TW201836986A - Method for treating tetrafluoroborate-containing wastewater - Google Patents
Method for treating tetrafluoroborate-containing wastewater Download PDFInfo
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- TW201836986A TW201836986A TW107106915A TW107106915A TW201836986A TW 201836986 A TW201836986 A TW 201836986A TW 107106915 A TW107106915 A TW 107106915A TW 107106915 A TW107106915 A TW 107106915A TW 201836986 A TW201836986 A TW 201836986A
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- boron
- tetrafluoroboric acid
- fluorine
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- 239000002351 wastewater Substances 0.000 title claims abstract description 63
- 238000000034 method Methods 0.000 title claims abstract description 18
- -1 tetrafluoroborate Chemical compound 0.000 title abstract description 15
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims abstract description 56
- 239000002253 acid Substances 0.000 claims abstract description 51
- 229910052796 boron Inorganic materials 0.000 claims abstract description 48
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 41
- 239000011737 fluorine Substances 0.000 claims abstract description 41
- 229920001429 chelating resin Polymers 0.000 claims abstract description 26
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims abstract 7
- 239000003957 anion exchange resin Substances 0.000 claims description 37
- 229920005989 resin Polymers 0.000 claims description 10
- 239000011347 resin Substances 0.000 claims description 10
- 239000013522 chelant Substances 0.000 claims description 6
- MSWZFWKMSRAUBD-IVMDWMLBSA-N glucosamine group Chemical group OC1[C@H](N)[C@@H](O)[C@H](O)[C@H](O1)CO MSWZFWKMSRAUBD-IVMDWMLBSA-N 0.000 claims description 4
- 239000003456 ion exchange resin Substances 0.000 abstract description 16
- 229920003303 ion-exchange polymer Polymers 0.000 abstract description 16
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 abstract description 11
- 125000000129 anionic group Chemical group 0.000 abstract 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 34
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 15
- 239000007788 liquid Substances 0.000 description 13
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 11
- 238000005349 anion exchange Methods 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- 239000002699 waste material Substances 0.000 description 6
- 239000004327 boric acid Substances 0.000 description 5
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical compound FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- 229910015900 BF3 Inorganic materials 0.000 description 4
- 125000000524 functional group Chemical group 0.000 description 4
- 239000011159 matrix material Substances 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical group CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 description 3
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-O ammonium group Chemical group [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 3
- 239000002585 base Substances 0.000 description 3
- 229920001577 copolymer Polymers 0.000 description 3
- 239000012458 free base Substances 0.000 description 3
- 238000005342 ion exchange Methods 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 239000012492 regenerant Substances 0.000 description 3
- 230000008929 regeneration Effects 0.000 description 3
- 238000011069 regeneration method Methods 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical group CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 3
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- 238000006386 neutralization reaction Methods 0.000 description 2
- 125000004433 nitrogen atom Chemical group N* 0.000 description 2
- 229920002223 polystyrene Polymers 0.000 description 2
- 125000001453 quaternary ammonium group Chemical group 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- LCTORNIWLGOBPB-GASJEMHNSA-N (3r,4s,5s,6r)-2-amino-6-(hydroxymethyl)oxane-2,3,4,5-tetrol Chemical compound NC1(O)O[C@H](CO)[C@@H](O)[C@H](O)[C@H]1O LCTORNIWLGOBPB-GASJEMHNSA-N 0.000 description 1
- RILZRCJGXSFXNE-UHFFFAOYSA-N 2-[4-(trifluoromethoxy)phenyl]ethanol Chemical compound OCCC1=CC=C(OC(F)(F)F)C=C1 RILZRCJGXSFXNE-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 229920002125 Sokalan® Polymers 0.000 description 1
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical group CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 1
- 239000002156 adsorbate Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 238000011001 backwashing Methods 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 229940043430 calcium compound Drugs 0.000 description 1
- 150000001674 calcium compounds Chemical class 0.000 description 1
- 239000002738 chelating agent Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000005345 coagulation Methods 0.000 description 1
- 230000015271 coagulation Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000010408 film Substances 0.000 description 1
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- QPJSUIGXIBEQAC-UHFFFAOYSA-N n-(2,4-dichloro-5-propan-2-yloxyphenyl)acetamide Chemical compound CC(C)OC1=CC(NC(C)=O)=C(Cl)C=C1Cl QPJSUIGXIBEQAC-UHFFFAOYSA-N 0.000 description 1
- 230000003204 osmotic effect Effects 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000002686 phosphate fertilizer Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 238000005554 pickling Methods 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 239000004584 polyacrylic acid Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 150000003512 tertiary amines Chemical group 0.000 description 1
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- Treatment Of Water By Ion Exchange (AREA)
- Water Treatment By Sorption (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
Description
本發明係關於含四氟硼酸之廢水的處理方法。The present invention relates to a method for treating wastewater containing tetrafluoroboric acid.
