TWI814139B - Method for removing boron from boron-containing solution - Google Patents
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- 229910052796 boron Inorganic materials 0.000 title claims abstract description 181
- 238000000034 method Methods 0.000 title claims abstract description 171
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 title claims abstract description 143
- 238000001556 precipitation Methods 0.000 claims abstract description 110
- 239000011575 calcium Substances 0.000 claims abstract description 101
- 239000000126 substance Substances 0.000 claims abstract description 95
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims abstract description 57
- 229910052791 calcium Inorganic materials 0.000 claims abstract description 57
- 230000035484 reaction time Effects 0.000 claims abstract description 26
- 150000001450 anions Chemical class 0.000 claims abstract description 13
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000004327 boric acid Substances 0.000 claims abstract description 6
- 150000002978 peroxides Chemical class 0.000 claims description 49
- 238000006243 chemical reaction Methods 0.000 claims description 44
- 150000001875 compounds Chemical class 0.000 claims description 41
- -1 boron ions Chemical group 0.000 claims description 39
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical group OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 36
- 238000001914 filtration Methods 0.000 claims description 28
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims description 15
- 239000001110 calcium chloride Substances 0.000 claims description 15
- 229910001628 calcium chloride Inorganic materials 0.000 claims description 15
- 239000007788 liquid Substances 0.000 claims description 15
- 239000006228 supernatant Substances 0.000 claims description 12
- 239000002244 precipitate Substances 0.000 claims description 10
- 238000005352 clarification Methods 0.000 claims description 7
- 239000007800 oxidant agent Substances 0.000 claims description 6
- 230000001590 oxidative effect Effects 0.000 claims description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims 1
- 239000001301 oxygen Substances 0.000 claims 1
- 229910052760 oxygen Inorganic materials 0.000 claims 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 10
- 239000002351 wastewater Substances 0.000 abstract description 6
- 230000000694 effects Effects 0.000 description 12
- 238000005516 engineering process Methods 0.000 description 9
- 238000005345 coagulation Methods 0.000 description 7
- 230000015271 coagulation Effects 0.000 description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 238000001179 sorption measurement Methods 0.000 description 4
- 238000009388 chemical precipitation Methods 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 238000000605 extraction Methods 0.000 description 3
- 238000005342 ion exchange Methods 0.000 description 3
- 238000005502 peroxidation Methods 0.000 description 3
- 238000001223 reverse osmosis Methods 0.000 description 3
- 239000013535 sea water Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 239000000701 coagulant Substances 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- PEYVWSJAZONVQK-UHFFFAOYSA-N hydroperoxy(oxo)borane Chemical compound OOB=O PEYVWSJAZONVQK-UHFFFAOYSA-N 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 125000000864 peroxy group Chemical group O(O*)* 0.000 description 2
- 230000001376 precipitating effect Effects 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- ZKQDCIXGCQPQNV-UHFFFAOYSA-N Calcium hypochlorite Chemical compound [Ca+2].Cl[O-].Cl[O-] ZKQDCIXGCQPQNV-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- WDIHJSXYQDMJHN-UHFFFAOYSA-L barium chloride Chemical compound [Cl-].[Cl-].[Ba+2] WDIHJSXYQDMJHN-UHFFFAOYSA-L 0.000 description 1
- 229910001626 barium chloride Inorganic materials 0.000 description 1
- RQPZNWPYLFFXCP-UHFFFAOYSA-L barium dihydroxide Chemical compound [OH-].[OH-].[Ba+2] RQPZNWPYLFFXCP-UHFFFAOYSA-L 0.000 description 1
- 229910001863 barium hydroxide Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000007844 bleaching agent Substances 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000010612 desalination reaction Methods 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
- 150000002009 diols Chemical class 0.000 description 1
- 230000035622 drinking Effects 0.000 description 1
- 239000002384 drinking water standard Substances 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003337 fertilizer Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
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Abstract
Description
本發明關於一種自含硼溶液中將硼移除的方法，特別是關於一種以三階段化學過氧沉澱程序將含硼溶液中之硼去除的方法。The present invention relates to a method for removing boron from a boron-containing solution, and in particular to a method for removing boron from a boron-containing solution using a three-stage chemical peroxide precipitation procedure.
硼的相關化合物在現代工業中有廣泛的應用，舉凡火力發電廠、核電廠、玻璃、陶瓷釉料廠，或是TFT-LCD廠製程中所使用的大量硼酸，都有含硼化物的身影，它還常用於洗衣用的漂白粉、洗衣劑，農業所使用的肥料、殺蟲劑等。而其釋放的廢棄物往往會進入環境當中，尤其含硼溶液的處理技術目前尚未成熟，往往高於海洋平均硼濃度5 ppm以上排放，對海洋造成汙染。Boron-related compounds are widely used in modern industry. The large amounts of boric acid used in thermal power plants, nuclear power plants, glass and ceramic glaze factories, or TFT-LCD factories contain boride. It is also commonly used as bleaching powder and detergent for laundry, fertilizers and pesticides used in agriculture, etc. The waste released often enters the environment. In particular, the treatment technology for boron-containing solutions is not yet mature. It is often discharged at a concentration higher than the average boron concentration of 5 ppm in the ocean, causing pollution to the ocean.
