TWI675007B - Secondary crystallization system for the formation of sodium fluoride and sodium fluoroaluminate crytals from hydrofluoric acid solution and its crystallization control method - Google Patents
Secondary crystallization system for the formation of sodium fluoride and sodium fluoroaluminate crytals from hydrofluoric acid solution and its crystallization control method Download PDFInfo
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Abstract
本發明提供一種自氫氟酸溶液生成氟化鈉與氟鋁酸鈉晶體之二次結晶系統及其結晶操作控制方法,其主要在第一階段結晶程序將包括氫氧化鈉及碳酸鈉的結晶藥劑,透過質量控制加藥添加至氟離子濃度達到40g/L以上的高濃度氫氟酸廢棄原液進行結晶反應,以獲得氟化鈉晶體以及氟離子濃度在25g/L以上的中低濃度氫氟酸反應液;並在第二階段結晶程序將包括鋁酸鈉的結晶藥劑,透過質量控制加藥添加至該中低濃度氫氟酸反應液進行結晶反應,以獲得氟鋁酸鈉晶體以及氟離子濃度在60mg/L以下的氫氟酸廢液,達到系統且穩定地產出結晶純度高且具高經濟效益的氟化鈉晶體及氟鋁酸鈉晶體之目的。The invention provides a secondary crystallization system for generating sodium fluoride and sodium fluoroaluminate crystals from a hydrofluoric acid solution and a crystallization operation control method thereof. The crystallization process mainly includes a crystallization agent of sodium hydroxide and sodium carbonate in the first stage. , Through the quality control dosing, add to the high-concentration hydrofluoric acid waste stock solution with a fluoride ion concentration of 40g / L or more to perform the crystallization reaction to obtain sodium fluoride crystals and medium-low concentration hydrofluoric acid with a fluoride ion concentration of 25g / L or more The reaction solution; and in the second stage crystallization procedure, a crystallization agent including sodium aluminate is added to the medium-low concentration hydrofluoric acid reaction solution through quality control to perform a crystallization reaction to obtain sodium fluoroaluminate crystals and fluoride ion concentration The hydrofluoric acid waste liquid below 60mg / L can achieve the purpose of systematic and stable production of sodium fluoride crystals and sodium fluoroaluminate crystals with high crystal purity and high economic benefits.
Description
本發明有關於一種結晶系統,特別是指一種利用氫氟酸溶液進行二次結晶以生成具高經濟效益之氟化鈉及氟鋁酸鈉晶體的二次結晶系統及其結晶操作控制方法。The present invention relates to a crystallization system, in particular to a secondary crystallization system using hydrofluoric acid solution for secondary crystallization to generate sodium fluoride and sodium fluoroaluminate crystals with high economic benefits, and a crystallization operation control method thereof.
按,高濃度氫氟酸(HF,49%)或氫氟酸混酸,系為半導體(IC)、液晶顯示面板(TFT-LCD)、太陽能電池等科技產業大量應用於蝕刻技術中,因而產出濃度高達49%或低至0.5%的各種濃度且體積龐大的氫氟酸廢酸,需要進行廢液處理。According to the fact, high-concentration hydrofluoric acid (HF, 49%) or hydrofluoric acid mixed acid is widely used in etching technology for semiconductors (IC), liquid crystal display panels (TFT-LCD), solar cells and other technology industries. Various concentrations of as high as 49% or as low as 0.5% of bulk hydrofluoric acid waste acid require waste liquid treatment.
目前氫氟酸廢液處理方法,以加入如CaO、Ca(OH)2、CaCl2等含鈣化合物與廢液中 氟離子反應生成氟化鈣(CaF2)污泥餅,或者,如台灣發明專利第I233428號,使氫氟酸廢液中的氟離子與特定藥劑進行化學混凝作用,藉以去除廢液中氟離子。惟前述兩種方法,前者有操作困難度及成本皆高的問題外,其氟化鈣污泥餅體積大且純度達回收標準的氟化鈣量相當有限,未能產生經濟效益;後者專利雖可形成氟鋁酸鈉晶體(Na3AlF6,俗稱冰晶石)供回收使用,然在混凝過程中須使用含氯化合物PAC(Polyalumi-num Chloride;多元聚氯化鋁)作為助凝劑,進而影響冰晶石的結晶純度,尤其該專利前案的冰晶石未以適合結晶程度及環境制得,純度更難以達到回收使用的標準。Current hydrofluoric acid waste liquid treatment methods include adding calcium-containing compounds such as CaO, Ca (OH) 2, and CaCl2 to react with fluoride ions in the waste liquid to form calcium fluoride (CaF2) sludge cake, or, for example, Taiwan Invention Patent No. No. I233428, the fluorine ions in the hydrofluoric acid waste liquid are chemically coagulated with specific agents to remove the fluoride ions in the waste liquid. However, the former two methods have the problems of difficulty in operation and high cost. In addition, the calcium fluoride sludge cake has a large volume and the purity of the calcium fluoride which reaches the recovery standard is quite limited, which fails to produce economic benefits. Can form sodium fluoroaluminate crystals (Na3AlF6, commonly known as cryolite) for recycling. However, in the coagulation process, PAC (Polyalumi-num Chloride) can be used as a coagulant to affect cryolite. The purity of the crystals, especially the cryolite in the pre-patent of the patent, was not made with suitable crystallization degree and environment, and the purity is more difficult to reach the standard for recycling.
值得注意的是,已有諸多文獻提出,氫氟酸與鋁酸鈉可經由如下反應式生成氟鋁酸鈉晶體:12HF+3NaAlO 2→Na 3AlF 6+2AlF 3+H 2O(參見TW 102144345先前技術);是以,本案發明人已據此技術提出申請第101125989號的台灣發明專利「自氫氟酸廢液生成氟鋁酸鈉晶體的結晶化系統及其結晶方法」,如圖1所示,該結晶化系統包括鋁酸鈉藥劑槽V2及高濃度氫氟酸廢液槽V1透過其批次定量控制段F1、F2,分別進流至位於系統反應槽上部的定流量與均勻分散加藥段A與反應槽下部的批次式結晶反應段R,藉由定流量與均勻分散加藥段A中分散盤的通孔分佈,控制鋁酸鈉藥劑以批次定量且均勻地加入氫氟酸廢液中進行反應,經靜置結晶後進入微過濾段S,以分離出冰晶石結晶並將過濾後液體輸送至低濃度氫氟酸廢液處理段W進行處理。 It is worth noting that many literatures have suggested that hydrofluoric acid and sodium aluminate can generate sodium fluoroaluminate crystals via the following reaction formula: 12HF + 3NaAlO 2 → Na 3 AlF 6 + 2AlF 3 + H 2 O (see TW 102144345 (Prior art); Therefore, the inventor of this case has filed an application for Taiwan Invention Patent No. 101125989 based on this technology, "Crystalization system and method for crystallization of sodium fluoroaluminate crystals from hydrofluoric acid waste liquid," as shown in Figure 1. As shown, the crystallization system includes a sodium aluminate medicament tank V2 and a high-concentration hydrofluoric acid waste liquid tank V1 through its batch quantitative control sections F1 and F2, respectively, and flows into a constant flow and uniformly dispersed addition located at the upper part of the system reaction tank. The drug section A and the batch-type crystallization reaction section R at the lower part of the reaction tank control the sodium aluminate medicament to be added in a batch quantitatively and uniformly by using a constant flow rate and the through-hole distribution of the dispersion plate in the uniformly added dosing section A. The reaction is carried out in the acid waste liquid. After standing for crystallization, it enters the microfiltration section S to separate the cryolite crystals and transport the filtered liquid to the low-concentration hydrofluoric acid waste liquid treatment section W for processing.
雖本案發明人先前提出的技術方案已可獲得純度高達96%的冰晶石結晶,惟影響結晶純度的因素不僅包括氫氟酸與鋁酸鈉的液流接觸反應方式,更包括溶劑中不純物的含量、溶液pH值等影響因素,故本案發明人進一步提出了申請第102144345號的台灣發明專利「自氫氟酸溶液生成氟鋁酸鈉晶體之結晶系統設備及其結晶操作控制方法」,其主要是透過設於系統反應槽內的分散盤與控制盤控制鋁酸鈉藥劑與氫氟酸廢液接觸反應的液流形態及流量,並藉呈回路形態與系統反應槽連通的pH值/氟離子檢測段,配合監控氫氟酸廢液及鋁酸鈉藥劑的反應溶液的pH值及氟離子濃度,有效控制系統操作過程中影響結晶純度的因素,確保系統穩定地產出結晶純度可供回收再使用的冰晶石,達到有效回收氟離子且生成具有高經濟效益的冰晶石晶體之目的。Although the technical solution previously proposed by the inventor of the present case has been able to obtain cryolite crystals with a purity of up to 96%, the factors affecting the purity of the crystals include not only the method of contacting the hydrofluoric acid with sodium aluminate in a liquid stream, but also the content of impurities in the solvent. And the pH value of the solution, the inventor of this case further proposed the Taiwan invention patent No. 102144345, "Crystal system equipment for generating sodium fluoroaluminate crystals from hydrofluoric acid solution and crystallization operation control method", which is mainly Through the dispersing disk and control disk provided in the system reaction tank, the liquid flow form and flow rate of the contact reaction of the sodium aluminate agent and the hydrofluoric acid waste liquid are controlled, and the pH value / fluoride ion detection connected to the system reaction tank through a loop shape In addition, it monitors the pH value and fluoride ion concentration of the reaction solution of the hydrofluoric acid waste solution and sodium aluminate agent to effectively control the factors affecting the purity of the crystal during the operation of the system and ensure that the system can stably produce the crystal purity for recycling and reuse. Cryolite achieves the purpose of effectively recovering fluoride ions and generating cryolite crystals with high economic benefits.
另值得注意的是,氟化鈉是一種離子化合物,分子式為NaF。室溫下為無色晶體或白色固體,無臭味;是一種重要的氟化物產品,廣泛用於木材防腐劑、釀酒殺菌劑、電解鋁調整劑、牙齒氟化劑等領域。目前,氫氟酸中和法是常用較成熟的氟化鈉生產工藝。氫氟酸中和法是用氫氧化鈉中和氫氟酸製得氟化鈉,其反應式如下:HF+NaOH→NaF+H2O。習知氟化鈉的生產過程包括:向鉛製反應釜中加入濃度40wt%的氫氟酸,再慢慢加入氫氧化鈉中和,直到反應溶液呈中性為止;最後經結晶、離心脫水、烘乾,即得氟化鈉產品。該工藝具有流程簡單、產品質量穩定的優點,然而,該工藝存在設備腐蝕嚴重的問題,因此對設備材質的要求很高,且該中和法使用市售氫氟酸作為原料等因素,皆導致氟化鈉的生產成本較高,在現階段已缺乏市場競爭力,有待進一步改進。It is also worth noting that sodium fluoride is an ionic compound with a molecular formula of NaF. At room temperature, it is a colorless crystal or white solid with no odor. It is an important fluoride product and is widely used in the fields of wood preservatives, wine fungicides, electrolytic aluminum regulators, dental fluoride agents, and other fields. At present, the hydrofluoric acid neutralization method is a commonly used and mature sodium fluoride production process. Hydrofluoric acid neutralization method uses sodium hydroxide to neutralize hydrofluoric acid to obtain sodium fluoride, and the reaction formula is as follows: HF + NaOH → NaF + H2O. The conventional production process of sodium fluoride includes: adding hydrofluoric acid with a concentration of 40% by weight to a lead reaction kettle, and then slowly adding sodium hydroxide to neutralize the reaction solution until it becomes neutral; finally, crystallization, centrifugal dehydration, Dry to obtain sodium fluoride product. This process has the advantages of simple process and stable product quality. However, this process has the problem of serious equipment corrosion, so the material requirements of the equipment are very high, and the neutralization method uses commercially available hydrofluoric acid as a raw material. The production cost of sodium fluoride is relatively high, and it lacks market competitiveness at this stage and needs further improvement.