包含氟及硼，且氟及硼的一部分形成硼氟化物的含有硼氟化物之廢水，除了製造半導體時清洗矽之步驟等以外，亦由鍍敷步驟、磷酸肥料之製造步驟、鋁之電解精鍊步驟、不鏽鋼之浸洗(pickling)步驟等排放。Boron fluoride-containing wastewater containing fluorine and boron, and a part of fluorine and boron forming boron fluoride, in addition to the step of cleaning silicon during the manufacture of semiconductors, etc., also includes a plating step, a manufacturing step of phosphate fertilizer, and electrolytic refining of aluminum Steps, stainless steel pickling steps and so on.
上述廢水中，作為硼氟化物，除了以鹽等形態包含四氟硼酸(氟硼酸(HBF4 ))以外，亦有亦包含三氟化硼(BF3 )之情形，該三氟化硼係藉由水來分解而生成四氟硼酸(HBF4 )及硼酸(H3 BO3 )(4BF3 ＋3H2 O→3HBF4 ＋H3 BO3 )。In the above-mentioned wastewater, in addition to tetrafluoroboric acid (fluoroboric acid (HBF 4 )) in the form of a salt or the like, boron trifluoride (BF 3 ) may also be contained. Decomposed by water to generate tetrafluoroboric acid (HBF 4 ) and boric acid (H 3 BO 3 ) (4BF 3 + 3H 2 O → 3HBF 4 + H 3 BO 3 ).
基於排放標準，係要求上述廢水中的硼及氟之含量抑制為一定値以下，然而例如四氟硼酸(HBF4 )之金屬鹽或銨鹽對水顯示可溶性，且均為在低溫下為安定，因此難以進行經由凝聚分離之去除。Based on the discharge standards, the content of boron and fluorine in the above-mentioned wastewater is required to be suppressed below a certain threshold. However, for example, the metal salt or ammonium salt of tetrafluoroboric acid (HBF 4 ) shows solubility in water and is stable at low temperatures. Therefore, it is difficult to perform the removal by coagulation separation.
作為處理這種含有四氟硼酸等硼氟化物之廢水的方法，專利文獻1(日本特開昭52-38772號公報)提案一種方法，其於包含硼之含氟廢水中添加水溶性鈣化合物與硫酸，經固液分離後，使所得之處理水接觸鹼性陰離子交換樹脂。 [先前技術文獻] [專利文獻]As a method for treating such a wastewater containing boron fluoride such as tetrafluoroboric acid, Patent Document 1 (Japanese Patent Application Laid-Open No. 52-38772) proposes a method of adding a water-soluble calcium compound to a fluorine-containing wastewater containing boron and After the sulfuric acid is subjected to solid-liquid separation, the obtained treated water is brought into contact with a basic anion exchange resin. [Prior Art Literature] [Patent Literature]
[專利文獻1]日本特開昭52-38772號公報[Patent Document 1] Japanese Patent Laid-Open No. 52-38772
[發明所欲解決之課題][Problems to be Solved by the Invention]
然而，經本案發明人等之探討，可知：專利文獻1記載之方法，其硼氟化物的去除效率未必充分，又，當為了去除硼氟化物而使用陰離子交換管柱時，在陰離子交換管柱中pH會從中性變成鹼性，因此會由四氟硼酸(HBF4 )生成硼酸(H3 BO3 )，而所生成之硼酸即使是強鹼性陰離子交換樹脂亦吸附量極小，因此不只所生成之硼酸(H3 BO3 )，連廢水中原本存在的硼酸(H3 BO3 )亦無法充分吸附去除，而早早發生滲漏、或廢水中的四氟硼酸(HBF4 )和硼酸(H3 BO3 )難以降低至預定的濃度。However, according to the inventors of the present case, it is understood that the method described in Patent Document 1 may not have sufficient removal efficiency of borofluoride. When an anion exchange column is used to remove borofluoride, the The neutral pH will change from neutral to alkaline, so boric acid (H 3 BO 3 ) will be generated from tetrafluoroboric acid (HBF 4 ), and the generated boric acid will have a very small adsorption amount even if it is a strongly basic anion exchange resin. the boric acid (H 3 BO 3), even boric acid originally present in the waste water (H 3 BO 3) also can not be sufficiently removed by adsorption, and the early occurrence of leakage, or tetrafluoroboric acid (HBF 4) and boric acid (H 3 wastewater BO 3 ) is difficult to reduce to a predetermined concentration.