目前的除硼技術約可大略分為5種，分別為化學沉澱法、離子交換法、吸附法、逆滲透與萃取法，但各個方法都有其限制。離子交換法、吸附法與逆滲透都只適用於低濃度的含硼廢液，離子交換法與吸附法擁有極佳的選擇性，且市面上已有商用的樹脂與吸附材可以購買，但多半要價不斐且再生不易。逆滲透是目前商轉最廣泛的技術，但都僅限於低濃度的含硼溶液或是海水淡化，尤其為了增加除硼效果，pH往往要調至10以上以產生帶負價的硼酸根離子，但若硬度過高往往會造成薄膜結垢的問題。化學沉澱法與萃取法都十分適合處理高濃度的含硼溶液，萃取法所使用的溶劑多為雙醇類，但溶劑的毒性及後續的處理相對棘手；而化學沉澱法在業界中是最廣為接受的技術，但是傳統的混凝沉澱法對於硼的處理效果非常有限，因為水中的硼不易與常見之混凝劑產生沉澱，因此傳統混凝沉澱法往往必須施以溫度與大量混凝劑/共沉澱劑投加量來達到較高的硼去除率。The current boron removal technology can be roughly divided into five types, namely chemical precipitation method, ion exchange method, adsorption method, reverse osmosis and extraction method, but each method has its limitations. Ion exchange method, adsorption method and reverse osmosis are only suitable for low concentration boron-containing waste liquid. Ion exchange method and adsorption method have excellent selectivity, and commercial resins and adsorption materials are available on the market, but most of them The asking price is high and it’s not easy to repurchase. Reverse osmosis is currently the most widely commercialized technology, but it is limited to low-concentration boron-containing solutions or seawater desalination. Especially in order to increase the boron removal effect, the pH often needs to be adjusted to above 10 to produce negative borate ions. However, if the hardness is too high, it will often cause the problem of film scaling. Both chemical precipitation and extraction methods are very suitable for processing high-concentration boron-containing solutions. The solvents used in the extraction method are mostly diols, but the toxicity of the solvent and subsequent treatment are relatively difficult; and the chemical precipitation method is the most widely used in the industry. It is an accepted technology, but the traditional coagulation and precipitation method has very limited effect on boron treatment, because the boron in the water is not easy to precipitate with common coagulants. Therefore, the traditional coagulation and precipitation method often requires the application of temperature and a large amount of coagulants. /Co-precipitant dosage to achieve higher boron removal rate.
台灣專利I594955號揭示一種高濃度含硼溶液之方法。此方法包含使用過氧化氫與硼離子反應的一道預處理程序以及使用沉澱劑(例如氫氧化鋇和氯化鋇)從含硼溶液中將硼大量移除以產生過硼酸鈣沉澱的一道沉澱程序。該方法為一種化學過氧沉澱法(COP)，其藉由過氧化氫的添加將硼酸轉換為易於沉澱的過硼酸，接著便能在室溫下與沉澱劑(含鈣化合物)產生過硼酸鈣沉澱，達到在室溫下高效地去除水中的硼。然而，該方法大致上只能從高濃度含硼溶液中將硼移除至海水硼的平均濃度5 ppm，除硼效率尚待進一步提升。此外，習用技術以鈣系化學過氧沉澱除硼，硼濃度只能降至約30 mg-B/L，高於放流水標準，且生成的沉澱物會有復溶的問題，導致硼濃度會隨時間提升。Taiwan Patent No. I594955 discloses a method for producing high-concentration boron-containing solutions. This method involves a pretreatment step using hydrogen peroxide to react with boron ions and a precipitation step using precipitating agents (such as barium hydroxide and barium chloride) to remove boron from boron-containing solutions in large quantities to produce calcium perborate precipitation. . This method is a chemical peroxygen precipitation (COP), which converts boric acid into easily precipitated perboric acid by adding hydrogen peroxide, and then combines it with a precipitating agent (calcium-containing compound) at room temperature to produce calcium perborate. Precipitate to effectively remove boron from water at room temperature. However, this method can generally only remove boron from high-concentration boron-containing solutions to an average boron concentration of 5 ppm in seawater, and the boron removal efficiency needs to be further improved. In addition, the conventional technology uses calcium-based chemical peroxide precipitation to remove boron, but the boron concentration can only be reduced to about 30 mg-B/L, which is higher than the discharge water standard, and the generated precipitate will have the problem of redissolution, causing the boron concentration to decrease. Improve over time.
緣此，本發明之主要目的在於提供一種自含硼溶液中將硼移除的方法，該方法包括三階段鈣系化學過氧沉澱除硼的技術，透過此三階段鈣系化學過氧沉澱與過濾技術可於反應15分鐘內將硼濃度由1000mg-B/L逐次下降至小於1 mg-B/L，去除率高達99.9%，遠小於台灣放流水標準(5mg-B/L)，並且該方法所選用的沉澱金屬為鈣，於放流水中沒有濃度規範，再加上其反應時間快，相對於鋇作為沉澱劑所花費的用藥成本少很多。因此，本發明的方法不只具有除硼效率的增進還具有技術與經濟可行性，有利於推廣至光電業等各種含有高濃度含硼廢水的產業。Therefore, the main purpose of the present invention is to provide a method for removing boron from a boron-containing solution. The method includes a three-stage calcium-based chemical peroxygen precipitation technology for boron removal. Through this three-stage calcium-based chemical peroxygen precipitation and The filtration technology can gradually reduce the boron concentration from 1000mg-B/L to less than 1 mg-B/L within 15 minutes of reaction. The removal rate is as high as 99.9%, which is much lower than Taiwan's discharge water standard (5mg-B/L). Moreover, the removal rate is as high as 99.9%. The precipitation metal selected for this method is calcium, and there is no concentration standard in the discharge water. In addition, its reaction time is fast, and the cost of medication is much less than that of barium as a precipitant. Therefore, the method of the present invention not only improves boron removal efficiency, but also has technical and economic feasibility, and is beneficial to be extended to various industries containing high-concentration boron-containing wastewater such as the photovoltaic industry.