本發明之目的在於提供一種自氫氟酸溶液生成氟化鈉與氟鋁酸鈉晶體之二次結晶系統,其主要在第一階段結晶程序將包括氫氧化鈉及碳酸鈉的第一階段結晶藥劑,透過質量控制加藥添加至氟離子濃度達到40g/L以上的高濃度氫氟酸廢棄原液進行結晶反應,以獲得氟化鈉晶體以及氟離子濃度在25g/L以上的中低濃度氫氟酸反應液;並在第二階段結晶程序將包括鋁酸鈉的第二階段結晶藥劑,透過質量控制加藥添加至該中低濃度氫氟酸反應液進行結晶反應,以獲得氟鋁酸鈉晶體以及氟離子濃度在60mg/L以下的氫氟酸廢液,達到系統且穩定地產出結晶純度高且具高經濟效益的氟化鈉晶體及氟鋁酸鈉晶體之目的。The purpose of the present invention is to provide a secondary crystallization system for generating sodium fluoride and sodium fluoroaluminate crystals from a hydrofluoric acid solution. The first-stage crystallization process will include a first-stage crystallization agent including sodium hydroxide and sodium carbonate. , Through the quality control dosing, add a high-concentration hydrofluoric acid waste stock solution with a fluoride ion concentration of more than 40g / L to perform a crystallization reaction to obtain sodium fluoride crystals and medium-low concentration hydrofluoric acid with a fluoride ion concentration of 25g / L A reaction solution; and in a second-stage crystallization procedure, a second-stage crystallization agent including sodium aluminate is added to the medium-low concentration hydrofluoric acid reaction solution through quality control to perform a crystallization reaction to obtain sodium fluoroaluminate crystals and The hydrofluoric acid waste liquid with a fluoride ion concentration below 60mg / L can achieve the purpose of systematically and stably producing sodium fluoride crystals and sodium fluoroaluminate crystals with high crystal purity and high economic benefits.
緣是,為達上述目的,本發明所提供一種自氫氟酸溶液生成氟化鈉與氟鋁酸鈉晶體之二次結晶系統,包括:一控制處理器;一第一結晶反應段,為該控制處理器電性控制;該第一結晶反應段透過該控制處理器批量控制輸入高濃度氫氟酸廢棄原液,並透過該控制處理器質量控制地加入第一結晶藥劑至該氫氟酸廢液中進行結晶反應,該第一結晶藥劑為含碳酸鈉的氫氧化鈉溶液,以生成氟化鈉晶體與中低濃度氫氟酸反應液;一第二結晶反應段,為該控制處理器電性控制並與該第一結晶反應段的輸出端連接;該第二結晶反應段透過該控制處理器批量控制輸入該中低濃度氫氟酸反應液,並透過該控制處理器質量控制地加入第二結晶藥劑至該中低濃度氫氟酸反應液中進行結晶反應,該第二結晶藥劑為鋁酸鈉溶液,以生成氟鋁酸鈉晶體與低濃度氫氟酸廢液。藉此,達到系統且穩定地產出結晶純度高且具高經濟效益的氟化鈉晶體及氟鋁酸鈉晶體之目的。The reason is that in order to achieve the above object, the present invention provides a secondary crystallization system for generating sodium fluoride and sodium fluoroaluminate crystals from a hydrofluoric acid solution, including: a control processor; a first crystallization reaction section, which is The control processor is electrically controlled; the first crystallization reaction section controls the batch input of a high-concentration hydrofluoric acid waste stock solution through the control processor, and adds the first crystallization agent to the hydrofluoric acid waste solution in a quality-controlled manner through the control processor. A crystallization reaction is performed in the first crystallization agent is a sodium hydroxide solution containing sodium carbonate to generate a reaction solution of sodium fluoride crystals and a medium-low concentration hydrofluoric acid; a second crystallization reaction section is for controlling the electrical properties of the processor. It is controlled and connected with the output end of the first crystallization reaction section; the second crystallization reaction section inputs the medium-low concentration hydrofluoric acid reaction solution through the control processor in batches, and is added to the second through the control processor under quality control A crystallization agent is crystallized into the medium-low concentration hydrofluoric acid reaction solution, and the second crystallization agent is a sodium aluminate solution to generate sodium fluoroaluminate crystals and a low-concentration hydrofluoric acid waste solution. Thereby, the purpose of systematically and stably producing sodium fluoride crystals and sodium fluoroaluminate crystals with high crystal purity and high economic benefits is achieved.
本發明另提供一種自氫氟酸溶液生成氟化鈉與氟鋁酸鈉晶體之二次結晶系統,包括:一控制處理器;一第一結晶反應段,為該控制處理器電性控制;該第一結晶反應段透過該控制處理器批量控制輸入高濃度氫氟酸廢棄原液,並透過該控制處理器質量控制地加入第一結晶藥劑至該氫氟酸廢液中進行結晶反應,該第一結晶藥劑為含碳酸鈉的氫氧化鈉溶液,以生成氟化鈉晶體與中低濃度氫氟酸反應液;一第二結晶反應段,為該控制處理器電性控制並與該第一結晶反應段的輸出端連接;該第二結晶反應段透過該控制處理器批量控制輸入該中低濃度氫氟酸反應液,並透過該控制處理器質量控制地加入第二結晶藥劑至該中低濃度氫氟酸反應液中進行結晶反應,該第二結晶藥劑為鋁酸鈉溶液,以生成氟鋁酸鈉晶體與低濃度氫氟酸廢液;該第二結晶反應段內部設有投藥空間及反應空間,該投藥空間及該反應空間通過設於該第二結晶反應段外部的一回流泵連通,該回流泵抽吸該反應空間內含有晶核的反應溶液至該投藥空間中形成植種晶核。藉此,除了達到系統且穩定地產出結晶純度高且具高經濟效益的氟化鈉晶體及氟鋁酸鈉晶體之目的,進一步利用回流泵將含有晶核的反應溶液回流,實現增加結晶率。The present invention further provides a secondary crystallization system for generating sodium fluoride and sodium fluoroaluminate crystals from a hydrofluoric acid solution, including: a control processor; a first crystallization reaction section for electrically controlling the control processor; The first crystallization reaction section controls the batch input of the high-concentration hydrofluoric acid waste stock solution through the control processor, and adds the first crystallization agent to the hydrofluoric acid waste liquid through the control processor to control the quality of the crystallization reaction. The crystallization agent is a sodium hydroxide solution containing sodium carbonate to generate a reaction solution of sodium fluoride crystals and low-concentration hydrofluoric acid. A second crystallization reaction section is electrically controlled by the control processor and reacts with the first crystal. The output end of the section is connected; the second crystallization reaction section inputs the medium-low concentration hydrofluoric acid reaction solution through the control processor in batches, and adds a second crystallization agent to the medium-low concentration hydrogen through the control processor in a quality control manner. A crystallization reaction is performed in a hydrofluoric acid reaction solution, and the second crystallization agent is a sodium aluminate solution to generate sodium fluoroaluminate crystals and a low-concentration hydrofluoric acid waste liquid; The medicine space and the reaction space, the medicine injection space and the reaction space are communicated through a reflux pump provided outside the second crystallization reaction section, and the reflux pump sucks the reaction solution containing crystal nuclei in the reaction space to the medicine injection space to form Seed nuclei. Therefore, in addition to achieving the purpose of systematically and stably producing sodium fluoride crystals and sodium fluoroaluminate crystals with high crystal purity and high economic benefits, the reaction solution containing crystal nuclei is further refluxed by a reflux pump to increase the crystallization rate.
進一步地,本發明二次結晶系統還包括用以測定第一階段結晶程序pH值反應終點的第一pH值檢測段,以及用以測定第二階段結晶程序pH值反應終點的第二pH值檢測段。Further, the secondary crystallization system of the present invention further includes a first pH detection section for determining a pH reaction end point of the crystallization process in the first stage, and a second pH detection for determining a pH reaction end point of the crystallization process in the second stage. segment.
進一步地,本發明二次結晶系統還包括用以測定第二階段結晶程序的氟離子濃度檢測段FD,以確定第二階段結晶程序的初始結晶反應終點,便於配合前述第二pH值檢測段D2進行pH值的微調,以達到精確的結晶反應終點,保證第二階段結晶程序最後輸出的低濃度氫氟酸廢液的濃度低於排放濃度。Further, the secondary crystallization system of the present invention further includes a fluoride ion concentration detection section FD for determining the second-stage crystallization procedure to determine the end point of the initial crystallization reaction of the second-stage crystallization procedure, which is convenient to cooperate with the second pH detection section D2. Fine-adjust the pH value to reach the precise end of the crystallization reaction, and ensure that the concentration of the low-concentration hydrofluoric acid waste liquid output at the end of the second-stage crystallization process is lower than the discharge concentration.
進一步地,本發明二次結晶系統中,該第一結晶藥劑經一第一質量控制加藥段輸出均勻分散的點滴狀液流至該第一結晶反應段內與該高濃度氫氟酸廢棄原液進行結晶反應;該鋁酸鈉溶液經一第二質量控制加藥段輸出均勻分散的點滴狀液流至該第二結晶反應段內與該中低濃度氫氟酸反應液進行結晶反應。藉此,透過將第一結晶藥劑與第二結晶藥劑形成點滴狀液流與氫氟酸廢液反應,以增加結晶反應的結晶率,提高從廢液中回收氟化鈉晶體及氟鋁酸鈉晶體的效率。Further, in the secondary crystallization system of the present invention, the first crystallization agent outputs a uniformly dispersed drip-shaped liquid through a first quality control dosing section to the first crystallization reaction section and the high-concentration hydrofluoric acid waste stock solution is discharged. A crystallization reaction is performed; the sodium aluminate solution flows through a second quality control dosing section to output uniformly dispersed droplets into the second crystallization reaction section to perform a crystallization reaction with the medium-low concentration hydrofluoric acid reaction solution. Thereby, by reacting the first crystalline agent and the second crystalline agent to form a drip-like liquid stream with the hydrofluoric acid waste liquid, the crystallization rate of the crystallization reaction is increased, and the sodium fluoride crystals and sodium fluoroaluminate are recovered from the waste liquid. Crystal efficiency.
進一步地,本發明二次結晶系統還包括第一固液分離段及第二固液分離段,用以將達到反應終點的反應溶液中的晶體與液體快速分離。且該第一固液分離段及該第二固液分離段還可進一步分別連接第一清洗處理段及第二清洗處理段,用以排出該分離後的液體,或者,輸入清水或其他適當的清潔液至第一固液分離段、第二固液分離段中進行晶體清洗,以避免雜質殘留,保證晶體的純度。Further, the secondary crystallization system of the present invention further includes a first solid-liquid separation section and a second solid-liquid separation section, which are used to quickly separate crystals and liquids in the reaction solution that reaches the end of the reaction. In addition, the first solid-liquid separation section and the second solid-liquid separation section may be further connected to the first cleaning treatment section and the second cleaning treatment section, respectively, to discharge the separated liquid, or input clean water or other appropriate The cleaning liquid is cleaned in the first solid-liquid separation section and the second solid-liquid separation section to avoid impurities remaining and ensure the purity of the crystals.
進一步地,本發明二次結晶系統的高濃度氫氟酸廢棄原液儲存在高濃度氫氟酸廢液槽中,並透過一計量進流控制段與第一結晶反應段連接以批量輸出高濃度氫氟酸廢棄原液至第一結晶反應段。該第一結晶藥劑儲存在含碳酸鈉的氫氧化鈉溶液儲槽中,該第二結晶藥劑儲存在鋁酸鈉溶液儲槽中。Further, the high-concentration hydrofluoric acid waste stock solution of the secondary crystallization system of the present invention is stored in a high-concentration hydrofluoric acid waste liquid tank, and is connected to the first crystallization reaction section through a metering inflow control section to output high-concentration hydrogen in batches. The hydrofluoric acid discards the stock solution to the first crystallization reaction section. The first crystalline agent is stored in a sodium carbonate solution storage tank containing sodium carbonate, and the second crystalline agent is stored in a sodium aluminate solution storage tank.