在這種狀況下，本發明之目的係提供一種新穎的處理方法，其簡便地降低在包含氟及硼的同時，氟及硼的一部分形成四氟硼酸的含四氟硼酸之廢水中的氟及硼之含量。 [用以解決課題之手段]Under these circumstances, an object of the present invention is to provide a novel treatment method which can easily reduce fluorine and tetrafluoroborate in waste water containing tetrafluoroborate while containing fluorine and boron, and part of the fluorine and boron form tetrafluoroborate. Content of boron. [Means to solve the problem]
本案發明人為了達成上述目的而不斷鑽研，結果發現藉由使在包含氟及硼的同時，氟及硼的一部分形成四氟硼酸的含四氟硼酸之廢水，依序接觸鹼性陰離子交換樹脂及具有硼選擇性之螯合樹脂，可解決上述技術課題，並且基於本見解而終臻完成本發明。 換言之，本發明係提供： (1)一種含四氟硼酸之廢水的處理方法，其特徵為：使在包含氟及硼的同時，氟及硼的一部分形成四氟硼酸的含四氟硼酸之廢水，接觸鹼性陰離子交換樹脂後，接觸具有硼選擇性之螯合樹脂； (2)如上述(1)記載之含四氟硼酸之廢水的處理方法，其中，前述鹼性陰離子交換樹脂為弱鹼性陰離子交換樹脂或強鹼性陰離子交換樹脂； (3)如上述(1)或(2)記載之含四氟硼酸之廢水的處理方法，其中，前述螯合樹脂具有N-甲基還原葡糖胺基。 [發明之效果]In order to achieve the above-mentioned object, the inventors of the present invention have continued to study, and found that by including fluorine and boron, a part of the fluorine and boron forms a tetrafluoroborate-containing wastewater, and sequentially contacts the basic anion exchange resin and A chelate resin having boron selectivity can solve the above technical problems, and finally complete the present invention based on this knowledge. In other words, the present invention provides: (1) A method for treating a waste water containing tetrafluoroboric acid, characterized in that while containing fluorine and boron, a part of the fluorine and boron forms a tetrafluoroboric acid-containing waste water After contacting a basic anion exchange resin, contact a chelating resin having boron selectivity; (2) A method for treating a wastewater containing tetrafluoroboric acid as described in (1) above, wherein the basic anion exchange resin is a weak base (3) The method for treating waste water containing tetrafluoroboric acid according to the above (1) or (2), wherein the chelating resin has N-methyl reducing glucose Amine. [Effect of the invention]
根據本發明，可提供一種新穎的處理方法，其簡便地降低包含氟及硼，且氟及硼的一部分形成四氟硼酸的含四氟硼酸之廢水中的氟及硼之含量。According to the present invention, it is possible to provide a novel treatment method which can simply reduce the content of fluorine and boron in a tetrafluoroboric acid-containing wastewater containing fluorine and boron, and a part of the fluorine and boron forms tetrafluoroboric acid.
本發明之含四氟硼酸之廢水的處理方法，其特徵為：使在包含氟及硼的同時，氟及硼的一部分形成四氟硼酸的含四氟硼酸之廢水，接觸鹼性陰離子交換樹脂後，接觸具有硼選擇性之螯合樹脂。The method for treating waste water containing tetrafluoroboric acid according to the present invention is characterized in that: while containing fluorine and boron, a part of the fluorine and boron forms a tetrafluoroboric acid-containing waste water, which is contacted with an alkaline anion exchange resin Contact a chelating resin with boron selectivity.
在本發明中，以處理對象之含四氟硼酸之廢水而言，係以酸性(小於pH7)者為適當，pH2～6者為更適當，pH2～4者為進一步更適當。 在本發明中，處理對象之含四氟硼酸之廢水，亦可於鹼性陰離子交換樹脂接觸處理前適宜地調整pH。 藉由使含四氟硼酸之廢水的pH於上述範圍內，可使四氟硼酸安定地存在於廢水中。In the present invention, the waste water containing tetrafluoroboric acid to be treated is preferably acidic (less than pH 7), more preferably pH 2 to 6, and more preferably pH 2 to 4. In the present invention, the pH of the waste water containing tetrafluoroboric acid to be treated can be appropriately adjusted before the alkaline anion exchange resin contact treatment. By setting the pH of the wastewater containing tetrafluoroborate to the above range, the tetrafluoroborate can be stably present in the wastewater.
在本發明中，處理對象之含四氟硼酸之廢水中的氟濃度，係以10～300質量ppm為適當，30～100質量ppm為更適當，50～70質量ppm為進一步更適當。In the present invention, the fluorine concentration in the waste water containing tetrafluoroboric acid to be treated is suitably 10 to 300 mass ppm, more preferably 30 to 100 mass ppm, and more preferably 50 to 70 mass ppm.
在本發明中，處理對象之含四氟硼酸之廢水中的硼濃度，係以5～200質量ppm為適當，10～100質量ppm為更適當，30～60質量ppm為進一步更適當。In the present invention, the boron concentration in the waste water containing tetrafluoroboric acid to be treated is suitably 5 to 200 mass ppm, 10 to 100 mass ppm is more appropriate, and 30 to 60 mass ppm is further more suitable.
在本發明中，處理對象之含四氟硼酸之廢水中的四氟硼酸濃度，係以10～350質量ppm為適當，30～120質量ppm為更適當，60～80質量ppm為進一步更適當。In the present invention, the concentration of tetrafluoroboric acid in the waste water containing tetrafluoroboric acid to be treated is suitably 10 to 350 mass ppm, more preferably 30 to 120 mass ppm, and more preferably 60 to 80 mass ppm.