根據本發明之自含硼溶液中將硼移除的方法包括：進行預處理程序，該預處理程序以氧化劑與含硼溶液混合反應，使含硼溶液中的硼酸轉換為過硼酸陰離子，其中控制反應酸鹼值在10至11之間；進行第一化學過氧沉澱程序，該第一化學過氧沉澱程序以含鈣化合物為沉澱劑而與預處理後的含硼溶液混合反應，使得含硼溶液中的過硼酸陰離子產生過硼酸鈣沉澱，其中控制反應酸鹼值在10.0至11.5之間，且控制反應時間在5至30分鐘之間；進行第一過濾程序，該第一過濾程序係過濾第一化學過氧沉澱程序的沉澱物以獲得第一上澄清液；進行第二化學過氧沉澱程序，該第二化學過氧沉澱程序以含鈣化合物為沉澱劑而與第一上澄清液混合反應，使得第一上澄清液中的過硼酸陰離子產生過硼酸鈣沉澱，其中控制反應酸鹼值控制在10.0至11.5之間，且控制反應時間在5至30分鐘之間；進行第二過濾程序，該第二過濾程序係過濾第二化學過氧沉澱程序的沉澱物以獲得第二上澄清液；及進行第三化學過氧沉澱程序，該第三化學過氧沉澱程序以含鈣化合物為沉澱劑而與第二上澄清液混合反應，使得第二上澄清液中的過硼酸陰離子產生過硼酸鈣沉澱以使溶液中的硼離子低於預設值，其中控制酸鹼值在10.0至11.5之間，且控制反應時間在5至30分鐘之間。 The method for removing boron from a boron-containing solution according to the present invention includes: performing a pretreatment procedure, which uses an oxidant and a boron-containing solution to mix and react to convert boric acid in the boron-containing solution into perborate anions, wherein control The pH value of the reaction is between 10 and 11; a first chemical peroxygen precipitation procedure is carried out, which uses a calcium-containing compound as a precipitant to react with the pretreated boron-containing solution, so that the boron-containing solution The perborate anion in the solution produces calcium perborate precipitation, wherein the pH value of the reaction is controlled between 10.0 and 11.5, and the reaction time is controlled between 5 and 30 minutes; a first filtration procedure is performed, and the first filtration procedure is filtration The precipitate of the first chemical peroxygen precipitation process is used to obtain the first super clear liquid; the second chemical peroxy precipitation process is performed, and the second chemical peroxy precipitation process uses a calcium-containing compound as a precipitant and is mixed with the first super clear liquid Reaction, causing the perborate anion in the first upper clarification liquid to produce calcium perborate precipitation, wherein the pH value of the reaction is controlled between 10.0 and 11.5, and the reaction time is controlled between 5 and 30 minutes; a second filtration procedure is performed , the second filtration process is to filter the precipitate of the second chemical peroxygen precipitation process to obtain the second upper clarification liquid; and perform the third chemical peroxygen precipitation process, the third chemical peroxygen precipitation process uses calcium-containing compounds as precipitates The agent is mixed and reacted with the second upper clarification liquid, so that the perborate anions in the second upper clarification liquid produce calcium perborate precipitation so that the boron ions in the solution are lower than the preset value, wherein the pH value is controlled between 10.0 and 11.5. time, and control the reaction time between 5 and 30 minutes.
在一實施例中，該預處理程序中的氧化劑為過氧化氫，且控制過氧化氫與含硼溶液的反應時間在10至20分鐘之間。 In one embodiment, the oxidizing agent in the pretreatment procedure is hydrogen peroxide, and the reaction time between hydrogen peroxide and the boron-containing solution is controlled to be between 10 and 20 minutes.
在一較佳實施例中，該預處理程序中的過氧化氫相對該含硼溶液中之硼離子之莫爾濃度比控制在1.0至4.0之間，且反應時間控制在5至30分鐘之間。 In a preferred embodiment, the molar concentration ratio of hydrogen peroxide in the pretreatment procedure to the boron ions in the boron-containing solution is controlled between 1.0 and 4.0, and the reaction time is controlled between 5 and 30 minutes. .
在一較佳實施例中，該預處理程序中的過氧化氫相對該含硼溶液中之硼離子之莫爾濃度比控制在2.5至3.5之間。 In a preferred embodiment, the molar concentration ratio of the hydrogen peroxide in the pretreatment procedure to the boron ions in the boron-containing solution is controlled between 2.5 and 3.5.
在一實施例中，該第一化學過氧沉澱程序中的含鈣化合物相對於含硼溶液的硼離子的莫耳濃度比控制在0.5至1.25之間；該第二化學過氧沉澱程序中的含鈣化合物相對於含硼溶液的硼離子的莫耳濃度比控制在0.4至1.0之間；該第三化學過氧沉澱程序中的含鈣化合物相對於含硼溶液的硼離子的莫耳濃度 比控制在0.1至1.0之間。 In one embodiment, the molar concentration ratio of the calcium-containing compound to the boron ions of the boron-containing solution in the first chemical peroxygen precipitation process is controlled between 0.5 and 1.25; The molar concentration ratio of the calcium-containing compound relative to the boron ions of the boron-containing solution is controlled between 0.4 and 1.0; the molar concentration ratio of the calcium-containing compound relative to the boron ions of the boron-containing solution in the third chemical peroxide precipitation procedure The ratio is controlled between 0.1 and 1.0.
在一較佳實施例中，該第一化學過氧沉澱程序中的含鈣化合物相對於含硼溶液的硼離子的莫耳濃度比控制在0.75至1.0之間；該第二化學過氧沉澱程序中的含鈣化合物相對於含硼溶液的硼離子的莫耳濃度比控制在0.5至0.75之間；該第三化學過氧沉澱程序中的含鈣化合物相對於含硼溶液的硼離子的莫耳濃度比控制在0.25至0.5之間。 In a preferred embodiment, the molar concentration ratio of the calcium-containing compound to the boron ions of the boron-containing solution in the first chemical peroxide precipitation process is controlled between 0.75 and 1.0; the second chemical peroxide precipitation process The molar concentration ratio of the calcium-containing compound relative to the boron ions of the boron-containing solution is controlled between 0.5 and 0.75; the molar concentration ratio of the calcium-containing compound in the third chemical peroxide precipitation procedure relative to the boron ions of the boron-containing solution The concentration ratio is controlled between 0.25 and 0.5.
在一實施例中，在該第一化學過氧沉澱程序、該第二化學過氧沉澱程序以及該第三化學過氧沉澱程序中的反應時間分別控制在5至20分鐘之間。 In one embodiment, the reaction times in the first chemical peroxygen precipitation process, the second chemical peroxygen precipitation process and the third chemical peroxygen precipitation process are respectively controlled between 5 and 20 minutes.
在一較佳實施例中，該第一化學過氧沉澱程序、該第二化學過氧沉澱程序以及該第三化學過氧沉澱程序中的反應時間分別控制在5至10分鐘之間。 In a preferred embodiment, the reaction times in the first chemical peroxygen precipitation process, the second chemical peroxygen precipitation process and the third chemical peroxygen precipitation process are respectively controlled between 5 and 10 minutes.
在一實施例中，含鈣化合物為氯化鈣。 In one embodiment, the calcium-containing compound is calcium chloride.
關於本發明之其它目的、優點及特徵，將可由以下較佳實施例的詳細說明並參照所附圖式來了解。 Other objects, advantages and features of the present invention will be understood from the following detailed description of the preferred embodiments and with reference to the accompanying drawings.