此外,為使本發明自氫氟酸溶液生成氟化鈉與氟鋁酸鈉晶體之二次結晶系統能確實產出具有高經濟效益的氟化鈉與氟鋁酸鈉晶體,本發明另提供該系統的結晶操作控制方法,該方法包括初步設定程序、第一階段結晶程序以及第二階段結晶程序,該初步設定程序包括參數設定步驟,該第一階段結晶程序包括高濃度氫氟酸廢棄原液輸入步驟、第一階段結晶藥劑添加步驟及氟化鈉晶體處理步驟,該第二階段結晶程序包括中低濃度氫氟酸反應液輸入步驟、第二階段結晶藥劑添加步驟及氟鋁酸鈉晶體處理步驟:其中:In addition, in order that the secondary crystallization system for generating sodium fluoride and sodium fluoroaluminate crystals from a hydrofluoric acid solution according to the present invention can surely produce sodium fluoride and sodium fluoroaluminate crystals with high economic benefits, the present invention provides the same System crystallization operation control method. The method includes a preliminary setting procedure, a first-stage crystallization procedure, and a second-stage crystallization procedure. The preliminary setting procedure includes a parameter setting step. The first-stage crystallization procedure includes input of a high-concentration hydrofluoric acid waste stock solution. Step, the first-stage crystallization agent adding step and the sodium fluoride crystal processing step, the second-stage crystallization procedure includes a medium-low concentration hydrofluoric acid reaction solution input step, the second-stage crystallization agent adding step, and the sodium fluoroaluminate crystal processing step :among them:
該參數設定步驟:透過控制處理器設定參數項目及其數值範圍;The parameter setting step: set the parameter item and its value range through the control processor;
該高濃度氫氟酸廢棄原液輸入步驟:根據該參數設定步驟的設定值,將高濃度氫氟酸廢棄原液批量輸入第一結晶反應段的反應空間內;The high-concentration hydrofluoric acid waste stock solution input step: inputting the high-concentration hydrofluoric acid waste stock solution in batches into the reaction space of the first crystallization reaction section according to the set value of the parameter setting step;
該第一階段結晶藥劑添加步驟:根據該參數設定步驟的設定值,將含碳酸鈉的氫氧化鈉溶液輸出至第一質量控制加藥段以形成點滴狀液流並落入至第一結晶反應段的反應空間內,令該含碳酸鈉的氫氧化鈉溶液與該高濃度氫氟酸廢棄原液進行結晶反應,並生成氟化鈉晶體與中低濃度氫氟酸反應液;The first-stage crystallization agent adding step: according to the setting value of the parameter setting step, output the sodium carbonate-containing sodium hydroxide solution to the first quality control dosing section to form a drip-like liquid flow and fall into the first crystallization reaction In the reaction space of the section, the sodium carbonate solution containing sodium carbonate and the high-concentration hydrofluoric acid waste stock solution are subjected to crystallization reaction, and a sodium fluoride crystal and a medium-low concentration hydrofluoric acid reaction solution are generated;
該氟化鈉晶體處理步驟:收集並清洗該氟化鈉晶體;The sodium fluoride crystal processing step: collecting and cleaning the sodium fluoride crystal;
該中低濃度氫氟酸反應液輸入步驟:根據該參數設定步驟的設定值,將該中低濃度氫氟酸反應液批量輸入第二結晶反應段的反應空間內;The medium-low-concentration hydrofluoric acid reaction solution input step: inputting the medium-low-concentration hydrofluoric acid reaction solution in batches into the reaction space of the second crystallization reaction section according to the set value of the parameter setting step;
該第二階段結晶藥劑添加步驟:根據該參數設定步驟的設定值,將鋁酸鈉溶液輸出至第二質量控制加藥段以形成點滴狀液流並落入至第二結晶反應段的反應空間內,令該鋁酸鈉溶液與該中低濃度氫氟酸反應液進行結晶反應,並生成氟鋁酸鈉晶體與低濃度氫氟酸廢液;The second-stage crystallization agent adding step: according to the set value of the parameter setting step, output the sodium aluminate solution to the second quality control dosing section to form a drip-like liquid flow and fall into the reaction space of the second crystallization reaction section Inside, the sodium aluminate solution is subjected to a crystallization reaction with the medium-low concentration hydrofluoric acid reaction solution to generate sodium fluoroaluminate crystals and a low-concentration hydrofluoric acid waste liquid;
氟鋁酸鈉晶體處理步驟:收集並清洗該氟鋁酸鈉晶體。Sodium fluoroaluminate crystal processing step: Collect and wash the sodium fluoroaluminate crystal.
進一步地,該結晶操作控制方法還包括在該第一階段結晶藥劑添加步驟及該氟化鈉晶體處理步驟之間進行第一階段pH值檢測步驟、靜置反應步驟及第一階段固液分離步驟,以利用測得的pH值判定結晶反應終點後,對氟化鈉晶體進行固液分離。Further, the crystallization operation control method further includes performing a first-stage pH detection step, a standing reaction step, and a first-stage solid-liquid separation step between the first-stage crystallization agent adding step and the sodium fluoride crystal processing step. After the end point of the crystallization reaction is determined by using the measured pH value, solid-liquid separation is performed on the sodium fluoride crystal.
進一步地,該結晶操作控制方法還包括在該第二階段結晶藥劑添加步驟及該氟鋁酸鈉晶體處理步驟之間進行第二階段氟離子檢測步驟、第二階段pH值檢測步驟、靜置反應步驟及第二階段固液分離步驟,以利用測得的氟離子濃度先判定初始的結晶反應終點後,再利用測得的pH值微調反應溶液至參數設定步驟設定的pH值,並對氟鋁酸鈉晶體進行固液分離。Further, the crystallization operation control method further includes performing a second-stage fluoride ion detection step, a second-stage pH value detection step, and a standing reaction between the second-stage crystallization agent adding step and the sodium fluoroaluminate crystal processing step. Step and the second-stage solid-liquid separation step, in order to determine the initial crystallization reaction end point by using the measured fluoride ion concentration, and then use the measured pH value to fine-tune the reaction solution to the pH value set in the parameter setting step, Sodium crystals were subjected to solid-liquid separation.
進一步地,該第二階段結晶藥劑添加步驟還包括從第二結晶反應段的反應空間內抽取含有晶核的反應溶液回流至投藥空間中,以提高第二階段結晶程序的氟鋁酸鈉晶體結晶率。Further, the second-stage crystallization agent adding step further includes extracting the reaction solution containing crystal nuclei from the reaction space of the second crystallization reaction section and returning the reaction solution to the dosing space, so as to improve the second-stage crystallization procedure of sodium fluoroaluminate crystals. rate.
有關於本發明為達成上述目的,所採用之技術、手段及其他功效,茲舉一較佳可行實施例並配合圖式詳細說明如後。Regarding the technology, means, and other effects adopted by the present invention to achieve the above-mentioned objectives, a preferred and feasible embodiment is described in detail below with reference to the drawings.
為利於對本發明的瞭解,以下結合附圖及實施例進行說明。In order to facilitate understanding of the present invention, the following is described with reference to the accompanying drawings and embodiments.
本發明特徵與優點的一些實施例將在以下說明中詳細敘述。應理解的是本發明能夠在不同的態樣上具有各種的變化,然其皆不脫離本發明的範圍,且其中的說明及圖式在本質上係當作說明之用,而非用於限制本發明。Some embodiments of the features and advantages of the present invention will be described in detail in the following description. It should be understood that the present invention can have various changes in different aspects, but they do not depart from the scope of the present invention, and the descriptions and drawings therein are essentially for the purpose of illustration, not for limitation. this invention.
如圖1所示,本發明自氫氟酸溶液生成氟化鈉與氟鋁酸鈉晶體之二次結晶系統主要包括第一階段結晶程序及第二階段結晶程序,該第一階段結晶程序是基於反應式:HF + NaOH → NaF + H 2O,2 HF + Na 2CO 3→ 2 NaF + CO 2+ H 2O,將含碳酸鈉的氫氧化鈉溶液作為第一結晶藥劑CR1與高濃度氫氟酸廢棄原液HHF進行第一次結晶反應,生成可回收使用的氟化鈉晶體C1及中低濃度氫氟酸反應液LHF;該第二階段結晶程序則是基於反應式:3Na ++ Al 3++ 6F- → Na 3AlF 6,將鋁酸鈉溶液作為第二結晶藥劑CR2與第一階段結晶程序反應後形成的中低濃度氫氟酸反應液LHF進行第二次結晶反應,生成可回收使用的氟鋁酸鈉晶體C2及符合排放標準的低濃度氫氟酸廢液。 As shown in FIG. 1, the secondary crystallization system for generating sodium fluoride and sodium fluoroaluminate crystals from a hydrofluoric acid solution according to the present invention mainly includes a first-stage crystallization procedure and a second-stage crystallization procedure. The first-stage crystallization procedure is based on Reaction formula: HF + NaOH → NaF + H 2 O, 2 HF + Na 2 CO 3 → 2 NaF + CO 2 + H 2 O, using sodium carbonate solution containing sodium carbonate as the first crystallization agent CR1 and high concentration hydrogen The first crystallization reaction of HHF waste raw liquid HHF is performed to generate recyclable sodium fluoride crystal C1 and medium-low concentration hydrofluoric acid reaction liquid LHF. The second-stage crystallization procedure is based on the reaction formula: 3Na + + Al 3 + + 6F- → Na 3 AlF 6 , using the sodium aluminate solution as the second crystallization agent CR2 to react with the low- and medium-concentration hydrofluoric acid reaction solution LHF formed after the first-stage crystallization procedure, and perform a second crystallization reaction to generate a recoverable Used sodium fluoroaluminate crystal C2 and low concentration hydrofluoric acid waste liquid that meets the discharge standards.
於本發明實施例中,該高濃度氫氟酸廢棄原液HHF的氟離子濃度為40g/L以上,且較佳為40至55g/L;該中低濃度氫氟酸反應液LHF的氟離子濃度為25g/L以上,且較佳為25至30g/L;該低濃度氫氟酸廢液的氟離子濃度為60mg/L以上。In the embodiment of the present invention, the fluoride ion concentration of the high-concentration hydrofluoric acid waste stock solution HHF is 40 g / L or more, and preferably 40 to 55 g / L; the fluoride ion concentration of the low-concentration hydrofluoric acid reaction solution LHF It is 25 g / L or more, and preferably 25 to 30 g / L. The fluoride ion concentration of the low-concentration hydrofluoric acid waste liquid is 60 mg / L or more.
具體地,如圖1所示,該第一階段結晶程序中的設備包括高濃度氫氟酸廢液槽V1及其計量進流控制段F、含碳酸鈉的氫氧化鈉溶液儲槽V2、第一質量控制加藥段A1、第一結晶反應段R1、第一pH值檢測段D1、第一固液分離段SE1及第一清洗處理段W1。該第二階段結晶程序中的設備包括鋁酸鈉溶液儲槽V3、第二質量控制加藥段A2、第二結晶反應段R2、氟離子濃度檢測段FD、第二pH值檢測段D2、第二固液分離段SE2及第二清洗處理段W2。其中,以上設備皆與控制處理器P電性連接並根據控制處理器P內部的設定值進行工作。Specifically, as shown in FIG. 1, the equipment in the first-stage crystallization process includes a high-concentration hydrofluoric acid waste liquid tank V1 and its metering inflow control section F, a sodium carbonate-containing sodium hydroxide solution storage tank V2, a first A quality control dosing section A1, a first crystallization reaction section R1, a first pH detection section D1, a first solid-liquid separation section SE1, and a first cleaning treatment section W1. The equipment in the second-stage crystallization program includes a sodium aluminate solution storage tank V3, a second quality control dosing section A2, a second crystallization reaction section R2, a fluoride ion concentration detection section FD, a second pH value detection section D2, The second solid-liquid separation section SE2 and the second cleaning treatment section W2. The above devices are all electrically connected to the control processor P and work according to a set value inside the control processor P.
該高濃度氫氟酸廢液槽V1透過該計量進流控制段F與第一結晶反應段R1連接,該計量進流控制段F為該控制處理器P電性控制以批量輸出該高濃度氫氟酸廢棄原液HHF至該第一結晶反應段R1。該含碳酸鈉的氫氧化鈉溶液儲槽V2為該控制處理器P電性控制以輸出該第一結晶藥劑CR1至該第一質量控制加藥段A1。The high-concentration hydrofluoric acid waste liquid tank V1 is connected to the first crystallization reaction section R1 through the metering inflow control section F. The metering inflow control section F is electrically controlled by the control processor P to output the high-concentration hydrogen in batches. The hydrofluoric acid waste stock solution HHF is passed to the first crystallization reaction section R1. The sodium carbonate-containing sodium hydroxide solution storage tank V2 is electrically controlled by the control processor P to output the first crystalline agent CR1 to the first quality control dosing section A1.
該第一結晶反應段R1為該控制處理器P電性控制;該第一結晶反應段R1透過該控制處理器P批量控制輸入高濃度氫氟酸廢棄原液HHF,並透過該控制處理器P質量控制地加入第一結晶藥劑CR1至該氫氟酸廢液中進行結晶反應,該第一結晶藥劑CR1為含碳酸鈉的氫氧化鈉溶液,以生成氟化鈉晶體C1與中低濃度氫氟酸反應液LHF。具體地,該第一結晶藥劑CR1經一第一質量控制加藥段A1輸出均勻分散的點滴狀液流至該第一結晶反應段R1內與該高濃度氫氟酸廢棄原液HHF進行結晶反應。The first crystallization reaction section R1 is electrically controlled by the control processor P. The first crystallization reaction section R1 inputs the high-concentration hydrofluoric acid waste stock solution HHF through the control processor P in batch control, and passes through the control processor P quality. The first crystallization agent CR1 is controlledly added to the hydrofluoric acid waste liquid for crystallization reaction. The first crystallization agent CR1 is a sodium hydroxide solution containing sodium carbonate to generate sodium fluoride crystal C1 and medium-low concentration hydrofluoric acid. Reaction liquid LHF. Specifically, the first crystallization agent CR1 outputs a uniformly dispersed drip-shaped liquid through a first quality control dosing section A1 to flow into the first crystallization reaction section R1 to perform a crystallization reaction with the high-concentration hydrofluoric acid waste stock solution HHF.