在本發明中，藉由使處理對象之含四氟硼酸之廢水中的氟濃度、硼濃度及四氟硼酸濃度於上述範圍內，可更有效地降低含四氟硼酸之廢水中的氟及硼之含量。In the present invention, by setting the fluorine concentration, boron concentration, and tetrafluoroboric acid concentration in the tetrafluoroborate-containing wastewater to be treated within the above ranges, the fluorine and boron in the tetrafluoroborate-containing wastewater can be more effectively reduced. Of content.
在本發明中，係使含四氟硼酸之廢水接觸鹼性陰離子交換樹脂後，接觸具有硼選擇性之螯合樹脂。In the present invention, after the waste water containing tetrafluoroboric acid is contacted with a basic anion exchange resin, it is contacted with a chelating resin having boron selectivity.
在本發明中，鹼性陰離子交換樹脂只要是於樹脂製的基體導入陰離子交換基之粒狀的離子交換體則未特別限制，可採用粉末狀、珠粒狀、膜狀等各種形態者，亦可為凝膠型離子交換樹脂或多孔性型離子交換樹脂之任一者。In the present invention, the basic anion exchange resin is not particularly limited as long as it is a granular ion exchanger in which an anion exchange group is introduced into a resin-made substrate, and various forms such as powder, bead, and film may be used. It may be either a gel type ion exchange resin or a porous type ion exchange resin.
凝膠型離子交換樹脂及多孔性型離子交換樹脂係基於離子交換樹脂的微結構之分類，其中，凝膠型離子交換樹脂係意指：將苯乙烯與二乙烯苯在無溶媒下聚合者作為基體之離子交換樹脂，且為具有不均勻地交聯之凝膠狀的結構之最古典的離子交換樹脂。Gel-type ion-exchange resins and porous ion-exchange resins are classified based on the microstructure of ion-exchange resins. Among them, gel-type ion-exchange resins are those in which styrene and divinylbenzene are polymerized without a solvent as The matrix ion exchange resin is the most classical ion exchange resin with a gel-like structure that is not uniformly crosslinked.
又，多孔性型離子交換樹脂係意指：將藉由於聚合時使用溶媒而形成有孔徑20nm至100nm左右的大孔(macropore)之樹脂作為基體之離子交換樹脂，亦包含被稱為MR型者。多孔性型離子交換樹脂由於即使極性低的溶媒亦可進入樹脂內部，因此即使非水溶液系亦可使用，雖然因為大孔不連續且亦欠缺均勻度而離子交換容量低於凝膠型樹脂，然而物理強度高且對於滲透壓或機械壓力之耐性優異。The porous ion-exchange resin refers to an ion-exchange resin using a resin having a macropore with a pore size of about 20 nm to 100 nm as a matrix by using a solvent during polymerization. . Porous ion-exchange resins can enter the resin even with low-polarity solvents, so they can be used even in non-aqueous systems. Although the ion exchange capacity is lower than gel-type resins because the macropores are discontinuous and lack uniformity, High physical strength and excellent resistance to osmotic pressure or mechanical pressure.
在本發明中，作為離子交換樹脂，係以將苯乙烯-二乙烯苯共聚物作為基體之MR型離子交換樹脂為較佳。In the present invention, as the ion exchange resin, an MR type ion exchange resin using a styrene-divinylbenzene copolymer as a matrix is preferred.
又，在本發明中，作為構成離子交換樹脂之陰離子交換基(negative ion-exchange group；anion-exchange group)，並未特別限制，只要是選自弱鹼性陰離子交換樹脂及強鹼性陰離子交換樹脂之一種以上即可。當處理對象之含四氟硼酸之廢水的pH為酸性(小於pH7)時，從再生效率的觀點來看，係以弱鹼性陰離子交換樹脂為較佳。In the present invention, the negative ion-exchange group (anion-exchange group) constituting the ion-exchange resin is not particularly limited as long as it is selected from a weakly basic anion exchange resin and a strongly basic anion exchange resin. One or more resins may be sufficient. When the pH of the waste water containing the tetrafluoroborate to be treated is acidic (less than pH 7), from the viewpoint of regeneration efficiency, a weakly basic anion exchange resin is preferred.
作為陰離子交換基，可列舉選自三甲基銨基、三乙基銨基、二甲基銨基等三級銨基等之一種以上。Examples of the anion exchange group include one or more selected from tertiary ammonium groups such as a trimethylammonium group, a triethylammonium group, and a dimethylammonium group.
作為陰離子交換樹脂，更詳細而言，可列舉選自下述之一種以上：具有四級銨基作為官能基，且鍵結於該銨基的氮原子之基僅為烷基的強鹼性I型；具有四級銨基作為官能基，且鍵結於該銨基的氮原子之基為烷基及烷醇基的強鹼性II型；具有一級～三級胺基作為官能基的弱鹼性。More specifically, as the anion exchange resin, one or more members selected from the group consisting of strong basic groups I having a quaternary ammonium group as a functional group, and a group of a nitrogen atom bonded to the ammonium group being only an alkyl group I Type; strong basic type II with a quaternary ammonium group as a functional group, and the group of the nitrogen atom bonded to the ammonium group is an alkyl group and an alkanol group; a weak base having a primary to tertiary amine group as a functional group Sex.
