparative Examples 1 to 4]

混酸廢液的種類與實施例1相同，但使用現有的陰離子交換樹脂來提取混酸廢液中的磷酸根離子，陰離子交換樹脂的種類與所對應磷酸根離子的去除結果記載於表1。 The type of mixed acid waste liquid is the same as in Example 1, but the existing anion exchange resin is used to extract the phosphate ions in the mixed acid waste liquid. The type of anion exchange resin and the corresponding phosphate ion removal results are listed in Table 1.

Figure 109120096-A0305-02-0009-1
Figure 109120096-A0305-02-0009-1

[實施例的有益效果] [Advantageous Effects of Embodiment]

本發明的其中一有益效果在於，本發明的從混酸廢液中回收磷酸銨鎂固體的系統及方法，其能利用鎂離子源(鎂鹽)與銨離子源(銨鹽)從混酸廢液中專一性地捕捉磷酸根離子並生成磷酸銨鎂固體，以大幅提高磷酸根的回收率(回收率可達99%以上)，從而實現磷資源的循環利用。 One of the beneficial effects of the present invention is that the system and method for reclaiming ammonium magnesium phosphate solids from mixed acid waste liquid of the present invention can utilize magnesium ion source (magnesium salt) and ammonium ion source (ammonium salt) to extract from mixed acid waste liquid Specifically capture phosphate ions and generate magnesium ammonium phosphate solids to greatly increase the recovery rate of phosphate (the recovery rate can reach more than 99%), thereby realizing the recycling of phosphorus resources.

更進一步來說，本發明的系統及方法可以在化學反應中將磷酸與硫酸分離，分離效率高，而且不需要複雜的分離提純工藝，適合大規模應用。 Furthermore, the system and method of the present invention can separate phosphoric acid and sulfuric acid in a chemical reaction, with high separation efficiency, and does not require complex separation and purification processes, and is suitable for large-scale applications.

以上所公開的內容僅為本發明的優選可行實施例，並非因此侷限本發明的申請專利範圍，所以凡是運用本發明說明書及圖式內容所做的等效技術變化，均包含於本發明的申請專利範圍內。 The content disclosed above is only a preferred feasible embodiment of the present invention, and does not therefore limit the scope of the patent application of the present invention. Therefore, all equivalent technical changes made by using the description and drawings of the present invention are included in the application of the present invention. within the scope of the patent.

S100-S300:方法步驟 S100-S300: method steps

Claims (3)

一種從混酸廢液中分離出磷酸的系統，包括：一反應單元，用於處理一混酸廢液，其中所述混酸廢液至少含有磷酸根離子以及硫酸根離子；一第一儲存單元，與所述反應單元流體連通，用於提供一鎂離子源至所述反應單元，其中所述鎂離子源為碳酸鎂；一第二儲存單元，與所述反應單元流體連通，用於提供一銨離子源至所述反應單元，其中所述銨鹽為碳酸氫銨；以及一固液分離單元，與所述反應單元流體連通；其中，當所述反應單元中收集有所述混酸廢液時，所述鎂離子源所提供的鎂離子和所述銨離子源所提供的銨離子能與磷酸根離子以莫耳比1：1：1發生反應，使得所述混酸廢液中99%以上的磷酸根轉換為磷酸銨鎂固體，且所述固液分離單元能將所述磷酸銨鎂固體從所述混酸廢液中分離；所述鎂離子源和所述銨離子源同時被提供至所述反應單元，或者先提供所述銨離子源至所述反應單元然後再提供所述鎂離子源至所述反應單元。 A system for separating phosphoric acid from mixed acid waste liquid, comprising: a reaction unit for treating a mixed acid waste liquid, wherein the mixed acid waste liquid contains at least phosphate ions and sulfate ions; a first storage unit and the The reaction unit is in fluid communication for providing a source of magnesium ions to the reaction unit, wherein the source of magnesium ions is magnesium carbonate; a second storage unit is in fluid communication with the reaction unit for providing a source of ammonium ions To the reaction unit, wherein the ammonium salt is ammonium bicarbonate; and a solid-liquid separation unit, in fluid communication with the reaction unit; wherein, when the mixed acid waste liquid is collected in the reaction unit, the The magnesium ions provided by the magnesium ion source and the ammonium ions provided by the ammonium ion source can react with phosphate ions in a molar ratio of 1:1:1, so that more than 99% of the phosphate in the mixed acid waste liquid is converted It is a magnesium ammonium phosphate solid, and the solid-liquid separation unit can separate the magnesium ammonium phosphate solid from the mixed acid waste liquid; the magnesium ion source and the ammonium ion source are simultaneously provided to the reaction unit, Alternatively, the source of ammonium ions is provided to the reaction unit first and then the source of magnesium ions is provided to the reaction unit. 如請求項1所述的從混酸廢液中分離出磷酸的系統，其中，所述第一儲存單元為一鎂離子源儲存槽，且所述第一儲存單元通過一輸送管線與所述反應單元流體連通；所述第二儲存單元為一銨離子源儲存槽，且所述第二儲存單元通過另一輸送管線與所述反應單元流體連通。 The system for separating phosphoric acid from mixed acid waste liquid according to claim 1, wherein the first storage unit is a magnesium ion source storage tank, and the first storage unit is connected to the reaction unit through a delivery pipeline Fluid communication; the second storage unit is an ammonium ion source storage tank, and the second storage unit is in fluid communication with the reaction unit through another delivery pipeline. 如請求項1所述的從混酸廢液中分離出磷酸的系統，其中，所述固液分離單元為一沉降式固液分離裝置或一過濾式固液分離裝置。 The system for separating phosphoric acid from mixed acid waste liquid according to claim 1, wherein the solid-liquid separation unit is a sedimentation type solid-liquid separation device or a filtration type solid-liquid separation device.
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CN102139975A (en) * 2011-02-22 2011-08-03 南京大学 Method for recovering phosphorus in crystallization way from semiconductor industrial waste water
TW201930201A (en) * 2017-11-23 2019-08-01 荷蘭商安科智諾貝爾化學國際公司 Process for the treatment of a phosphite-containing waste stream

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102139975A (en) * 2011-02-22 2011-08-03 南京大学 Method for recovering phosphorus in crystallization way from semiconductor industrial waste water
TW201930201A (en) * 2017-11-23 2019-08-01 荷蘭商安科智諾貝爾化學國際公司 Process for the treatment of a phosphite-containing waste stream

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