本發明在於提出一種自含硼溶液中將硼移除的方法，其可從高濃度含硼溶液中將硼移除至符合放流水標準，在較佳實施例中，可從高濃度含硼溶液中將硼移除至海水硼的平均濃度1ppm以下。如圖1所示，該方法包含：進行一預處理程序100、進行一第一化學過氧沉澱程序110、進行一第一過濾程序120、進行一第二化學過氧沉澱程序130、進行一第二過濾程序140、以及進行一第三化學過氧沉澱程序150。 The present invention proposes a method for removing boron from a boron-containing solution, which can remove boron from a high-concentration boron-containing solution to meet discharge water standards. In a preferred embodiment, the method can remove boron from a high-concentration boron-containing solution. Remove boron to an average boron concentration of less than 1 ppm in seawater. As shown in Figure 1, the method includes: performing a pretreatment procedure 100, performing a first chemical peroxygen precipitation procedure 110, performing a first filtration procedure 120, performing a second chemical peroxygen precipitation procedure 130, and performing a first a second filtration process 140, and a third chemical peroxide precipitation process 150.
在預處理程序100中，係以氧化劑與含硼溶液混合反應，使含硼溶液中的硼酸轉換為過硼酸陰離子。根據本發明的方法，預處理程序100之操作條件將影響後續化學過氧沉澱程序的成效。在本實施例中，預處理程序100中的氧化劑為過氧化氫且所添加的過氧化氫相對含硼溶液中之硼離子若以莫爾濃度比([H2O2]/[B])來計算，莫爾濃度比應控制在1.0至4.0之間，最好控制在2.5至3.5之間。預處理程序100中的反應酸鹼值應控制在10.0至11.0之間，最好控制在10.5。再者，過氧化氫與含硼溶液之反應時間應控制在5至30分鐘之間，最好控制在10至20分鐘之間。 In the pretreatment process 100, an oxidizing agent and a boron-containing solution are mixed and reacted to convert boric acid in the boron-containing solution into perborate anions. According to the method of the present invention, the operating conditions of the pretreatment process 100 will affect the effectiveness of the subsequent chemical peroxide precipitation process. In this embodiment, the oxidizing agent in the pretreatment process 100 is hydrogen peroxide, and the added hydrogen peroxide relative to the boron ions in the boron-containing solution is at a molar concentration ratio ([H 2 O 2 ]/[B]) To calculate, the molar concentration ratio should be controlled between 1.0 and 4.0, preferably between 2.5 and 3.5. The pH value of the reaction in the pretreatment program 100 should be controlled between 10.0 and 11.0, preferably 10.5. Furthermore, the reaction time between hydrogen peroxide and boron-containing solution should be controlled between 5 and 30 minutes, preferably between 10 and 20 minutes.
在第一、第二、第三化學過氧沉澱程序110、130、150中，係分別以含鈣化合物為沉澱劑而與預處理後的含硼溶液混合反應，使得含硼溶液中的過硼酸陰離子產生過硼酸鈣沉澱。根據本發明的方法，第一、第二、第三化學過氧沉澱程序之操作條件將影響硼處理之效率。在本實施例中，第一、第二、 第三化學過氧沉澱程序110、130、150之三個階段中的含鈣化合物為氯化鈣且分別控制反應酸鹼值在10.0至11.5之間，最好控制在11.0。再者，第一、第二、第三化學過氧沉澱程序120之三個階段的反應時間控制在5至30分鐘之間，最好控制在5至10分鐘之間。此外，第一化學過氧沉澱程序110中的含鈣化合物相對於含硼溶液的硼離子的莫耳濃度比([Ca]I/[B]0)控制在0.5至1.25之間，在較佳實施例中，控制在0.75至1.0之間；第二化學過氧沉澱程序130中的含鈣化合物相對於含硼溶液的硼離子的莫耳濃度比([Ca]Ⅱ/[B]0)控制在0.4至1.0之間，在較佳實施例中，控制在0.5至0.75之間；第三化學過氧沉澱程序150中的含鈣化合物相對於含硼溶液的硼離子的莫耳濃度比([Ca]Ⅲ/[B]0)控制在0.1至1.0之間，在較佳實施例中，控制在0.25至0.5之間。 In the first, second, and third chemical peroxygen precipitation procedures 110, 130, and 150, a calcium-containing compound is used as a precipitant to mix and react with the pretreated boron-containing solution, so that the perboric acid in the boron-containing solution Anion produces calcium perborate precipitation. According to the method of the present invention, the operating conditions of the first, second, and third chemical peroxide precipitation procedures will affect the efficiency of boron treatment. In this embodiment, the calcium-containing compound in the three stages of the first, second, and third chemical peroxide precipitation procedures 110, 130, and 150 is calcium chloride, and the pH value of the reaction is controlled to be between 10.0 and 11.5 respectively. , it is best to control it at 11.0. Furthermore, the reaction time of the three stages of the first, second, and third chemical peroxidation precipitation procedures 120 is controlled between 5 and 30 minutes, preferably between 5 and 10 minutes. In addition, the molar concentration ratio ([Ca] I /[B] 0 ) of the calcium-containing compound relative to the boron ions of the boron-containing solution in the first chemical peroxide precipitation procedure 110 is controlled between 0.5 and 1.25, preferably In the embodiment, it is controlled between 0.75 and 1.0; the molar concentration ratio ([Ca] Ⅱ / [B] 0 ) of the calcium-containing compound relative to the boron ions of the boron-containing solution in the second chemical peroxide precipitation procedure 130 is controlled Between 0.4 and 1.0, in a preferred embodiment, controlled between 0.5 and 0.75; the molar concentration ratio of the calcium-containing compound in the third chemical peroxygen precipitation procedure 150 relative to the boron ions of the boron-containing solution ([ Ca] Ⅲ /[B] 0 ) is controlled between 0.1 and 1.0. In a preferred embodiment, it is controlled between 0.25 and 0.5.