作為弱鹼性陰離子交換樹脂，係以具有二甲基銨基作為陰離子交換基者為佳；作為強鹼性陰離子交換樹脂，係以具有三甲基銨基作為陰離子交換基者為佳。As the weakly basic anion exchange resin, it is preferable to use a dimethylammonium group as an anion exchange group; as the strongly basic anion exchange resin, it is preferable to use a trimethylammonium group as an anion exchange group.
在本發明中，當陰離子交換樹脂具有粒狀時，其平均粒徑係以0.2～1.0mm為較佳，0.4～0.8mm為更佳。In the present invention, when the anion exchange resin has a granular shape, the average particle diameter is preferably 0.2 to 1.0 mm, and more preferably 0.4 to 0.8 mm.
此外，在本說明書中，平均粒徑係意指藉由粒度分布測定裝置(Beckman Coulter公司製雷射繞射散射式粒度分布測定裝置(商品名：LS 13 320(濕式系統))所測定之値。In addition, in this specification, the average particle diameter means a particle size distribution measurement device (a laser diffraction scattering type particle size distribution measurement device (trade name: LS 13 320 (wet system) manufactured by Beckman Coulter)). value.
使含四氟硼酸之廢水接觸鹼性陰離子交換樹脂時之通水速度並未特別限制，而以SV(空間速度)為2～20hr－ 1 為較佳，3～10hr－ 1 為更佳，4～6hr－ 1 為進一步更佳。Tetrafluoroborate-containing wastewater into contact through the basic anion exchange resin is the speed at which water is not particularly limited but in order to SV (space velocity) of 2 ~ 20hr - 1 is preferred, 3 ~ 10hr - 1 is more preferred, 4 ~ 6hr - 1 in order to further better.
藉由使含四氟硼酸之廢水接觸鹼性陰離子交換樹脂，BF4 － 等陰離子被吸附，因此可將廢水中的四氟硼酸(HBF4 )濃度降低至一定程度以下。By contacting the wastewater containing tetrafluoroboric acid with the basic anion exchange resin, anions such as BF 4 − are adsorbed, so that the concentration of tetrafluoroboric acid (HBF 4 ) in the wastewater can be reduced to a certain level or less.
在本發明中係使含四氟硼酸之廢水接觸鹼性陰離子交換樹脂後，接觸具有硼選擇性之螯合樹脂。In the present invention, after the wastewater containing tetrafluoroboric acid is contacted with the basic anion exchange resin, the chelating resin having boron selectivity is contacted.
螯合樹脂係藉由導入容易與金屬形成螯合鍵結之螯合生成基(以下亦稱為「螯合基」)來取代離子交換樹脂中的離子交換基，而可選擇性地吸附特定的金屬之樹脂。The chelating resin is capable of selectively adsorbing a specific metal by introducing a chelate-forming group (hereinafter also referred to as a "chelating group") that easily forms a chelate bond with a metal to replace the ion-exchange group in the ion-exchange resin. The resin.
在本發明中，作為上述螯合生成基所鍵結的基體，可列舉與上述構成鹼性陰離子交換樹脂之基體相同者，例如選自交聯聚苯乙烯、苯乙烯-二乙烯苯共聚物等苯乙烯系化合物、酚類、醛類之縮合物、交聯聚丙烯酸等之一種以上為較佳，交聯聚苯乙烯或苯乙烯-二乙烯苯共聚物為更佳。In the present invention, examples of the substrate to which the chelation-forming group is bonded include the same as the substrate constituting the basic anion exchange resin. For example, the substrate is selected from the group consisting of crosslinked polystyrene, styrene-divinylbenzene copolymer, and the like. One or more of a styrenic compound, a phenol, an aldehyde condensate, and a cross-linked polyacrylic acid are preferable, and a cross-linked polystyrene or a styrene-divinylbenzene copolymer is more preferable.
螯合基係與一般的螯合劑相同地組合並包含同種或異種2個以上的N、S、O、P等元素作為提供電子的元素之基，例如可列舉N-O系、S-N系、N-N系、O-O系等種類。若此等螯合基鍵結於三次元高分子基體，則可得到因應螯合基而對特定的金屬具有選擇性之螯合樹脂。The chelating group is the same as a general chelating agent, and contains two or more elements of the same or different types, such as N, S, O, and P, as a base for providing an electron. Examples include NO, SN, NN, OO series and other types. If these chelating groups are bonded to a three-dimensional polymer matrix, a chelating resin having selectivity to a specific metal in accordance with the chelating group can be obtained.