在第一階段結晶程序,結晶反應終點的判定是經由啟動第二pH值檢測段D2配合第一質量控制加藥段A1調節鋁酸鈉溶液的加藥量,直到pH測定值達到控制處理器P的設定值後停止加藥。該第一pH值檢測段D1為該控制處理器P電性控制並與該第一結晶反應段R1連接;該第一pH值檢測段D1透過該控制處理器P控制測量該第一結晶反應段R1內部的反應溶液的pH值,所述控制處理器P根據測得的pH值判定該第一結晶反應段R1的反應終點。具體地,該第一pH值檢測段D1包括pH值計以及連接在pH值計與該第一結晶反應段R1之間的回路管道,令控制處理器P控制第一pH值檢測段D1工作抽取第一結晶反應段R1的反應溶液進行pH值測定後,再輸送回到第一結晶反應段R1內持續反應。In the first stage of the crystallization process, the end point of the crystallization reaction is determined by starting the second pH detection section D2 and the first quality control dosing section A1 to adjust the dosing amount of the sodium aluminate solution until the pH measurement value reaches the control processor P Dosing stops after the set value of. The first pH detection section D1 is electrically controlled by the control processor P and is connected to the first crystallization reaction section R1. The first pH detection section D1 controls and measures the first crystallization reaction section through the control processor P. The pH value of the reaction solution inside R1, and the control processor P determines the reaction end point of the first crystallization reaction section R1 according to the measured pH value. Specifically, the first pH detection section D1 includes a pH meter and a loop pipe connected between the pH meter and the first crystallization reaction section R1, so that the control processor P controls the work extraction of the first pH detection section D1. After the pH of the reaction solution of the first crystallization reaction section R1 is measured, it is transported back to the first crystallization reaction section R1 to continue the reaction.
該第一固液分離段SE1為該控制處理器P電性控制並與該第一結晶反應段R1的輸出端連接;該第一固液分離段SE1透過該控制處理器P控制分離該第一結晶反應段R1輸出的氟化鈉晶體C1與中低濃度氫氟酸反應液LHF。較佳的,為了保證第一固液分離段SE1的清潔,該第一固液分離段SE1的液體輸出端與該第一清洗處理段W1連接,該第一清洗處理段W1為該控制處理器P電性控制,供形成輸出該中低濃度氫氟酸反應液LHF的路徑或者輸入清水清洗該第一固液分離段SE1中的氟化鈉晶體C1。The first solid-liquid separation section SE1 is electrically controlled by the control processor P and is connected to the output of the first crystallization reaction section R1. The first solid-liquid separation section SE1 controls and separates the first through the control processor P. The sodium fluoride crystal C1 output from the crystallization reaction section R1 and the medium-low concentration hydrofluoric acid reaction solution LHF. Preferably, in order to ensure the cleaning of the first solid-liquid separation section SE1, the liquid output end of the first solid-liquid separation section SE1 is connected to the first cleaning processing section W1, and the first cleaning processing section W1 is the control processor. P is electrically controlled for forming a path for outputting the medium-low concentration hydrofluoric acid reaction solution LHF or inputting clean water to clean the sodium fluoride crystal C1 in the first solid-liquid separation section SE1.
該鋁酸鈉溶液儲槽V3為該控制處理器P電性控制以輸出該第二結晶藥劑CR2至該第二質量控制加藥段A2。該第二結晶反應段R2為該控制處理器P電性控制並與該第一結晶反應段R1的輸出端連接;該第二結晶反應段R2透過該控制處理器P批量控制輸入該中低濃度氫氟酸反應液LHF,並透過該控制處理器P質量控制地加入第二結晶藥劑CR2至該中低濃度氫氟酸反應液LHF中進行結晶反應,該第二結晶藥劑CR2為鋁酸鈉溶液,以生成氟鋁酸鈉晶體C2與低濃度氫氟酸廢液。具體地,該鋁酸鈉溶液經一第二質量控制加藥段A2輸出均勻分散的點滴狀液流至該第二結晶反應段R2內與該中低濃度氫氟酸反應液LHF進行結晶反應。The sodium aluminate solution storage tank V3 is electrically controlled by the control processor P to output the second crystalline agent CR2 to the second quality control dosing section A2. The second crystallization reaction section R2 is electrically controlled by the control processor P and is connected to the output terminal of the first crystallization reaction section R1. The second crystallization reaction section R2 is input to the low-medium concentration through the control processor P in batch control. Hydrofluoric acid reaction liquid LHF, and through the control processor P, a second crystallization agent CR2 is added to the medium-low concentration hydrofluoric acid reaction liquid LHF for crystallization reaction. The second crystallization agent CR2 is a sodium aluminate solution. To generate sodium fluoroaluminate crystal C2 and low concentration hydrofluoric acid waste liquid. Specifically, the sodium aluminate solution flows through a second quality control dosing section A2 to output uniformly dispersed droplets into the second crystallization reaction section R2 to perform a crystallization reaction with the medium-low concentration hydrofluoric acid reaction solution LHF.
在第二階段結晶程序中,結晶反應終點的判定是經由氟離子濃度檢測段FD進行初步的氟離子測定值達到控制處理器P的設定值後,再啟動第二pH值檢測段D2配合第二質量控制加藥段A2微調鋁酸鈉溶液的加藥量,直到pH測定值達到控制處理器P的設定值後停止加藥。In the second-stage crystallization procedure, the end point of the crystallization reaction is determined through the preliminary determination of the fluoride ion value through the fluoride ion concentration detection section FD to reach the set value of the control processor P, and then the second pH detection section D2 is started to cooperate with the second The quality control dosing section A2 finely adjusts the dosing amount of the sodium aluminate solution, and stops the dosing until the measured value of the pH reaches the set value of the control processor P.
該氟離子濃度檢測段FD為該控制處理器P電性控制並與該第二結晶反應段R2連接;該氟離子濃度檢測段FD透過該控制處理器P控制測量該第二結晶反應段R2內部的反應溶液的氟離子濃度;令該控制處理器P根據測得的氟離子判定該第二結晶反應段R2的初始反應終點,該控制處理器P並根據該第二pH值檢測段D2測得的pH值判定第二結晶反應段R2的最終反應終點。具體地,該氟離子濃度檢測段FD包括氟量計以及連接在氟量計與該第二結晶反應段R2之間的回路管道,令控制處理器P控制氟離子濃度檢測段FD工作抽取第二結晶反應段R2的反應溶液進行氟離子濃度測定後,再輸送回到第二結晶反應段R21內持續反應。The fluoride ion concentration detection section FD is electrically controlled by the control processor P and is connected to the second crystallization reaction section R2; the fluoride ion concentration detection section FD controls and measures the inside of the second crystallization reaction section R2 through the control processor P The concentration of fluoride ion in the reaction solution; the control processor P determines the initial reaction end point of the second crystallization reaction section R2 based on the measured fluoride ion, and the control processor P measures the second crystal reaction section R2 according to the measured value. The final pH of the second crystallization reaction section R2 determines the end point of the reaction. Specifically, the fluoride ion concentration detection section FD includes a fluorine meter and a loop pipe connected between the fluorine meter and the second crystallization reaction section R2, so that the control processor P controls the fluorine ion concentration detection section FD to extract a second After measuring the fluoride ion concentration in the reaction solution of the crystallization reaction section R2, it is transported back to the second crystallization reaction section R21 to continue the reaction.
該第二pH值檢測段D2為該控制處理器P電性控制並與該第二結晶反應段R2連接;該第二pH值檢測段D2透過該控制處理器P控制測量該第二結晶反應段R2內部的反應溶液pH值,所述控制處理器P根據測得的pH值判定該第二結晶反應段R2的反應終點。具體地,該第二pH值檢測段D2包括pH值計以及連接在pH值計與該第二結晶反應段R2之間的回路管道,令控制處理器P控制第二pH值檢測段D2工作抽取第二結晶反應段R2的反應溶液進行pH值測定後,再輸送回到第二結晶反應段R21內持續反應。The second pH detection section D2 is electrically controlled by the control processor P and is connected to the second crystallization reaction section R2. The second pH detection section D2 controls and measures the second crystallization reaction section through the control processor P. The pH value of the reaction solution in R2, and the control processor P determines the reaction end point of the second crystallization reaction section R2 according to the measured pH value. Specifically, the second pH detection section D2 includes a pH meter and a loop pipeline connected between the pH meter and the second crystallization reaction section R2, so that the control processor P controls the work extraction of the second pH detection section D2. After the pH value of the reaction solution in the second crystallization reaction section R2 is measured, it is transported back to the second crystallization reaction section R21 to continue the reaction.
該第二固液分離段SE2為該控制處理器P電性控制並與該第二結晶反應段R2的輸出端連接;該第二固液分離段SE2透過該控制處理器P控制分離該第二結晶反應段R2輸出的氟鋁酸鈉晶體C2與中低濃度氫氟酸反應液LHF。較佳的,為了保證第二固液分離段SE2的清潔,該第二固液分離段SE2的液體輸出端與該第二清洗處理段W2連接,該第二清洗處理段W2為該控制處理器P電性控制,供形成輸出該低濃度氫氟酸廢液的路徑或者輸入清水清洗該第二固液分離段SE2中的氟鋁酸鈉晶體C2。The second solid-liquid separation section SE2 is electrically controlled by the control processor P and is connected to the output of the second crystallization reaction section R2; the second solid-liquid separation section SE2 controls and separates the second through the control processor P The sodium fluoroaluminate crystal C2 output from the crystallization reaction section R2 and the medium-low concentration hydrofluoric acid reaction solution LHF. Preferably, in order to ensure the cleaning of the second solid-liquid separation section SE2, the liquid output end of the second solid-liquid separation section SE2 is connected to the second cleaning processing section W2, and the second cleaning processing section W2 is the control processor. P is electrically controlled for forming a path for outputting the low-concentration hydrofluoric acid waste liquid or inputting clean water to clean the sodium fluoroaluminate crystal C2 in the second solid-liquid separation section SE2.
於本發明實施例中,如圖4所示,該第一結晶反應段R1及該第二結晶反應段R2的主體皆為結晶反應槽;該第一質量控制加藥段A1及該第二質量控制加藥段A2皆分別包括有一具多個液孔的分散盤以及一位於該分散盤上且具多個通孔的控制盤;其中,該第一質量控制加藥段A1的分散盤及控制盤設於該第一結晶反應段R1的結晶反應槽中,該第二質量控制加藥段A2的分散盤及控制盤設於該第二結晶反應段R2的結晶反應槽中;藉此,令該結晶反應槽內部為該分散盤及該控制盤隔開形成位於上部的投藥空間(對應圖4的質量控制加藥部A21的內部空間)以及位於下部的反應空間(對應圖4的晶體沉積部A22的內部空間),該第一質量控制加藥段A1透過該控制處理器P控制轉動該控制盤,以調整該控制盤的通孔與該分散盤的液孔對合孔數並調節從該投藥空間落至該反應空間的點滴狀液流的流量。該第一質量控制加藥段A1的控制盤及分散盤對合孔數調節機構及其調節方法已公開於本案發明人先前提出的申請第101125989號的台灣發明專利「自氫氟酸廢液生成氟鋁酸鈉晶體的結晶化系統及其結晶方法」中,故在此不再贅述。In the embodiment of the present invention, as shown in FIG. 4, the bodies of the first crystallization reaction section R1 and the second crystallization reaction section R2 are both crystallization reaction tanks; the first quality control dosing section A1 and the second quality. The control dosing section A2 includes a dispersion plate with a plurality of liquid holes and a control plate on the dispersion plate with a plurality of through holes. Among them, the dispersion plate and control of the first quality control dosing section A1. The plate is set in the crystallization reaction tank of the first crystallization reaction section R1, and the dispersion plate and the control plate of the second quality control dosing section A2 are set in the crystallization reaction tank of the second crystallization reaction section R2; The inside of the crystallization reaction tank is separated from the dispersion plate and the control plate to form an upper injection space (corresponding to the internal space of the quality control dosing unit A21 in FIG. 4) and a lower reaction space (corresponding to the crystal deposition portion in FIG. 4). Internal space of A22), the first quality control dosing section A1 controls the control disc to rotate through the control processor P to adjust the number of through holes of the control disc and the liquid holes of the dispersion disc and adjust the number of Drops from the dosing space to the reaction space The flow of the sap flow. The control panel and dispersing disc number of holes in the first quality control dosing section A1 and the adjusting mechanism and adjusting method thereof have been disclosed in the Taiwan invention patent No. 101125989 previously filed by the inventor of the present application "Self-generating hydrofluoric acid waste liquid" The crystallization system of sodium fluoroaluminate crystals and its crystallization method "will not be repeated here.