在第一過濾程序120中係過濾第一化學過氧沉澱程序110的沉澱物以獲得一第一上澄清液。在第二過濾程序140中，係過濾第二化學過氧沉澱程序130的沉澱物以獲得一第二上澄清液。藉由第一與第二過濾程序120、140過濾沉澱物能有效避免第一與第二化學過氧沉澱程序120中的過硼酸鈣復溶，以使硼濃度能穩定地降至更低。 In the first filtration process 120, the precipitate of the first chemical peroxide precipitation process 110 is filtered to obtain a first supernatant liquid. In the second filtration process 140, the precipitate of the second chemical peroxide precipitation process 130 is filtered to obtain a second supernatant liquid. Filtering the precipitate through the first and second filtration procedures 120 and 140 can effectively avoid the redissolution of calcium perborate in the first and second chemical peroxygen precipitation procedures 120, so that the boron concentration can be stably reduced to a lower level.
請參照圖2，其繪示依據本發明的方法在不同階段反應時間(a)5分鐘(b)10分鐘(c)20分鐘(d)30分鐘對於除硼效果影響的實驗實施例，在本實施例中的操作參數，預處理程序100中的過氧化氫相對含硼溶液中之硼離子之莫爾濃度比([H2O2]/[B])控制在3.0，第一化學過氧沉澱程序110中的含鈣化合物相對於含硼溶液的硼離子的莫耳濃度比([Ca]I/[B]0)控制在1；第二化學過氧沉澱程序130中的含鈣化合物相對於含硼溶液的硼離子的莫耳濃度比([Ca]Ⅱ/[B]0)控制在0.25；第三化學過氧沉澱程序中的含鈣化合物相對於含硼溶液的硼離子的莫耳濃度比([Ca]Ⅲ/[B]0)控制在0.25。在本實驗的步驟中，係配製含硼量1000ppm-B的廢水進行測試，加入過氧化氫(H2O2)並控制反應酸鹼值(pHp)=10.5，以150轉速(rpm)的混凝(Coagulation)進行預處理程序約15分鐘(min)；接著，加入氯化鈣([Ca] Ⅰ/[B] 0= 1)，並將反應酸鹼值(pH r)控制在11以進行第一化學過氧沉澱程序110，反應每隔2.5(5、10、15) min取樣並維持pH = 11，反應5(10、20、30) min後進行第一過濾程序120；接著，將過濾後的上清液加入氯化鈣( [Ca] 2/[B] 0= 0.25)，並將反應酸鹼值(pH r)控制在11以進行第二化學過氧沉澱程序130，直至反應10(20、40、60) min後進行第二過濾程序140；接著，將過濾後的上清液加入氯化鈣([Ca] Ⅲ/[B] 0= 0.25)，並將反應酸鹼值(pH r)控制在11以進行第三化學過氧沉澱程序150，直至反應15(30、60、90) min停止反應。接著，靜置溶液一天至三天，並同時取樣分析。從圖2(a)與(b)中的實驗結果可以看到，依據本發明的方法當各階段化學過氧沉澱程序的反應時間縮短為5與10分鐘時，得到的最終硼濃度皆可以達到約1 mg-B/L，接近台灣硼濃度飲用水標準。 Please refer to Figure 2, which illustrates experimental examples of the effect of reaction time (a) 5 minutes (b) 10 minutes (c) 20 minutes (d) 30 minutes on the boron removal effect at different stages according to the method of the present invention. In this The operating parameters in the embodiment, the molar concentration ratio of hydrogen peroxide to boron ions in the boron-containing solution ([H 2 O 2 ]/[B]) in the pretreatment program 100 is controlled at 3.0, and the first chemical peroxidation The molar concentration ratio ([Ca] I /[B] 0 ) of the calcium-containing compound in the precipitation procedure 110 relative to the boron ions of the boron-containing solution is controlled at 1; the calcium-containing compound in the second chemical peroxide precipitation procedure 130 is relatively The molar concentration ratio of boron ions in the boron-containing solution ([Ca] Ⅱ / [B] 0 ) is controlled at 0.25; the molar concentration ratio of the calcium-containing compound in the third chemical peroxide precipitation procedure relative to the boron ions of the boron-containing solution The concentration ratio ([Ca] III /[B] 0 ) is controlled at 0.25. In the steps of this experiment, wastewater containing 1000 ppm-B boron was prepared for testing. Hydrogen peroxide (H 2 O 2 ) was added and the reaction pH value (pH p ) = 10.5 was controlled. The reaction was carried out at 150 rotational speed (rpm). Coagulation (Coagulation) is performed for about 15 minutes (min); then, calcium chloride ([Ca] Ⅰ / [B] 0 = 1) is added, and the reaction pH value (pH r ) is controlled above 11 Carry out the first chemical peroxide precipitation procedure 110, take samples every 2.5 (5, 10, 15) minutes during the reaction and maintain the pH = 11, perform the first filtration procedure 120 after the reaction for 5 (10, 20, 30) minutes; then, Calcium chloride ([Ca] 2 /[B] 0 = 0.25) is added to the filtered supernatant, and the reaction pH value (pH r ) is controlled at 11 to perform the second chemical peroxide precipitation procedure 130 until the reaction After 10 (20, 40, 60) minutes, perform the second filtration procedure 140; then, add calcium chloride ([Ca] Ⅲ / [B] 0 = 0.25) to the filtered supernatant, and adjust the reaction pH (pH r ) is controlled at 11 to perform the third chemical peroxide precipitation procedure 150 until the reaction is stopped at 15 (30, 60, 90) minutes. The solution is then left to stand for one to three days while samples are taken for analysis. It can be seen from the experimental results in Figure 2(a) and (b) that according to the method of the present invention, when the reaction time of each stage of the chemical peroxygen precipitation process is shortened to 5 and 10 minutes, the final boron concentration obtained can reach About 1 mg-B/L, close to Taiwan’s drinking water standard for boron concentration.