作為螯合基，只要是具有選擇性地吸附硼之選擇性的螯合基則未特別限定，例如可列舉選自N-甲基還原葡糖胺基等多元醇之一種以上的官能基，而以N-甲基還原葡糖胺基為較佳。The chelating group is not particularly limited as long as it is a selective chelating group capable of selectively adsorbing boron, and examples thereof include one or more functional groups selected from polyhydric alcohols such as N-methyl reduced glucosamine groups, and N-methyl is preferred to reduce the glucosamine group.
在本發明中，螯合樹脂之形狀亦未特別限制，而例如當螯合樹脂具有粒狀時，其平均粒徑係以0.2～1.0mm為較佳，0.4～0.8mm為更佳。In the present invention, the shape of the chelate resin is also not particularly limited. For example, when the chelate resin has a granular shape, the average particle diameter is preferably 0.2 to 1.0 mm, and more preferably 0.4 to 0.8 mm.
含四氟硼酸之廢水係於與上述鹼性陰離子交換樹脂接觸處理時，進行中和及中和鹽分解而廢水的pH成為鹼性。 在本發明中，以接觸鹼性陰離子交換樹脂後，接觸具有硼選擇性之螯合樹脂之廢水而言，係以pH8～11者為適當，pH8～10者為更適當，pH8.5～10者為進一步更適當。 在本發明中，處理對象之含四氟硼酸之廢水，亦可於與具有硼選擇性之螯合樹脂接觸處理前適宜地調整pH。 藉由使含四氟硼酸之廢水的pH於上述範圍內，可使硼酸安定地存在於廢水中。The wastewater containing tetrafluoroboric acid is subjected to neutralization and neutralization salt decomposition during the contact treatment with the basic anion exchange resin, and the pH of the wastewater becomes alkaline. In the present invention, in the case of contacting wastewater having a boron-selective chelating resin after contacting the basic anion exchange resin, a pH of 8 to 11 is suitable, a pH of 8 to 10 is more suitable, and a pH of 8.5 to 10 It is more appropriate for further. In the present invention, the pH of the waste water containing tetrafluoroboric acid to be treated can be suitably adjusted before contacting with the chelating resin having boron selectivity. By setting the pH of the wastewater containing tetrafluoroboric acid to the above range, boric acid can be stably present in the wastewater.
四氟硼酸(HBF4 )一旦液中的pH成為鹼性就會發生分解反應(HBF4 ＋3H2 O→H3 BO3 ＋4HF)而生成硼酸(H3 BO3 )與氟酸(HF)，而硼酸(H3 BO3 )難以藉由鹼性陰離子交換樹脂去除，當廢水中原本即包含硼酸(H3 BO3 )時，則變得更容易殘存於廢液中。 另一方面，藉由使含四氟硼酸之廢水接觸鹼性陰離子交換樹脂後，接觸具有硼選擇性之螯合樹脂，可將廢液中殘存的硼酸濃度降低至一定程度以下。Tetrafluoroboric acid (HBF 4 ) will decompose once the pH of the liquid becomes alkaline (HBF 4 + 3H 2 O → H 3 BO 3 + 4HF) to generate boric acid (H 3 BO 3 ) and hydrofluoric acid (HF), and Boric acid (H 3 BO 3 ) is difficult to remove by basic anion exchange resin. When boric acid (H 3 BO 3 ) is originally contained in the wastewater, it becomes easier to remain in the waste liquid. On the other hand, after the wastewater containing tetrafluoroboric acid is contacted with the basic anion exchange resin and then the chelating resin having boron selectivity is contacted, the residual boric acid concentration in the waste liquid can be reduced to a certain level or less.
使含四氟硼酸之廢水接觸具有硼選擇性之螯合樹脂時的通水速度並未特別限制，而以SV(空間速度)為2～20hr－ 1 為較佳，3～10hr－ 1 為更佳，4～6hr－ 1 為進一步更佳。Water passing speed at the contact with the wastewater containing boron tetrafluoroborate selectivity of the chelate resin is not particularly limited but in order to SV (space velocity) of 2 ~ 20hr - 1 is preferred, 3 ~ 10hr - 1 is more Jia, 4 ~ 6hr - 1 is further preferable.
處理預定通水量之廢水後的鹼性陰離子交換樹脂或具有硼選擇性之螯合樹脂，可藉由因應需要而進行逆洗後，使再生劑通過，使吸附物溶離而再生。藉由使上述再生劑通過，而生成含有高濃度的氟及硼之再生廢液。The alkaline anion exchange resin or boron-selective chelating resin after treating wastewater with a predetermined water flow rate can be regenerated by passing back the regenerant and dissolving the adsorbate after backwashing as required. By passing the regenerant, a regeneration waste liquid containing fluorine and boron at a high concentration is generated.
鹼性陰離子交換樹脂之再生，係可藉由使氫氧化鈉等作為再生劑通過而再生。The regeneration of the basic anion exchange resin can be performed by passing sodium hydroxide or the like as a regenerant.