進一步地,如圖4所示,該第二結晶反應段R2包括了第二結晶反應槽A20,該第二結晶反應槽A20的上部形成質量控制加藥部A21(即投藥空間),下部形成晶體沉積部A22(即反應空間),令鋁酸鈉溶液從質量控制加藥部A21點滴落入反應空間後與中低濃度氫氟酸反應液LHF進行結晶反應,並在晶體沉積部A22內形成顆粒較大的晶體C21與顆粒較小的晶核C22。為了提高氟鋁酸鈉晶體C2的結晶率,該質量控制加藥部A21及該晶體沉積部A22之間可進一步在該第二結晶反應槽A20外部設置一回流泵A23連通,藉此,利用該回流泵A23抽吸該反應空間內含有晶核C22的反應溶液至該投藥空間中形成植種晶核,令該晶核C22與鋁酸鈉溶液一起點滴落入中低濃度氫氟酸反應液LHF中,從而提高了本發明第二階段結晶程序的氟鋁酸鈉晶體結晶率。Further, as shown in FIG. 4, the second crystallization reaction section R2 includes a second crystallization reaction tank A20, and the upper part of the second crystallization reaction tank A20 forms a quality control dosing section A21 (ie, a dosing space), and the lower part forms a crystal. Deposition part A22 (that is, reaction space), so that the sodium aluminate solution drips from the quality control dosing part A21 into the reaction space, and then performs a crystallization reaction with the low-concentration hydrofluoric acid reaction solution LHF, and forms particles in the crystal deposition part A22 The larger crystal C21 and the smaller crystal nucleus C22. In order to increase the crystallization rate of the sodium fluoroaluminate crystal C2, a reflux pump A23 can be further provided outside the second crystallization reaction tank A20 between the quality control dosing section A21 and the crystal deposition section A22, thereby utilizing the The reflux pump A23 sucks the reaction solution containing the crystal nucleus C22 in the reaction space to form a seed crystal nucleus in the injection space, so that the crystal nucleus C22 and the sodium aluminate solution are dropped into the low- and medium-concentration hydrofluoric acid reaction solution LHF. In this way, the crystallinity of sodium fluoroaluminate in the second-stage crystallization procedure of the present invention is improved.
於本發明自氫氟酸溶液生成氟化鈉與氟鋁酸鈉晶體之二次結晶系統中,各段設備之間具有管道、泵浦及閥件連接,用以調控液體的輸送狀態及輸送量。其中,該泵浦皆與控制處理器P電性連接並受其控制工作;該閥件包括電動閥及/或手動控制閥,以配合控制系統整體的液態輸送。此外,該高濃度氫氟酸廢液槽V1、含碳酸鈉的氫氧化鈉溶液儲槽V2、鋁酸鈉溶液儲槽V3以及第一結晶反應段R1、第二結晶反應段R2內部較佳設有液位計,令控制處理器P通過液位計偵測各段設備內的液位狀態。In the secondary crystallization system for generating sodium fluoride and sodium fluoroaluminate crystals from a hydrofluoric acid solution according to the present invention, pipes, pumps, and valve connections are connected between each section of equipment to control the liquid transportation state and quantity. . The pump is electrically connected to the control processor P and controlled by the control processor P. The valve includes an electric valve and / or a manual control valve to cooperate with the overall liquid conveyance of the control system. In addition, the high-concentration hydrofluoric acid waste liquid tank V1, the sodium carbonate-containing sodium hydroxide solution storage tank V2, the sodium aluminate solution storage tank V3, and the first crystallization reaction section R1 and the second crystallization reaction section R2 are preferably provided inside. There is a liquid level gauge, so that the control processor P can detect the liquid level status in each section of equipment through the liquid level gauge.
以上說明了本發明自氫氟酸溶液生成氟化鈉與氟鋁酸鈉晶體之二次結晶系統的設備間連接關係及作用。以下請以圖2配合參閱圖3,說明本發明自氫氟酸溶液生成氟化鈉與氟鋁酸鈉晶體之二次結晶系統的結晶操作控制方法。The above explained the connection relationship and function between the devices of the secondary crystallization system for generating sodium fluoride and sodium fluoroaluminate crystals from the hydrofluoric acid solution of the present invention. Below, please refer to FIG. 2 with reference to FIG. 3 to describe the crystallization operation control method of the secondary crystallization system for generating sodium fluoride and sodium fluoroaluminate crystals from a hydrofluoric acid solution according to the present invention.
本發明結晶操作控制方法包括初步設定程序、第一階段結晶程序以及第二階段結晶程序,該初步設定程序包括參數設定步驟S1,該第一階段結晶程序包括高濃度氫氟酸廢棄原液輸入步驟S2、第一階段結晶藥劑添加步驟S3、第一階段pH值檢測步驟S4、靜置反應步驟S5、第一階段固液分離步驟S6及氟化鈉晶體處理步驟S7,該第二階段結晶程序包括中低濃度氫氟酸反應液輸入步驟S8、第二階段結晶藥劑添加步驟S9、第二階段氟離子檢測步驟S10、第二階段pH值檢測步驟S11、靜置反應步驟S12、第二階段固液分離步驟S13及氟鋁酸鈉晶體處理步驟S14。The crystallization operation control method of the present invention includes a preliminary setting procedure, a first-stage crystallization procedure, and a second-stage crystallization procedure. The preliminary setting procedure includes a parameter setting step S1. The first-stage crystallization procedure includes a high-concentration hydrofluoric acid waste stock solution input step S2. 1. The first-stage crystallization agent adding step S3, the first-stage pH detection step S4, the standing reaction step S5, the first-stage solid-liquid separation step S6, and the sodium fluoride crystal processing step S7. The second-stage crystallization process includes the following steps: Low-concentration hydrofluoric acid reaction solution input step S8, second-stage crystallization agent addition step S9, second-stage fluoride ion detection step S10, second-stage pH detection step S11, standing reaction step S12, and second-stage solid-liquid separation Step S13 and the sodium fluoroaluminate crystal processing step S14.
該參數設定步驟S1:透過控制處理器P設定參數項目及其數值範圍。其中,該參數設定步驟S1還包括,在完成參數設定後,依第一階段結晶藥劑流量需求設置第一質量控制加藥段A1的分散盤及控制盤,以調控含碳酸鈉的氫氧化鈉溶液落入第一結晶反應段R1內反應空間的流速;以及,依第二階段結晶藥劑流量需求設置第第二質量控制加藥段A2的分散盤及控制盤,以調控鋁酸鈉溶液落入第二結晶反應段R2內反應空間的流速。The parameter setting step S1: Set parameter items and their numerical ranges through the control processor P. Wherein, the parameter setting step S1 further includes, after completing the parameter setting, setting a dispersion plate and a control plate of the first quality control dosing section A1 according to the flow demand of the first-stage crystalline agent to regulate the sodium hydroxide solution containing sodium carbonate The flow velocity falling into the reaction space in the first crystallization reaction section R1; and, according to the crystallization agent flow demand in the second stage, a dispersion plate and a control plate of the second quality control dosing section A2 are set to regulate the sodium aluminate solution falling into the first The flow rate of the reaction space in the second crystallization reaction section R2.
該高濃度氫氟酸廢棄原液輸入步驟S2:根據該參數設定步驟S1的設定值,將高濃度氫氟酸廢棄原液HHF批量輸入第一結晶反應段R1的反應空間內。The high-concentration hydrofluoric acid waste stock solution input step S2: According to the setting value of the parameter setting step S1, the high-concentration hydrofluoric acid waste stock solution HHF is input into the reaction space of the first crystallization reaction section R1 in batches.
該第一階段結晶藥劑添加步驟S3:根據該參數設定步驟S1的設定值,將含碳酸鈉的氫氧化鈉溶液輸出至第一質量控制加藥段A1以形成點滴狀液流並落入至第一結晶反應段R1的反應空間內,令該含碳酸鈉的氫氧化鈉溶液與該高濃度氫氟酸廢棄原液HHF進行結晶反應,並生成氟化鈉晶體C1與中低濃度氫氟酸反應液LHF。具體地,於本步驟中,待高濃度氫氟酸廢棄原液HHF進流完成後,開始採用點滴緩慢進流方式,配合第二質量控制加藥段A2質量控制添加含碳酸鈉的氫氧化鈉溶液(第一結晶藥劑CR1)。此階段為靜止反應添加藥劑,以pH值=3為控制反應終點。The first-stage crystallization agent adding step S3: according to the setting value of the parameter setting step S1, the sodium carbonate solution containing sodium carbonate is output to the first quality control dosing section A1 to form a drip-like liquid flow and fall to the first In a reaction space of a crystallization reaction section R1, the sodium carbonate-containing sodium hydroxide solution is caused to crystallize with the high-concentration hydrofluoric acid waste stock solution HHF, and a sodium fluoride crystal C1 and a medium-low concentration hydrofluoric acid reaction solution are generated. LHF. Specifically, in this step, after the completion of the high-concentration hydrofluoric acid waste stock solution HHF inflow, the slow infusion method is started, and the second quality control dosing section A2 is added to add sodium carbonate-containing sodium hydroxide solution. (The first crystallizing agent CR1). At this stage, a medicament is added for the stationary reaction, and the pH is controlled as the endpoint of the reaction.
該第一階段pH值檢測步驟S4:將第一結晶反應段R1中的反應溶液導入第一pH值檢測段D1中測定該反應溶液的pH值;其中,該第一階段pH值檢測步驟S4的反應終點判斷步驟S41是根據該參數設定步驟S1的pH值反應終點設定值,在該反應溶液的pH值未到設定值時,重覆執行該第一階段結晶藥劑添加步驟S3及第一階段pH值檢測步驟S4,直至該反應溶液的pH值達到設定值時,進入該靜置反應步驟S5。The first stage pH detection step S4: introducing the reaction solution in the first crystallization reaction section R1 into the first pH detection section D1 to measure the pH of the reaction solution; wherein, in the first stage pH detection step S4, The reaction end point determination step S41 is a set value of the reaction end point according to the pH value of the parameter setting step S1. When the pH value of the reaction solution does not reach the set value, the first-stage crystallization agent adding step S3 and the first-stage pH are repeatedly performed. The value detection step S4 is performed until the pH value of the reaction solution reaches a set value, and the process proceeds to the standing reaction step S5.
該靜置反應步驟S5:停止將含碳酸鈉的氫氧化鈉溶液輸出至第一質量控制加藥段A1,並根據該參數設定步驟S1的設定值靜置第一結晶反應段R1中的反應溶液,以進行結晶反應生成氟化鈉晶體C1。The standing reaction step S5: Stop outputting the sodium carbonate-containing sodium hydroxide solution to the first quality control dosing section A1, and leave the reaction solution in the first crystallization reaction section R1 to stand according to the value set in the parameter setting step S1. To perform a crystallization reaction to generate sodium fluoride crystal C1.
該第一階段固液分離步驟S6:將生成的氟化鈉晶體C1自該反應溶液中固液分離。In the first solid-liquid separation step S6, the generated sodium fluoride crystal C1 is solid-liquid separated from the reaction solution.
該氟化鈉晶體處理步驟S7:收集並清洗該氟化鈉晶體。The sodium fluoride crystal processing step S7: collecting and washing the sodium fluoride crystal.