請參照圖3，其繪示第一化學過氧沉澱程序中含鈣化合物相對於硼離子在不同莫耳濃度比([Ca] Ⅰ/[B] 0) = 0.5、0.75、1、1.25、1.5)下對於除硼效果影響的實驗實施例，在本實施例中的操作參數，各階段化學過氧沉澱程序的反應時間為5分鐘，預處理程序中的過氧化氫相對含硼溶液中之硼離子之莫爾濃度比([H 2O 2]/[B])控制在3.0；第二化學過氧沉澱程序130中的含鈣化合物相對於硼離子的莫耳濃度比([Ca] Ⅱ/[B] 0)控制在0.25；第三化學過氧沉澱程序中含鈣化合物相對於硼離子的莫耳濃度比([Ca] Ⅲ/[B] 0)控制在0.25。在本實驗的步驟中，係配製含硼量1000 ppm-B的廢水進行測試，加入過氧化氫(H 2O 2)並控制反應酸鹼值(pH p) =10.5，以150 轉速的混凝進行預處理程序100約15分鐘；接著，分別加入氯化鈣([Ca] Ⅰ/[B] 0) = 0.5、0.75、1、1.25、1.5) ，並將反應酸鹼值(pH r)控制在11以進行第一化學過氧沉澱程序110，反應5 min後進行第一過濾程序120；接著，將過濾後的上清液加入氯化鈣([Ca] 2/[B] 0= 0.25)，並將反應酸鹼值(pH r)控制在11以進行第二化學過氧沉澱程序130，直至反應10 min後進行第二過濾程序140；接著，將過濾後的上清液加入氯化鈣([Ca] Ⅲ/[B] 0= 0.25)，並將反應酸鹼值(pH r)控制在11以進行第三化學過氧沉澱程序150，直至反應15min停止反應。從圖3中的實驗結果可以看到，在[Ca] 1/[B] 0= 1其硼濃度為最低，可達1.75 mg-B/L。 Please refer to Figure 3, which shows the calcium-containing compound relative to boron ions at different molar concentration ratios ([Ca] Ⅰ / [B] 0 ) = 0.5, 0.75, 1, 1.25, 1.5 in the first chemical peroxide precipitation process. ) under the experimental example on the effect of boron removal. In this example, the operating parameters, the reaction time of each stage of the chemical peroxygen precipitation process is 5 minutes, the hydrogen peroxide in the pretreatment process is relatively small compared to the boron in the boron-containing solution. The molar concentration ratio of ions ([H 2 O 2 ]/[B]) is controlled at 3.0; the molar concentration ratio of the calcium-containing compound in the second chemical peroxide precipitation procedure 130 relative to the boron ion ([Ca] Ⅱ / [B] 0 ) is controlled at 0.25; in the third chemical peroxide precipitation procedure, the molar concentration ratio of calcium-containing compounds relative to boron ions ([Ca] Ⅲ / [B] 0 ) is controlled at 0.25. In the steps of this experiment, wastewater containing 1000 ppm-B boron was prepared for testing. Hydrogen peroxide (H 2 O 2 ) was added and the reaction pH value (pH p ) =10.5 was controlled. Coagulation was carried out at 150 rpm. Carry out the pretreatment procedure 100 for about 15 minutes; then, add calcium chloride ([Ca] Ⅰ / [B] 0 ) = 0.5, 0.75, 1, 1.25, 1.5), and control the reaction pH (pH r ) The first chemical peroxide precipitation procedure 110 is performed at 11, and the first filtration procedure 120 is performed after 5 minutes of reaction; then, calcium chloride ([Ca] 2 /[B] 0 = 0.25) is added to the filtered supernatant. , and control the reaction pH value (pH r ) at 11 to perform the second chemical peroxygen precipitation procedure 130, until the second filtration procedure 140 is performed after the reaction for 10 minutes; then, add calcium chloride to the filtered supernatant ([Ca] III /[B] 0 = 0.25), and the reaction pH value (pH r ) is controlled at 11 to perform the third chemical peroxide precipitation procedure 150 until the reaction is stopped after 15 minutes. It can be seen from the experimental results in Figure 3 that the boron concentration is the lowest at [Ca] 1 /[B] 0 = 1, which can reach 1.75 mg-B/L.
請參照圖4，其繪示第二化學過氧沉澱程序中含鈣化合物相對於硼離子在不同莫耳濃度比([Ca] Ⅱ/[B] 0= 0.25、0.5、0.75、1)下對於除硼效果影響的實驗實施例，在本實施例中的操作參數，各階段化學過氧沉澱程序的反應時間為5分鐘，預處理程序100中的過氧化氫相對含硼溶液中之硼離子之莫爾濃度比([H 2O 2]/[B])控制在3.0；第一化學過氧沉澱程序130中的含鈣化合物相對於硼離子的莫耳濃度比([Ca] 1/[B] 0)控制在1；第三化學過氧沉澱程序150中含鈣化合物相對於硼離子的莫耳濃度比([Ca] Ⅲ/[B] 0)控制在0.25。在本實驗步驟中，係配製含硼量1000 ppm-B的廢水進行測試，加入過氧化氫(H 2O 2)並控制反應酸鹼值(pH p) =10.5，以150 轉速的混凝進行預處理程序100約15分鐘(min)；接著，加入氯化鈣([Ca] Ⅰ/[B] 0) = 1) ，並將反應酸鹼值(pH r)控制在11以進行第一化學過氧沉澱程序110，反應每隔2.5 min取樣並維持pH = 11，反應5 min後進行第一過濾程序120；接著，將過濾後的上清液分別加入氯化鈣([Ca] Ⅱ/[B] 0= 0.25、0.5、0.75、1 )，並將反應酸鹼值(pH r)控制在11以進行第二化學過氧沉澱程序130，直至反應10 min後進行第二過濾程序140；接著，將過濾後的上清液加入氯化鈣([Ca] Ⅲ/[B] 0= 0.25)，並將反應酸鹼值(pH r)控制在11以進行第三化學過氧沉澱程序150，並在加入NaOH調整pH值之前加入部份HCl到溶液中，至反應15 min時停止反應。從圖4中的實驗結果可以看到，在[Ca] Ⅱ/[B] 0= 0.5其硼濃度為最低，能降至最低濃度0.87 mg-B/L，比[Ca] II/[B] 0=0.25時硼濃度為1.75 mg-B/L還來的低，但當[Ca] II/[B] 0=1時，硼濃度反而上升。 Please refer to Figure 4, which shows the calcium-containing compound relative to boron ions in the second chemical peroxide precipitation process at different molar concentration ratios ([Ca] Ⅱ / [B] 0 = 0.25, 0.5, 0.75, 1). Experimental example of the effect of boron removal. In this example, the operating parameters, the reaction time of each stage of the chemical peroxygen precipitation process are 5 minutes, and the hydrogen peroxide in the pretreatment process 100 is relative to the boron ions in the boron-containing solution. The molar concentration ratio ([H 2 O 2 ]/[B]) is controlled at 3.0; the molar concentration ratio of the calcium-containing compound relative to the boron ion in the first chemical peroxide precipitation procedure 130 ([Ca] 1 /[B ] 0 ) is controlled at 1; in the third chemical peroxide precipitation procedure 150 , the molar concentration ratio of the calcium-containing compound relative to the boron ion ([Ca] III /[B] 0 ) is controlled at 0.25. In this experimental step, wastewater containing 1000 ppm-B boron was prepared for testing. Hydrogen peroxide (H 2 O 2 ) was added and the reaction pH value (pH p ) =10.5 