根據本發明，可提供一種新穎的處理方法，其簡便地降低包含氟及硼，且氟及硼的一部分形成四氟硼酸的含四氟硼酸之廢水中的氟及硼之含量。According to the present invention, it is possible to provide a novel treatment method which can simply reduce the content of fluorine and boron in a tetrafluoroboric acid-containing wastewater containing fluorine and boron, and a part of the fluorine and boron forms tetrafluoroboric acid.
(實施例) 其次，列舉實施例來更具體地說明本發明，惟其為單純的例示，並未限制本發明。(Examples) Next, the present invention will be described more specifically with reference to examples, but these are merely examples and do not limit the present invention.
(實施例1) 如圖1所示，分別準備內徑1.8cm、高度100cm的壓克力管柱C1、C2，將該2根管柱C1、C2中長度方向的一端彼此以可通液的方式連接為直列。 在於前段的壓克力管柱C1填充100mL的遊離鹼型弱鹼性陰離子交換樹脂(Dow Chemical公司製Amberlite IRA96RF，包含二甲基銨基作為陰離子交換基者)的同時，於後段的壓克力管柱C2填充100mL的還原葡糖胺型螯合樹脂(Dow Chemical公司製Amberlite IRA743，包含N-甲基還原葡糖胺基作為螯合基者)，對於前段的壓克力管柱C1之注入口，使用泵P由廢液槽1導入硼濃度為56mg/L、氟濃度為66mg/L、pH2.9、導電率為40mS/cm之含四氟硼酸之廢水，以通水速度：5L/hr由前段的壓克力管柱C1通液至後段的壓克力管柱C2後，由後段的壓克力管柱C2之(與壓克力管柱C1連接側端部相反側的)端部排液至排液槽2。 將1L的含四氟硼酸之廢水由廢液槽1連續地通液2次(合計2L)至壓克力管柱C1、C2。 測定所得之排液中的硼濃度及氟濃度。將結果示於表1及表2。(Example 1) As shown in FIG. 1, acrylic tubing columns C1 and C2 having an inner diameter of 1.8 cm and a height of 100 cm were prepared, and one end in the longitudinal direction of the two tubing strings C1 and C2 was fluid-permeable to each other. The mode connection is in-line. The acrylic column C1 at the front stage is filled with 100 mL of a free-base weakly basic anion exchange resin (Amberlite IRA96RF manufactured by Dow Chemical Co., which contains a dimethyl ammonium group as an anion exchange group), and the acrylic at the rear stage Column C2 is filled with 100 mL of reduced glucosamine-type chelating resin (Amberlite IRA743 manufactured by Dow Chemical Co., which contains N-methyl reduced glucosamine groups as chelating groups). Note for the previous acrylic column C1 At the inlet, waste water containing tetrafluoroboric acid with a boron concentration of 56 mg / L, a fluorine concentration of 66 mg / L, a pH of 2.9, and a conductivity of 40 mS / cm is introduced from the waste liquid tank 1 using a pump P at a water passing rate of 5 L / After passing the liquid from the former acrylic column C1 to the latter acrylic column C2, the end of the latter acrylic column C2 (the side opposite to the end of the connecting side of the acrylic column C1) The part is drained to the drain tank 2. 1 L of waste water containing tetrafluoroboric acid was continuously passed through the waste liquid tank 1 twice (total 2 L) to the acrylic column C1 and C2. The boron concentration and fluorine concentration in the obtained discharged liquid were measured. The results are shown in Tables 1 and 2.
(實施例2) 除了在實施例1中，於前段的壓克力管柱C1填充100mL的OH型強鹼性陰離子交換樹脂(Dow Chemical公司製 Amberlite IRA402BL，包含三甲基銨基作為陰離子交換基者)以外，與實施例1同樣地處理含四氟硼酸之廢水，測定所得之排液中的硼濃度及氟濃度。將結果示於表1及表2。(Example 2) Except in Example 1, an acrylic column C1 in the preceding stage was filled with 100 mL of an OH-type strongly basic anion exchange resin (Amberlite IRA402BL manufactured by Dow Chemical Co., which contained a trimethylammonium group as an anion exchange group). Except that), the wastewater containing tetrafluoroboric acid was treated in the same manner as in Example 1, and the boron concentration and fluorine concentration in the obtained discharged liquid were measured. The results are shown in Tables 1 and 2.
(比較例1) 除了在實施例1中，於前段及後段的壓克力管柱C1、C2均填充100mL的遊離鹼型弱鹼性陰離子交換樹脂(Dow Chemical公司製Amberlite IRA96RF)以外，與實施例1同樣地處理含四氟硼酸之廢水，測定所得之排液中的硼濃度及氟濃度。將結果示於表1及表2。(Comparative Example 1) Except that in Example 1, the acrylic column C1 and C2 in the front stage and the rear stage were filled with 100 mL of a free base weakly basic anion exchange resin (Amberlite IRA96RF, manufactured by Dow Chemical Co., Ltd.), Example 1 The wastewater containing tetrafluoroboric acid was treated in the same manner, and the boron concentration and the fluorine concentration in the obtained discharged liquid were measured. The results are shown in Tables 1 and 2.