具體地,於靜置反應步驟S5、第一階段固液分離步驟S6及氟化鈉晶體處理步驟S7中,當確定達到第一階段反應終點並停止加藥後,維持30-60分鐘靜置反應,開始以第一固液分離段SE1進行固液分離,液體部分將進入第二結晶反應段R2的結晶反應槽內,而固體(氟化納晶體C1)則留在第一固液分離段SE1,待該液體部分全部進入第二結晶反應段R2後,啟動第一清洗處理段W1清洗第一固液分離段SE1中的氟化鈉晶體C1,清洗完畢後,再將晶體取出。於此步驟中獲得的氟化鈉晶體C1含水率約50wt%,可進入乾燥程序進一步降低含水率。Specifically, in the standing reaction step S5, the first-stage solid-liquid separation step S6, and the sodium fluoride crystal processing step S7, when it is determined that the first-stage reaction end point is reached and the dosing is stopped, the standing reaction is maintained for 30-60 minutes. Start the solid-liquid separation with the first solid-liquid separation section SE1. The liquid part will enter the crystallization reaction tank of the second crystallization reaction section R2, and the solid (sodium fluoride crystal C1) will remain in the first solid-liquid separation section SE1. After all the liquid part enters the second crystallization reaction section R2, the first cleaning treatment section W1 is started to clean the sodium fluoride crystal C1 in the first solid-liquid separation section SE1. After the cleaning is completed, the crystal is taken out. The water content of the sodium fluoride crystal C1 obtained in this step is about 50% by weight, and the water content can be further reduced by entering a drying process.
該中低濃度氫氟酸反應液輸入步驟S8:根據該參數設定步驟S1的設定值,將該中低濃度氫氟酸反應液LHF批量輸入第二結晶反應段R2的反應空間內。於本步驟中,該中低濃度氫氟酸反應液LHF是氟離子濃度約為25g/L以上的氫氟酸廢液。The medium-low-concentration hydrofluoric acid reaction solution input step S8: according to the parameter setting step S1, the medium-low-concentration hydrofluoric acid reaction solution LHF is input into the reaction space of the second crystallization reaction section R2 in batches. In this step, the medium-low concentration hydrofluoric acid reaction liquid LHF is a hydrofluoric acid waste liquid having a fluoride ion concentration of about 25 g / L or more.
該第二階段結晶藥劑添加步驟S9:根據該參數設定步驟S1的設定值,將鋁酸鈉溶液輸出至第二質量控制加藥段A2以形成點滴狀液流並落入至第二結晶反應段R2的反應空間內,令該鋁酸鈉溶液與該中低濃度氫氟酸反應液LHF進行結晶反應,並生成氟鋁酸鈉晶體C2與低濃度氫氟酸廢液。其中,該第二階段結晶藥劑添加步驟S9還包括從第二結晶反應段R2的反應空間內抽取含有晶核C22的反應溶液回流至投藥空間中,從而形成動態結晶反應,以提高第二階段結晶程序中的氟鋁酸鈉晶體C2結晶率。The second-stage crystallization agent adding step S9: according to the parameter setting step S1, the sodium aluminate solution is output to the second quality control dosing section A2 to form a drip-like liquid stream and fall into the second crystallization reaction section. In the reaction space of R2, the sodium aluminate solution is subjected to a crystallization reaction with the medium-low concentration hydrofluoric acid reaction solution LHF, and sodium fluoroaluminate crystal C2 and a low-concentration hydrofluoric acid waste liquid are generated. Wherein, the second-stage crystallization agent adding step S9 further includes extracting the reaction solution containing the crystal nucleus C22 from the reaction space of the second crystallization reaction section R2 and returning it to the dosing space, thereby forming a dynamic crystallization reaction to improve the second-stage crystallization. C2 crystallization rate of sodium fluoroaluminate crystals in the program.
該第二階段氟離子檢測步驟S10,將第二結晶反應段R2中的反應溶液導入氟離子濃度檢測段FD中測定該反應溶液的氟離子溶度;其中該第二階段氟離子檢測步驟S10的反應終點判斷步驟S101是根據該參數設定步驟S1的氟離子濃度反應終點設定值,在該反應溶液的氟離子濃度未到設定值時,重覆執行該第二階段結晶藥劑添加步驟S9及第二階段氟離子檢測步驟S10,直至該反應溶液的氟離子濃度達到設定值時,進入該第二階段pH值檢測步驟S11。具體地,於本步驟中,該氟離子濃度的反應終點設定值為低於3g/L。In the second stage fluoride ion detection step S10, the reaction solution in the second crystallization reaction section R2 is introduced into the fluoride ion concentration detection section FD to determine the fluoride ion solubility of the reaction solution; wherein the second stage fluoride ion detection step S10 is The reaction end point determination step S101 is the set value of the fluoride ion concentration reaction end point according to the parameter setting step S1. When the fluoride ion concentration of the reaction solution does not reach the set value, the second-stage crystallization agent adding step S9 and the second step are repeatedly performed. In step S10 of the fluoride ion detection step, until the fluoride ion concentration of the reaction solution reaches a set value, the process proceeds to the second step of pH value detection step S11. Specifically, in this step, the set value of the reaction endpoint of the fluoride ion concentration is lower than 3 g / L.
該第二階段pH值檢測步驟S11:將第二結晶反應段R2中的反應溶液導入第二pH值檢測段D2中測定該反應溶液的pH值;其中,該第二階段pH值檢測步驟S11的反應終點判斷步驟S111是根據該參數設定步驟S1的pH值反應終點設定值,在該反應溶液的pH值未到設定值時,重覆執行該水樣pH值微調步驟S112及第二階段pH值檢測步驟S11,直至該反應溶液的pH值達到設定值時,進入該靜置反應步驟S12。具體地,於本步驟中,該pH值的反應終點設定值為7;藉此,令反應溶液的pH測定值達到7時,反應溶液中的氟離子濃度約可降至60mg/L以下,達到排放標準濃度。The second stage pH detection step S11: introducing the reaction solution in the second crystallization reaction section R2 into the second pH detection section D2 to measure the pH value of the reaction solution; wherein, in the second stage pH detection step S11, The reaction end point judgment step S111 is based on the pH value of the parameter setting step S1. The reaction end point setting value is repeatedly executed when the pH value of the reaction solution does not reach the set value, and the water sample pH adjustment step S112 and the second stage pH value are repeatedly performed. Step S11 is detected, and when the pH value of the reaction solution reaches a set value, the process proceeds to the standing reaction step S12. Specifically, in this step, the set value of the reaction endpoint of the pH value is 7; thereby, when the pH measurement value of the reaction solution reaches 7, the fluoride ion concentration in the reaction solution can be reduced to about 60 mg / L or less, Emission standard concentration.
該靜置反應步驟S12:停止將鋁酸鈉溶液輸出至第二質量控制加藥段A2,並根據該參數設定步驟S1的設定值靜置第二結晶反應段R2中的反應溶液,以進行結晶反應生成氟鋁酸鈉晶體C2。The standing reaction step S12: Stop outputting the sodium aluminate solution to the second quality control dosing section A2, and leave the reaction solution in the second crystallization reaction section R2 to stand for crystallization according to the value set in the parameter setting step S1. The reaction produces sodium fluoroaluminate crystal C2.
該第二階段固液分離步驟S13:將生成的氟鋁酸鈉晶體C2自該反應溶液中固液分離。In the second solid-liquid separation step S13, the generated sodium fluoroaluminate crystal C2 is solid-liquid separated from the reaction solution.
該氟鋁酸鈉晶體處理步驟S14:收集並清洗該氟鋁酸鈉晶體C2。The sodium fluoroaluminate crystal processing step S14: Collect and clean the sodium fluoroaluminate crystal C2.
具體地,於靜置反應步驟S12、第二階段固液分離步驟S13及氟鋁酸鈉晶體處理步驟S14中,當確定第二反應階段到達反應終點並停止加藥後,維持10分鐘動態反應時間後,再停止回流泵A23上下循環導流,並靜置反應溶液30分鐘後,啟動第二固液分離段SE2進行固液分離。該第二固液分離段SE2的液體部份進入後續放流程序,固體部分(氟鋁酸鈉晶體C2,冰晶石)將留在第二固液分離段SE2,待液體全部進入後續放流程序後,開始以清水清洗第二固液分離段SE2中的氟鋁酸鈉晶體C2,清洗完畢後,再將晶體取出。於此步驟中獲得的氟鋁酸鈉晶體C2含水率約50wt%,可進入乾燥程序進一步降低含水率。Specifically, in the standing reaction step S12, the second-stage solid-liquid separation step S13, and the sodium fluoroaluminate crystal processing step S14, when it is determined that the second reaction stage reaches the end of the reaction and the dosing is stopped, the dynamic reaction time is maintained for 10 minutes. After that, the reflux pump A23 was stopped to conduct circulation up and down, and the reaction solution was left to stand for 30 minutes, and then the second solid-liquid separation section SE2 was started for solid-liquid separation. The liquid portion of the second solid-liquid separation section SE2 enters the subsequent discharge procedure, and the solid portion (sodium fluoroaluminate crystal C2, cryolite) will remain in the second solid-liquid separation section SE2. After the liquid has entered the subsequent discharge procedure, Start to clean the sodium fluoroaluminate crystal C2 in the second solid-liquid separation section SE2 with clean water. After cleaning, remove the crystal. The moisture content of the sodium fluoroaluminate crystal C2 obtained in this step is about 50% by weight, and the moisture content can be further reduced by entering a drying process.
於本發明實施例中,如圖3所示,本發明方法還包括自動模式判斷步驟S15,該自動模式判斷步驟S15是由控制處理器P預設當次操作為自動模式或手動模式;當為自動模式時,由控制處理器P自動控制從該高濃度氫氟酸廢棄原液輸入步驟S2開始重覆執行前述步驟;當為手動模式時,控制處理器P停止自動控制,並回至參數設定步驟S1完成參數設定後啟動自動控制。In the embodiment of the present invention, as shown in FIG. 3, the method of the present invention further includes an automatic mode determination step S15. The automatic mode determination step S15 is preset by the control processor P as an automatic mode or a manual mode. In the automatic mode, the control processor P automatically controls the high-concentration hydrofluoric acid waste stock solution input step S2 to repeatedly execute the foregoing steps. When in the manual mode, the control processor P stops automatic control and returns to the parameter setting step. After S1 finishes parameter setting, it starts automatic control.
此外,本發明整體系統可為批次式操作,或者連續式批次操作。若使用連續式批次操作時,當反應溶液進到第二結晶反應段R2時,下一批高濃度氫氟酸廢棄原液HHF即可進流至第一結晶反應段R1。In addition, the overall system of the present invention may be a batch operation or a continuous batch operation. If continuous batch operation is used, when the reaction solution enters the second crystallization reaction section R2, the next batch of high-concentration hydrofluoric acid waste stock solution HHF can flow to the first crystallization reaction section R1.
以下提供本發明自氫氟酸溶液生成氟化鈉與氟鋁酸鈉晶體之二次結晶系統及其結晶操作控制方法的具體實施例,其包括實驗室級之實施例:實施例一、實施例二,以及模廠級之實施例:實施例三、實施例四。The following provides specific embodiments of the secondary crystallization system for generating sodium fluoride and sodium fluoroaluminate crystals from a hydrofluoric acid solution according to the present invention, and a method for controlling the crystallization operation thereof, which includes laboratory-level embodiments: Example 1, Example Second, and mold factory-level embodiments: Embodiment three, embodiment four.
在實施例一、實施例二中,第一階段結晶程序及第二階段結晶程序皆采用體積為10公升的結晶反應槽(第一結晶反應段R1、第二結晶反應段R2);批次反應的高濃度氫氟酸廢棄原液為5公升。更具體地,該結晶反應槽為PP材質的圓型塑膠桶,反應槽體積為10公升;該高濃度氫氟酸廢棄原液是取自半導體廠的實際氫氟酸廢液。In Example 1 and Example 2, both the first-stage crystallization process and the second-stage crystallization process used a 10-liter crystallization reaction tank (first crystallization reaction section R1, second crystallization reaction section R2); batch reaction The high concentration of hydrofluoric acid waste stock solution is 5 liters. More specifically, the crystallization reaction tank is a round plastic barrel made of PP, and the volume of the reaction tank is 10 liters; the high-concentration hydrofluoric acid waste stock solution is an actual hydrofluoric acid waste solution taken from a semiconductor factory.
實施例一、實施例二的實驗室級試驗步驟說明如下:The laboratory-level test steps of the first embodiment and the second embodiment are described as follows:
(1)以人工計量的方式,將5公升高濃度氫氟酸廢棄原液倒入第一結晶反應槽。(1) Manually measure, pour 5 liters of concentrated hydrofluoric acid waste stock solution into the first crystallization reaction tank.