was controlled. Coagulation was performed at 150 rpm. The pretreatment program 100 is about 15 minutes (min); then, add calcium chloride ([Ca] Ⅰ / [B] 0 ) = 1), and control the reaction pH (pH r ) at 11 to perform the first chemical Peroxygen precipitation procedure 110, the reaction takes samples every 2.5 minutes and maintains pH = 11. After 5 minutes of reaction, the first filtration procedure 120 is performed; then, the filtered supernatant is added with calcium chloride ([Ca] Ⅱ /[ B] 0 = 0.25, 0.5, 0.75, 1), and the reaction pH value (pH r ) is controlled at 11 to perform the second chemical peroxide precipitation procedure 130, until the second filtration procedure 140 is performed after 10 minutes of reaction; then , add calcium chloride ([Ca] Ⅲ / [B] 0 = 0.25) to the filtered supernatant, and control the reaction pH (pH r ) at 11 to perform the third chemical peroxide precipitation procedure 150, And before adding NaOH to adjust the pH value, add part of HCl to the solution, and stop the reaction after 15 minutes. It can be seen from the experimental results in Figure 4 that the boron concentration is the lowest at [Ca] Ⅱ /[B] 0 = 0.5, and can be reduced to the lowest concentration of 0.87 mg-B/L, which is lower than [Ca] II /[B] When 0 =0.25, the boron concentration is 1.75 mg-B/L which is still low, but when [Ca] II /[B] 0 =1, the boron concentration increases instead.
請參照圖5，其繪示第三化學過氧沉澱程序中含鈣化合物相對於硼離子在不同莫耳濃度比([Ca] Ⅱ/[B] 0=0、0.25、0.5、0.75)下對於除硼效果影響的實驗實施例，在本實施例中的操作參數，各階段化學過氧沉澱程序的反應時間為5分鐘，預處理程序100中的過氧化氫相對含硼溶液中之硼離子之莫爾濃度比([H 2O 2]/[B])控制在3.0；第一化學過氧沉澱程序110中的含鈣化合物相對於硼離子的莫耳濃度比([Ca] 1/[B] 0控制在1；第二化學過氧沉澱程序130中含鈣化合物相對於硼離子的莫耳濃度比([Ca] Ⅲ/[B] 0)控制在0.5。在本實驗步驟中，係配製含硼量1000 ppm-B的廢水進行測試，加入過氧化氫(H 2O 2)並控制反應酸鹼值(pH p) =10.5，以150 轉速的混凝進行預處理程序約15分鐘(min)；接著，加入氯化鈣([Ca] Ⅰ/[B] 0) = 1)，並將反應酸鹼值(pH r)控制在11以進行第一化學過氧沉澱程序110，反應每隔2.5 min取樣並維持pH = 11，反應5 min後進行第一過濾程序120；接著，將過濾後的上清液加入氯化鈣([Ca] Ⅱ/[B] 0= 0.5 )，並將反應酸鹼值(pH r)控制在11以進行第二化學過氧沉澱程序130，直至反應10 min後進行第二過濾程序140；接著，將過濾後的上清液分別加入氯化鈣([Ca] Ⅲ/[B] 0=0、0.25、0.5、0.75)，並將反應酸鹼值(pH r)控制在11以進行第三化學過氧沉澱程序150，並在加入NaOH調整pH值之前加入部份HCl到溶液中，至反應15 min時停止反應。從圖5中的實驗結果可以看到，反應最終硼濃度在[Ca] Ⅲ/[B] 0= 0.75時可達最低(0.28 mg-B/L)，也可以看到[Ca] Ⅲ/[B] 0= 0.5及[Ca] Ⅲ/[B] 0= 0.75，在反應12.5 min時的硼濃度才是最低點。再者，當[Ca] Ⅲ/[B] 0= 0.25時可達最低(0.87 mg-B/L)，且第三階段硼濃度仍在穩定下降。 Please refer to Figure 5, which shows the calcium-containing compound relative to boron ions in the third chemical peroxide precipitation process at different molar concentration ratios ([Ca] Ⅱ / [B] 0 =0, 0.25, 0.5, 0.75). Experimental example of the effect of boron removal. In this example, the operating parameters, the reaction time of each stage of the chemical peroxygen precipitation process are 5 minutes, and the hydrogen peroxide in the pretreatment process 100 is relative to the boron ions in the boron-containing solution. The molar concentration ratio ([H 2 O 2 ]/[B]) is controlled at 3.0; the molar concentration ratio of the calcium-containing compound relative to the boron ion in the first chemical peroxide precipitation procedure 110 ([Ca] 1 /[B ] 0 is controlled at 1; in the second chemical peroxide precipitation procedure 130, the molar concentration ratio of the calcium-containing compound relative to the boron ion ([Ca] Ⅲ / [B] 0 ) is controlled at 0.5. In this experimental step, the system Wastewater containing 1000 ppm-B boron was tested. Hydrogen peroxide (H 2 O 2 ) was added and the reaction pH value (pH p ) was controlled to 10.5. The pretreatment process was carried out with coagulation at 150 rpm for about 15 minutes (min ); then, add calcium chloride ([Ca] Ⅰ / [B] 0 ) = 1), and control the reaction pH value (pH r ) at 11 to perform the first chemical peroxide precipitation procedure 110 , the reaction is Take a sample for 2.5 minutes and maintain pH = 11. After reacting for 5 minutes, perform the first filtration procedure 120; then, add calcium chloride ([Ca] Ⅱ / [B] 0 = 0.5) to the filtered supernatant, and react The acid-base value (pH r ) is controlled at 11 to perform the second chemical peroxygen precipitation procedure 130 until the second filtration procedure 140 is performed after 10 minutes of reaction; then, the filtered supernatant is added to calcium chloride ([Ca ] Ⅲ /[B] 0 =0, 0.25, 0.5, 0.75), and control the reaction pH value (pH r ) at 11 to perform the third chemical peroxide precipitation procedure 150, and add NaOH before adjusting the pH value Part of the HCl was added to the solution, and the reaction was stopped after 15 minutes. It can be seen from the experimental results in Figure 5 that the final boron concentration of the reaction reaches the lowest (0.28 mg-B/L) when [Ca] Ⅲ /[B] 0 = 0.75. It can also be seen that [Ca] Ⅲ /[ B] 0 = 0.5 and [Ca] Ⅲ /[B] 0 = 0.75, the boron concentration at the reaction time of 12.5 min is the lowest point. Furthermore, when [Ca] Ⅲ /[B] 0 = 0.25, it reaches the lowest level (0.87 mg-B/L), and the boron concentration is still decreasing steadily in the third stage.