(比較例2) 除了在實施例1中，於前段及後段的壓克力管柱C1、C2均填充100mL的還原葡糖胺型螯合樹脂(Dow Chemical公司製Amberlite IRA743)以外，與實施例1同樣地處理含四氟硼酸之廢水，測定所得之排液中的硼濃度及氟濃度。將結果示於表1及表2。(Comparative Example 2) Except that in Example 1, the acrylic columns C1 and C2 in the first and subsequent stages were each filled with 100 mL of a reduced glucosamine-type chelating resin (Amberlite IRA743 manufactured by Dow Chemical Co., Ltd.). 1 Treat the waste water containing tetrafluoroboric acid in the same manner, and measure the boron concentration and fluorine concentration in the obtained discharged liquid. The results are shown in Tables 1 and 2.
(比較例3) 除了在實施例1中，於前段的壓克力管柱C1填充100mL的還原葡糖胺型螯合樹脂(Dow Chemical公司製Amberlite IRA743)且於後段的壓克力管柱C2填充100mL的遊離鹼型弱鹼性陰離子交換樹脂(Dow Chemical公司製Amberlite IRA96RF)以外，與實施例1同樣地處理含四氟硼酸之廢水，測定所得之排液中的硼濃度及氟濃度。將結果示於表1及表2。(Comparative Example 3) Except in Example 1, the acrylic column C1 at the front stage was filled with 100 mL of a reduced glucosamine-type chelating resin (Amberlite IRA743 manufactured by Dow Chemical Co.), and the acrylic column C2 at the subsequent stage Except that 100 mL of a free-base weakly basic anion exchange resin (Amberlite IRA96RF manufactured by Dow Chemical Co., Ltd.) was filled, waste water containing tetrafluoroboric acid was treated in the same manner as in Example 1, and the boron concentration and fluorine concentration in the obtained discharged liquid were measured. The results are shown in Tables 1 and 2.
【表1】
【表2】
根據表1，可知由於在實施例1及實施例2中，使含四氟硼酸之廢水接觸鹼性陰離子交換樹脂後，接觸具有硼選擇性之螯合樹脂，因此可使廢水中的硼濃度及氟濃度降低至更低濃度。 另一方面，可知由於在比較例1中，僅使含四氟硼酸之廢水接觸鹼性陰離子交換樹脂，在比較例2中，僅使含四氟硼酸之廢水接觸具有硼選擇性之螯合樹脂，又，在比較例3中，使含四氟硼酸之廢水接觸具有硼選擇性之螯合樹脂後，接觸鹼性陰離子交換樹脂，因此廢水中的硼濃度及氟濃度無法充分地降低。 [產業上的可利用性]According to Table 1, it can be seen that in Example 1 and Example 2, after the wastewater containing tetrafluoroboric acid was contacted with the basic anion exchange resin and then the chelating resin having boron selectivity was contacted, the boron concentration and The fluorine concentration is reduced to a lower concentration. On the other hand, it can be seen that in Comparative Example 1, only the tetrafluoroboric acid-containing wastewater was contacted with the basic anion exchange resin, and in Comparative Example 2, only the tetrafluoroboric acid-containing wastewater was contacted with the boron-selective chelating resin. Furthermore, in Comparative Example 3, after the wastewater containing tetrafluoroboric acid was brought into contact with a chelating resin having boron selectivity and then contacted with a basic anion exchange resin, the boron concentration and fluorine concentration in the wastewater could not be sufficiently reduced. [Industrial availability]
根據本發明，可提供一種新穎的處理方法，其簡便地降低包含氟及硼，且氟及硼的一部分形成四氟硼酸的含四氟硼酸之廢水中的氟及硼之含量。According to the present invention, it is possible to provide a novel treatment method which can simply reduce the content of fluorine and boron in a tetrafluoroboric acid-containing wastewater containing fluorine and boron, and a part of the fluorine and boron forms tetrafluoroboric acid.
1‧‧‧廢液槽1‧‧‧waste tank
2‧‧‧排液槽2‧‧‧ drainage tank
C1、C2‧‧‧壓克力管柱C1, C2‧‧‧‧Acrylic tubing
P‧‧‧泵P‧‧‧Pump
【圖1】圖1係表示本發明之實施例及比較例所使用之處理裝置之圖。[Fig. 1] Fig. 1 is a diagram showing a processing device used in Examples and Comparative Examples of the present invention.
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| CN111085278A (en) * | 2018-10-18 | 2020-05-01 | 中国石油化工股份有限公司 | Method for removing boron trifluoride |
| CN112452308B (en) * | 2020-12-09 | 2022-10-25 | 昆明理工大学 | A kind of synthetic method and application of pyridine amide-containing adsorption polymer |
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| TWI894434B (en) * | 2021-07-07 | 2025-08-21 | 日商奧璐佳瑙股份有限公司 | Method for removing boron |
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