(2)進行第一階段結晶程序:待氫氟酸進流完成後,開始以1公升的滴定管,以點滴緩慢進流方式添加含氫氧化鈉/碳酸鈉的液態藥劑(含碳酸鈉的氫氧化鈉溶液),該液態藥劑的成分比例為:1公升質量濃度為22.5wt%的氫氧化鈉溶液添加50克純度為99%的碳酸鈉粉末。在第一階段結晶程序中,採用靜止反應添加藥劑,並在反應當中,監控酸鹼度值的變化,第一階段結晶程序中的反應是以pH值=3為控制反應終點。(2) Carry out the first-stage crystallization procedure: After the completion of the hydrofluoric acid inflow, begin to add a liquid reagent containing sodium hydroxide / sodium carbonate (a sodium carbonate-containing hydroxide in a slow inflow manner) by using a 1-liter burette. Sodium solution), the composition ratio of the liquid medicament is: 1 liter of sodium hydroxide solution with a mass concentration of 22.5 wt% is added with 50 g of sodium carbonate powder with a purity of 99%. In the first-stage crystallization program, a static reaction is used to add a medicament, and the change in the pH value is monitored during the reaction. The reaction in the first-stage crystallization program uses pH = 3 as the control endpoint.
(3)確定達到第一階段反應終點後,停止加藥,待維持30-60分鐘靜置反應,再開始以有真空抽氣裝置的過濾器,進行固液分離。固體(氟化納晶體)會留在過濾器的薄膜濾紙上,液體部分則再倒入原反應桶中。薄膜濾紙上的晶體,以清水清洗之,清洗完畢後,再將晶體取出,並以烘箱乾燥之。待完成乾燥程序後,裝瓶送樣分析成分純度。(3) After confirming that the end point of the first-stage reaction is reached, stop the dosing, wait for 30-60 minutes to stand for the reaction, and then start the solid-liquid separation with a filter with a vacuum suction device. The solid (sodium fluoride crystal) will remain on the membrane filter paper of the filter, and the liquid part will be poured into the original reaction barrel. The crystals on the membrane filter paper are washed with water. After cleaning, the crystals are taken out and dried in an oven. After the drying process is completed, the samples are bottled and analyzed for purity.
(4)進行第二階段結晶程序:對進入第二結晶反應槽的氫氟酸溶液,取樣分析氟離子濃度。而後開始以1公升的滴定管,以點滴緩慢進流方式,添加液態藥劑鋁酸鈉,此鋁酸鈉溶液為自行配置,成份質量比例為Na/Al=1.6。(4) Perform the second-stage crystallization procedure: sample the hydrofluoric acid solution entering the second crystallization reaction tank, and analyze the fluoride ion concentration. Then, a 1-liter burette was used to add the liquid medicament sodium aluminate in a slow instillation manner. This sodium aluminate solution was self-configured and the component mass ratio was Na / Al = 1.6.
(5)在第二階段結晶程序中,先以氟離子濃度控制鋁酸鈉加藥量,當氟離子濃度低於3g/L後,再以酸鹼值(pH值),微調加藥鋁酸鈉,並以pH值=7為控制反應終點。經此步驟反應後的反應溶液中氟離子濃度可下降至 60 mg/L以下。(5) In the second-stage crystallization procedure, the dosage of sodium aluminate is controlled by the fluoride ion concentration. When the fluoride ion concentration is lower than 3g / L, the pH value is used to fine-tune the dosage of aluminate. Sodium, and pH = 7 was used as the control endpoint. The fluoride ion concentration in the reaction solution after the reaction in this step can be reduced to below 60 mg / L.
(6)確定第二階段結晶程序到達反應終點,停止加藥後,維持10分鐘反應時間,再開始以有真空抽氣裝置的過濾器,進行固液分離。(6) Make sure that the second-stage crystallization program reaches the end of the reaction. After stopping the dosing, maintain the reaction time for 10 minutes, and then start the solid-liquid separation with a filter with a vacuum suction device.
(7)固體(氟鋁酸鈉,冰晶石)會留在過濾器的薄膜濾紙上,液體部分則可放流水槽。薄膜濾紙上的晶體,以清水清洗之,清洗完畢後,再將晶體取出,以烘箱乾燥之。待完成乾燥程序後,裝瓶送樣分析成分純度。(7) The solid (sodium fluoroaluminate, cryolite) will remain on the membrane filter paper of the filter, and the liquid part can be discharged into the water tank. The crystals on the membrane filter paper are washed with water. After cleaning, the crystals are taken out and dried in an oven. After the drying process is completed, the samples are bottled and analyzed for purity.
以上實施例一、實施例二的具體實驗條件與測定結果如後表一所示。The specific experimental conditions and measurement results of the above Example 1 and Example 2 are shown in Table 1 below.
實施例三、實施例四的模廠級試驗步驟說明如下:於實施例三、實施例四中,均採用模廠系統的自動模式,具體的系統設備可以采用本案發明人先前提出的申請第102144345號的台灣發明專利「自氫氟酸溶液生成氟鋁酸鈉晶體之結晶系統設備及其結晶操作控制方法」中的結晶系統設備,於此不再贅述。以下步驟為自動模式下的運轉步驟。The third embodiment and the fourth embodiment of the mold factory-level test steps are described as follows: In the third and fourth embodiments, the automatic mode of the mold factory system is used, and the specific system equipment can use the application previously filed by the inventor of the present case 102144345 The crystallization system equipment in the "Taiwan invention patent" Crystal system equipment for generating sodium fluoroaluminate crystals from hydrofluoric acid solution and crystallization operation control method "will not be repeated here. The following steps are the operation steps in the automatic mode.
A.第一階段結晶程序(氟化鈉晶體)A. First stage crystallization procedure (sodium fluoride crystal)
(1)確認以下的操作參數後,啟動自動模式開始運轉。
(2)啟動高濃度氫氟酸廢棄原液(High-HF,HHF)的輸出泵浦(計量進流控制段F),依照處理量之設定,注入至第一結晶反應槽(第一結晶反應段R1)內。(2) Start the output pump of the high-concentration hydrofluoric acid waste stock solution (High-HF, HHF) (metering inflow control section F) and inject it into the first crystallization reaction tank (the first crystallization reaction section) according to the setting of the processing capacity. R1) within.
(3)待高濃度氫氟酸廢棄原液完全注入第一結晶反應槽後,啟動含碳酸鈉的氫氧化鈉溶液儲槽的輸出泵浦,依照質量控制加藥使藥劑進入反應槽內。(3) After the high-concentration hydrofluoric acid waste stock solution is completely injected into the first crystallization reaction tank, the output pump of the sodium carbonate-containing sodium hydroxide solution storage tank is started, and the medicine is added into the reaction tank according to quality control.
(4)依照反應靜置時間的設定,系統靜置。(4) According to the setting of the reaction standing time, the system is standing still.
(5)到達反應靜置時間後,啟動各氣動閥(導入與排入反應槽之氣動閥)與監測系統的泵浦,水樣(反應溶液)被導入監測系統(第一pH值檢測段D1)中,待監測系統測定時間的設定,數據讀取判斷是否為反應終點。於本發明實施例三、實施例四中,系統還包括設於第一結晶反應槽外部的氟化鈉結晶物的儲存裝置,該儲存裝置與該第一結晶反應槽連通形成封閉內循環回路;藉此,當啟動監測系統之泵浦時,水流會將儲存氟化鈉結晶物的儲存裝置中的結晶物透過該封閉內循環回路帶入反應槽中,進行植晶種的程序。(5) After the reaction standing time is reached, the pumps of the pneumatic valves (pneumatic valves introduced and discharged into the reaction tank) and the monitoring system are started, and the water sample (reaction solution) is introduced into the monitoring system (the first pH detection section D1) ), Set the measurement time of the system to be monitored, and read the data to determine whether it is the end point of the reaction. In the third and fourth embodiments of the present invention, the system further includes a storage device for sodium fluoride crystals provided outside the first crystallization reaction tank, and the storage device communicates with the first crystallization reaction tank to form a closed internal circulation loop; Therefore, when the pump of the monitoring system is started, the water current will bring the crystals in the storage device storing the sodium fluoride crystals into the reaction tank through the closed internal circulation loop, and the seeding process is performed.
(6)若未達反應終點pH值設定值,關閉監測系統泵浦與各氣動閥,進入微調投入第一結晶藥劑(含碳酸鈉的氫氧化鈉溶液)程序;即啟動第一結晶藥劑儲槽的輸出泵浦,依照微調投入含碳酸鈉的氧氧化鈉溶液質量的設定,注入到第一結晶反應槽的上部分散盤槽體。(6) If the pH value of the end point of the reaction is not reached, close the pump of the monitoring system and each pneumatic valve, and enter the procedure for fine adjustment and input of the first crystallization agent (sodium hydroxide solution containing sodium carbonate); that is, start the first crystallization agent storage tank The output pump is injected into the upper dispersion disk tank body of the first crystallization reaction tank according to the setting of the fine adjustment of the mass of the sodium oxyoxide solution containing sodium carbonate.
(7)到達微調反應靜置時間後,啟動各氣動閥(導入與排入反應槽之氣動閥)與監測系統泵浦,水樣(反應溶液)會導入監測系統(第一pH值檢測段D1)中,待監測系統測定時間的設定,數據讀取判斷是否為反應終點,若未到達反應終點pH值設定值,則持續重複(6)的步驟,直至到達反應終點pH值設定值。(7) After the fine-tuning reaction standing time is reached, start the pneumatic valves (pneumatic valves introduced and discharged into the reaction tank) and the pump of the monitoring system, and the water sample (reaction solution) will be introduced into the monitoring system (the first pH detection section D1) ), The measurement time of the system to be monitored is set, and the data is read to determine whether it is the end point of the reaction. If the pH value of the end point of the reaction is not reached, continue to repeat step (6) until the end value of the pH value of the reaction is reached.
(8)到達反應終點pH值設定值後,啟動第一分離器進行結晶物的分離清洗作業,結晶物與中低濃度氫氟酸反應液(Low-HF,LHF)會以重力流排入脫水機中,先經過第一次的固液分離,將中低濃度氫氟酸反應液LHF先排放至第二階段結晶反應槽中貯存,再啟動清水氣動閥進行清洗作業,當注入清水水位到達設定值後關閉清水氣動閥,隨即進行固液分離,分離後的清洗廢水則排放至清洗廢水槽貯存。此清洗動作將重複三次。(8) After reaching the set pH value at the end of the reaction, start the first separator to separate and clean the crystals. The crystals and low-HF hydrofluoric acid reaction solution (Low-HF, LHF) will be discharged into the dehydration by gravity flow. In the machine, after the first solid-liquid separation, the low- and medium-concentration hydrofluoric acid reaction liquid LHF is first discharged to the second-stage crystallization reaction tank for storage, and then the clean water pneumatic valve is started for cleaning operations. When the clean water level reaches the setting, After the value is closed, the clean water pneumatic valve is closed, and then solid-liquid separation is performed, and the separated washing wastewater is discharged to the washing wastewater tank for storage. This cleaning action will be repeated three times.
(9)清洗廢水槽設有高低液位來控制清洗廢水泵浦,將清洗廢液排出系統外。(9) The cleaning waste water tank is provided with high and low liquid levels to control the cleaning waste water pump and discharge the cleaning waste liquid out of the system.
(10)當清洗作業達到設定值後,系統即進入第二階段結晶程序,存放至第一分離器的氟化鈉晶體由人工取出。(10) When the cleaning operation reaches the set value, the system enters the second-stage crystallization procedure, and the sodium fluoride crystals stored in the first separator are manually taken out.
B.第二階段結晶程序(氟鋁酸鈉晶體)B. Second-stage crystallization procedure (sodium fluoroaluminate crystals)
(1)當第二結晶反應槽到達設定液位後,系統開啟第二結晶反應槽迴流泵浦(回流泵A23)。(1) When the second crystallization reaction tank reaches the set liquid level, the system turns on the second crystallization reaction tank reflux pump (reflow pump A23).
(2)啟動鋁酸鈉溶液儲槽的輸出泵浦,依照質量控制加藥使鋁酸鈉藥劑進入第二結晶反應槽內。(2) Start the output pump of the sodium aluminate solution storage tank, and add the sodium aluminate agent into the second crystallization reaction tank according to the quality control.
(3)到達設定反應時間時,啟動各氣動閥(導入與排入反應槽之氣動閥)與監測系統泵浦,水樣(反應溶液)被導入監測系統(氟離子濃度檢測段FD、第二pH值檢測段D2)中,待監測系統測定時間的設定,數據讀取判斷是否為反應終點。(3) When the set reaction time is reached, each pneumatic valve (pneumatic valve introduced and discharged into the reaction tank) and the pump of the monitoring system are started, and the water sample (reaction solution) is introduced into the monitoring system (fluoride ion concentration detection section FD, second In the pH detection section D2), the measurement time of the system to be monitored is set, and the data is read to determine whether it is the end point of the reaction.