根據本發明之方法，利用三階段化學過氧沉澱程序能夠穩定地使含硼溶液中之過硼酸陰離子產生過硼酸鈣沉澱，而將含硼溶液中之硼有效去除，從而改善習用技術鈣系化學過氧沉澱技術無法將硼濃度降至放流水標準的問題，並且相較於以往技術可縮短反應時間(可於短時間(15 min)將硼濃度降至0.87 mg-B/L)，以有效避免反應中的硼濃度回升，達成最終硼濃度能降至台灣放流水標準(5 mg-B/L)以下，甚至達成最終硼濃度能降至1 mg-B/L以下，接近台灣硼濃度飲用水的標準。According to the method of the present invention, the three-stage chemical peroxygen precipitation process can stably cause the perborate anion in the boron-containing solution to precipitate calcium perborate, thereby effectively removing the boron in the boron-containing solution, thereby improving the conventional calcium-based chemistry. Peroxygen precipitation technology cannot reduce the boron concentration to the discharge water standard. Compared with previous technologies, the reaction time can be shortened (the boron concentration can be reduced to 0.87 mg-B/L in a short time (15 minutes)) to effectively Prevent the boron concentration from rising during the reaction, and achieve the final boron concentration that can be reduced to less than Taiwan's discharge water standard (5 mg-B/L), or even achieve the final boron concentration that can be reduced to less than 1 mg-B/L, which is close to Taiwan's boron concentration for drinking. water standards.
在前述說明書中，本發明僅是就特定實施例做描述，而依本發明的特徵仍可有多種變化或修改。是以，對於熟悉此項技藝人士可作之明顯替換與修改，仍將併入於本發明所主張的專利範圍之內。In the foregoing description, the present invention is only described with respect to specific embodiments, and various changes or modifications may still be made according to the features of the present invention. Therefore, obvious substitutions and modifications that can be made by those skilled in the art will still be included in the patent scope claimed by the present invention.
100.預處理程序 110.第一化學過氧沉澱程序100. Pretreatment procedure 110. First chemical peroxide precipitation procedure
120.第一過濾程序 130.第二化學過氧沉澱程序120. The first filtration procedure 130. The second chemical peroxide precipitation procedure
140.第二過濾程序 150.第三化學過氧沉澱程序140. The second filtration procedure 150. The third chemical peroxide precipitation procedure
圖1係繪示本發明之自含硼溶液中將硼移除的方法之流程方塊圖。 Figure 1 is a block diagram illustrating a method for removing boron from a boron-containing solution of the present invention.
圖2(a)、(b)、(c)、(d)係繪示在不同階段化學過氧沉澱程序中的反應時間分別為5、10、20、30分鐘對於除硼效果影響的關係圖。 Figure 2(a), (b), (c), and (d) are diagrams illustrating the effects of reaction times of 5, 10, 20, and 30 minutes on the boron removal effect in different stages of the chemical peroxidation precipitation process. .
圖3係繪示第一化學過氧沉澱程序中的含鈣化合物相對於含硼溶液的硼離子在不同莫耳濃度比([Ca]I/[B]0)下對於除硼效果影響的關係圖。 Figure 3 illustrates the relationship between the calcium-containing compound and the boron ions in the boron-containing solution in the first chemical peroxide precipitation procedure at different molar concentration ratios ([Ca] I /[B] 0 ) on the boron removal effect. Figure.
圖4係繪示第二化學過氧沉澱程序中的含鈣化合物相對於含硼溶 液的硼離子在不同莫耳濃度比([Ca]Ⅱ/[B]0)下對於除硼效果影響的關係圖。 Figure 4 illustrates the relationship between the calcium-containing compound in the second chemical peroxide precipitation process and the boron ions in the boron-containing solution at different molar concentration ratios ([Ca] Ⅱ / [B] 0 ) on the boron removal effect. Figure.
圖5係繪示第三化學過氧沉澱程序中的含鈣化合物相對於含硼溶液的硼離子在不同莫耳濃度比([Ca]Ⅲ/[B]0)下對於除硼效果影響的關係圖。 Figure 5 shows the relationship between the calcium-containing compound in the third chemical peroxide precipitation process and the boron ions in the boron-containing solution at different molar concentration ratios ([Ca] Ⅲ / [B] 0 ) on the boron removal effect. Figure.
100.預處理程序 110.第一化學過氧沉澱程序 120.第一過濾程序 130.第二化學過氧沉澱程序 140.第二過濾程序 150.第三化學過氧沉澱程序 100. Preprocessor 110. The first chemical peroxide precipitation procedure 120. The first filtering procedure 130. Second chemical peroxide precipitation procedure 140.Second filtering procedure 150. The third chemical peroxide precipitation procedure
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| TW201738185A (en) * | 2016-04-22 | 2017-11-01 | 萬年清環境工程股份有限公司 | Method for treating boron-containing wastewater using fluidized-bed homogeneous granulation technique |
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| TW201711966A (en) * | 2015-09-17 | 2017-04-01 | 萬年清環境工程股份有限公司 | A monitoring method for a boron-containing wastewater treatment procedure |
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