(4)若未達反應終點pH值或氟離子濃度設定值,關閉監測系統泵浦與各氣動閥,進入微調投入第二結晶藥劑(鋁酸鈉溶液)程序;即啟動第二結晶藥劑儲槽的輸出泵浦,依照微調投入鋁酸鈉質量的設定,注入到第二結晶反應槽內部。(4) If the pH value or fluoride ion concentration set point is not reached, close the pump of the monitoring system and each pneumatic valve, and enter the procedure for fine adjustment and input of the second crystallization agent (sodium aluminate solution); that is, start the second crystallization agent storage tank The output pump is injected into the second crystallization reaction tank according to the setting of the fine-tuning input sodium aluminate quality.
(5)到達微調反應靜置時間後,啟動各氣動閥(導入與排入反應槽之氣動閥)與監測系統泵浦,水樣(反應溶液)會導入監測系統(氟離子濃度檢測段FD、第二pH值檢測段D2)中,待監測系統測定時間的設定,數據讀取判斷是否為反應終點,若未到達反應終點pH值與氟離子設定值,則持續重複(4)的步驟,直至到達反應終點pH值與氟離子設定值。(5) After reaching the fine-tuning reaction stand-by time, start each pneumatic valve (pneumatic valve introduced and discharged into the reaction tank) and the pump of the monitoring system, and the water sample (reaction solution) will be introduced into the monitoring system (fluoride ion concentration detection section FD, In the second pH detection section D2), the measurement time of the system to be monitored is set, and the data is read to determine whether it is the end of the reaction. If the pH and the set value of fluoride ion are not reached, continue to repeat step (4) until Reached the end of the reaction pH value and fluoride ion set value.
(6)到達反應終點pH值與氟離子設定值後,啟動第二分離器進行結晶物的分離清洗作業,結晶物與低濃度氫氟酸廢液會以重力流排入脫水機中,先經過第一次的固液分離,將低濃度氫氟酸廢液排放至清洗廢水槽,再啟動清水氣動閥進行清洗作業,當注入清水水位到達設定值後關閉清水氣動閥,隨即進行固液分離,分離後的清洗廢水則排放至清洗廢水槽貯存。此清洗動作將重複三次。(6) After reaching the end of the reaction pH value and fluoride ion set value, start the second separator to separate and clean the crystals. The crystals and low-concentration hydrofluoric acid waste liquid will be discharged into the dehydrator by gravity flow, and then pass through For the first solid-liquid separation, discharge the low-concentration hydrofluoric acid waste liquid to the cleaning wastewater tank, and then start the clean water pneumatic valve for cleaning operations. When the injected clean water level reaches the set value, close the clean water pneumatic valve, and then perform solid-liquid separation. The separated washing wastewater is discharged to the washing wastewater tank for storage. This cleaning action will be repeated three times.
(7)清洗廢水槽設有高低液位來控制清洗廢水泵浦,將清洗廢液排出系統外。(7) The cleaning waste water tank is provided with high and low liquid levels to control the cleaning waste water pump and discharge the cleaning waste liquid out of the system.
(8)當清洗作業達到設定值後,系統即可重新開始進行第一階段結晶作業,存放至第二分離器的晶體需人工取出。(8) After the cleaning operation reaches the set value, the system can restart the first-stage crystallization operation, and the crystal stored in the second separator needs to be manually taken out.
以上實施例三、實施例四的具體實驗條件與測定結果如後表一所示。The specific experimental conditions and measurement results of the above Examples 3 and 4 are shown in Table 1 below.
藉此,本發明自氫氟酸溶液生成氟化鈉與氟鋁酸鈉晶體之二次結晶系統及其結晶操作控制方法,透過第一階段結晶程序及第二階段結晶程序的結合,達到將高濃度氫氟酸廢棄原液充分反應生成具有經濟效益的氟化鈉晶體及氟鋁酸鈉晶體,同時有效降低廢棄原液的氟離子濃度至符合排放標準,無法再額外處理即可集中排放,降低高濃度氫氟酸廢棄原液的處理成本。同時,本發明透過各結晶程序中的pH值檢測及/或氟離子濃度檢測以及固液分離段、清洗處理段,有效控制了系統操作過程中影響結晶純度之因素,確保系統穩定地產出結晶純度可供回收再使用之氟化鈉晶體、氟鋁酸鈉晶體(冰晶石),達到將氟離子回收率提高且生成之晶體純度高而具有高經濟效益之目的。Therefore, the secondary crystallization system for generating sodium fluoride and sodium fluoroaluminate crystals from a hydrofluoric acid solution according to the present invention and a method for controlling the crystallization operation thereof, through the combination of the first-stage crystallization procedure and the second-stage crystallization procedure, can achieve a high Concentrated hydrofluoric acid waste stock solution fully reacts to produce economical sodium fluoride crystals and sodium fluoroaluminate crystals. At the same time, it effectively reduces the concentration of fluoride ions in the waste stock solution to meet the emission standards. It can be concentratedly discharged without additional treatment, reducing high concentrations. Disposal cost of hydrofluoric acid waste stock solution. At the same time, the present invention effectively controls the factors affecting the purity of the crystal during the operation of the system through the pH value detection and / or fluoride ion concentration detection in each crystallization program, and the solid-liquid separation section and the cleaning treatment section to ensure that the system can stably produce crystal purity Sodium fluoride crystals and sodium fluoroaluminate crystals (cryolite) that can be recovered and reused can achieve the purpose of improving the recovery rate of fluoride ions and the purity of the resulting crystals with high economic benefits.
P‧‧‧控制處理器P‧‧‧Control Processor
V1‧‧‧高濃度氫氟酸廢液槽 V1‧‧‧High-concentration hydrofluoric acid waste tank
F‧‧‧計量進流控制段 F‧‧‧Measurement inflow control section
V2‧‧‧含碳酸鈉的氫氧化鈉溶液儲槽 V2‧‧‧Sodium hydroxide solution storage tank containing sodium carbonate
V3‧‧‧鋁酸鈉溶液儲槽 V3‧‧‧Sodium Aluminate Solution Storage Tank
A1‧‧‧第一質量控制加藥段 A1‧‧‧The first quality control dosing section
A2‧‧‧第二質量控制加藥段 A2‧‧‧Second Quality Control Dosing Section
R1‧‧‧第一結晶反應段 R1‧‧‧First crystallization reaction section
R2‧‧‧第二結晶反應段 R2‧‧‧Second crystallization reaction section
D1‧‧‧第一pH值檢測段 D1‧‧‧The first pH detection section
D2‧‧‧第二pH值檢測段 D2‧‧‧Second pH detection section
FD‧‧‧氟離子濃度檢測段 FD‧‧‧Fluoride ion concentration detection section
W1‧‧‧第一清洗處理段 W1‧‧‧The first cleaning treatment section
W2‧‧‧第二清洗處理段 W2‧‧‧Second cleaning treatment section
SE1‧‧‧第一固液分離段 SE1‧‧‧The first solid-liquid separation section
SE2‧‧‧第二固液分離段 SE2‧‧‧Second solid-liquid separation section
C1‧‧‧氟化鈉晶體 C1‧‧‧Sodium fluoride crystal
C2‧‧‧氟鋁酸鈉晶體 C2‧‧‧Sodium Fluoroaluminate Crystal
HHF‧‧‧高濃度氫氟酸廢棄原液 HHF‧‧‧High concentration hydrofluoric acid waste stock solution
LHF‧‧‧中低濃度氫氟酸反應液 LHF‧‧‧ Medium-low concentration hydrofluoric acid reaction solution
CR1‧‧‧第一結晶藥劑 CR1‧‧‧First Crystallizer
CR2‧‧‧第二結晶藥劑 CR2‧‧‧Second Crystallizer
A20‧‧‧第二結晶反應槽 A20‧‧‧Second crystallization reaction tank
A21‧‧‧質量控制加藥部 A21‧‧‧Quality Control Dosing Department
A22‧‧‧晶體沉積部 A22‧‧‧ Crystal Deposit Department
A23‧‧‧回流泵 A23‧‧‧Return pump
C21‧‧‧晶體 C21‧‧‧ Crystal
C22‧‧‧晶核 C22‧‧‧ crystal core
S1‧‧‧參數設定步驟 S1‧‧‧Parameter setting procedure
S2‧‧‧高濃度氫氟酸廢棄原液輸入步驟 S2‧‧‧High concentration hydrofluoric acid waste stock solution
S3‧‧‧第一階段結晶藥劑添加步驟 S3‧‧‧The first step of crystallizing agent adding step
S4‧‧‧第一階段pH值檢測步驟 S4‧‧‧The first stage pH detection step
S41‧‧‧反應終點判斷步驟 S41‧‧‧Reaction end judgment steps
S5‧‧‧靜置反應步驟 S5‧‧‧Still reaction step
S6‧‧‧第一階段固液分離步驟 S6‧‧‧The first solid-liquid separation step
S7‧‧‧氟化鈉晶體處理步驟 S7‧‧‧Sodium fluoride crystal processing steps
S8‧‧‧中低濃度氫氟酸反應液輸入步驟 S8‧‧‧Medium and low concentration hydrofluoric acid reaction solution input steps
S9‧‧‧第二階段結晶藥劑添加步驟 S9‧‧‧Second-stage crystallizing agent adding step
S10‧‧‧第二階段氟離子檢測步驟 S10‧‧‧Second stage fluoride ion detection step
S101‧‧‧反應終點判斷步驟 S101‧‧‧Reaction end judgment steps
S11‧‧‧第二階段pH值檢測步驟 S11‧‧‧Second stage pH detection step
S111‧‧‧反應終點判斷步驟 S111‧‧‧Reaction end judgment steps
S112‧‧‧反應溶液pH值微調步驟 S112‧‧‧ Fine adjustment step of pH value of reaction solution
S12‧‧‧靜置反應步驟 S12‧‧‧Still reaction step
S13‧‧‧第二階段固液分離步驟 S13‧‧‧Second stage solid-liquid separation step
S14‧‧‧氟鋁酸鈉晶體處理步驟 S14‧‧‧Sodium fluoroaluminate crystal processing steps
S15‧‧‧自動模式判斷步驟 S15‧‧‧Automatic mode judgment steps
圖1係習知自氫氟酸溶液生成氟鋁酸鈉晶體的結晶化系統架構示意圖。 圖2係本發明自氫氟酸溶液生成氟化鈉與氟鋁酸鈉晶體之二次結晶系統之整體架構示意圖。 圖3係本發明系統的結晶操作控制方法流程示意圖。 圖4係本發明的第二階段結晶程序在第一結晶反應段的結晶反應槽進行動態結晶反應的操作示意圖。FIG. 1 is a schematic diagram of a conventional crystallization system for generating sodium fluoroaluminate crystals from a hydrofluoric acid solution. FIG. 2 is a schematic diagram of the overall structure of a secondary crystallization system for generating sodium fluoride and sodium fluoroaluminate crystals from a hydrofluoric acid solution according to the present invention. FIG. 3 is a schematic flowchart of a crystallization operation control method of the system of the present invention. FIG. 4 is a schematic diagram of an operation of performing a dynamic crystallization reaction in a crystallization reaction tank of a first crystallization reaction stage in a second-stage crystallization procedure of the present invention.
Claims (24)
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CN114516650A (en) * | 2021-11-05 | 2022-05-20 | 广州市鸿浩光电半导体有限公司 | Crystallization system and crystallization method for generating sodium fluoroaluminate crystals from acid etching aluminum slag |
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TWI353343B (en) * | 2008-01-09 | 2011-12-01 | Yeon Chun Lee | Method of recycling fluoride from a waste solution |
TWI518041B (en) * | 2014-08-19 | 2016-01-21 | 虹京金屬股份有限公司 | A method of recycling sodium hexafluoroaluminate from hydrofluoric acid waste liquid |
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TWI353343B (en) * | 2008-01-09 | 2011-12-01 | Yeon Chun Lee | Method of recycling fluoride from a waste solution |
TWI518041B (en) * | 2014-08-19 | 2016-01-21 | 虹京金屬股份有限公司 | A method of recycling sodium hexafluoroaluminate from hydrofluoric acid waste liquid |
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CN114516650A (en) * | 2021-11-05 | 2022-05-20 | 广州市鸿浩光电半导体有限公司 | Crystallization system and crystallization method for generating sodium fluoroaluminate crystals from acid etching aluminum slag |
CN114516650B (en) * | 2021-11-05 | 2023-12-01 | 广东鸿浩半导体设备有限公司 | Crystallization system and crystallization method for generating sodium fluoroaluminate crystals from acid etched aluminum slag |
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