JP2011201770A - Method for producing valuable substance from waste liquid - Google Patents
Method for producing valuable substance from waste liquid Download PDFInfo
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- JP2011201770A JP2011201770A JP2011115371A JP2011115371A JP2011201770A JP 2011201770 A JP2011201770 A JP 2011201770A JP 2011115371 A JP2011115371 A JP 2011115371A JP 2011115371 A JP2011115371 A JP 2011115371A JP 2011201770 A JP2011201770 A JP 2011201770A
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- sodium
- waste liquid
- hydrofluoric acid
- acid
- silicofluoride
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- 239000007788 liquid Substances 0.000 title claims abstract description 49
- 239000002699 waste material Substances 0.000 title claims abstract description 45
- 238000004519 manufacturing process Methods 0.000 title claims description 22
- 239000000126 substance Substances 0.000 title description 4
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims abstract description 78
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims abstract description 42
- 239000011734 sodium Substances 0.000 claims abstract description 42
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 42
- 239000002253 acid Substances 0.000 claims abstract description 36
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims abstract description 30
- 239000011737 fluorine Substances 0.000 claims abstract description 30
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 30
- 238000006243 chemical reaction Methods 0.000 claims abstract description 26
- 238000000034 method Methods 0.000 claims abstract description 25
- -1 silicon oxide compound Chemical class 0.000 claims abstract description 25
- 150000003388 sodium compounds Chemical class 0.000 claims abstract description 25
- 229910052814 silicon oxide Inorganic materials 0.000 claims abstract description 16
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 32
- 239000000377 silicon dioxide Substances 0.000 claims description 14
- 235000012239 silicon dioxide Nutrition 0.000 claims description 14
- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Inorganic materials [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 14
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 10
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical compound [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 claims description 10
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 8
- 239000004115 Sodium Silicate Substances 0.000 claims description 5
- 239000010703 silicon Substances 0.000 claims description 5
- 229910052710 silicon Inorganic materials 0.000 claims description 5
- 235000017557 sodium bicarbonate Nutrition 0.000 claims description 5
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 5
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 5
- 229910052911 sodium silicate Inorganic materials 0.000 claims description 5
- 239000007864 aqueous solution Substances 0.000 claims description 4
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 4
- 239000002994 raw material Substances 0.000 abstract description 11
- 239000003317 industrial substance Substances 0.000 abstract description 8
- 229910000040 hydrogen fluoride Inorganic materials 0.000 abstract description 6
- 239000000243 solution Substances 0.000 description 9
- 239000013078 crystal Substances 0.000 description 7
- 150000001875 compounds Chemical class 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 description 6
- 239000000706 filtrate Substances 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 239000004698 Polyethylene Substances 0.000 description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 4
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 229920000573 polyethylene Polymers 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 239000004973 liquid crystal related substance Substances 0.000 description 3
- 239000004065 semiconductor Substances 0.000 description 3
- 239000011775 sodium fluoride Substances 0.000 description 3
- 235000013024 sodium fluoride Nutrition 0.000 description 3
- BFXAWOHHDUIALU-UHFFFAOYSA-M sodium;hydron;difluoride Chemical compound F.[F-].[Na+] BFXAWOHHDUIALU-UHFFFAOYSA-M 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 239000002440 industrial waste Substances 0.000 description 2
- 150000003112 potassium compounds Chemical class 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- SRLLRIILXLQLHZ-UHFFFAOYSA-N sodium;hydrofluoride Chemical compound F.[Na] SRLLRIILXLQLHZ-UHFFFAOYSA-N 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 159000000007 calcium salts Chemical class 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 238000003486 chemical etching Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- LRCFXGAMWKDGLA-UHFFFAOYSA-N dioxosilane;hydrate Chemical compound O.O=[Si]=O LRCFXGAMWKDGLA-UHFFFAOYSA-N 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 230000003100 immobilizing effect Effects 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 150000003377 silicon compounds Chemical class 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W10/00—Technologies for wastewater treatment
- Y02W10/30—Wastewater or sewage treatment systems using renewable energies
- Y02W10/37—Wastewater or sewage treatment systems using renewable energies using solar energy
Landscapes
- Silicon Compounds (AREA)
- Removal Of Specific Substances (AREA)
Abstract
Description
本発明は、フッ素系廃液に含まれる、或いはフッ素系廃液の処理過程で発生するケイフッ化水素酸を原料として、工業用薬品として有用なケイフッ化ナトリウムを製造する方法に関するものである。 The present invention relates to a method for producing sodium silicofluoride useful as an industrial chemical, using hydrosilicofluoric acid contained in a fluorine-based waste liquid or generated in the process of treatment of a fluorine-based waste liquid as a raw material.
半導体製造産業、液晶製造産業、及び太陽電池製造産業等の産業では、ケイ素化合物のエッチングやケイ素基盤洗浄等の工程において、多量のフッ化水素酸が、単独或いは塩酸等の酸と適当な比率で混合された混酸として使用されている。それに伴い、使用後のフッ素系廃液量も増加しており、地球環境保全及び資源の有効利用の観点からその適切な処理が望まれている。そして、その処理も産業廃棄物として処理するのではなく、フッ素資源の有効利用のため、その廃液を原料として使用し、工業薬品を製造する方法の確立が求められている。 In industries such as the semiconductor manufacturing industry, the liquid crystal manufacturing industry, and the solar cell manufacturing industry, a large amount of hydrofluoric acid alone or in an appropriate ratio with acids such as hydrochloric acid is used in processes such as etching of silicon compounds and cleaning of silicon substrates. Used as a mixed acid. Along with this, the amount of fluorinated waste liquid after use has also increased, and appropriate treatment is desired from the viewpoint of global environmental conservation and effective use of resources. And the treatment is not treated as industrial waste, but establishment of a method for producing industrial chemicals using the waste liquid as a raw material is required for effective utilization of fluorine resources.
フッ素系廃液の廃物の負荷を軽減するためのいくつかの方法が報告されている。その例として、ケイ素を含む場合、難溶性のケイフッ化ナトリウムを生成するナトリウム化合物やカリウム化合物を加え、ケイフッ化ナトリウムやケイフッ化カリウムとして取り除き、処理後の液をガラスのケミカルエッチング剤として再利用する方法がある（例えば、特許文献１参照）。 Several methods have been reported to reduce the waste load of fluorinated effluents. As an example, when silicon is included, a sodium compound or potassium compound that forms poorly soluble sodium silicofluoride is added, removed as sodium silicofluoride or potassium silicofluoride, and the treated liquid is reused as a chemical etchant for glass. There exists a method (for example, refer patent document 1).
また、ガラスのケミカルエッチング廃液に対して、まずナトリウム化合物やカリウム化合物を加えて廃液中のケイフッ化水素酸及びホウフッ化水素酸を難溶性のケイフッ化ナトリウムまたはホウフッ化物として固定化処理した後、カルシウム塩を加えてフッ素を固定化するか、ホウフッ化物を含有する場合はあらかじめアルミニウム化合物を加えてホウフッ化物をホウ酸とフッ化物に分解した後、カルシウム塩を加えてフッ素の固定化処理を行う方法がある（例えば、特許文献２参照）。 In addition, after adding sodium compound and potassium compound to the chemical etching waste liquid of glass and fixing the hydrofluoric acid and borofluoric acid in the waste liquid as hardly soluble sodium silicofluoride or borofluoride, calcium A method of immobilizing fluorine by adding salt or, if borofluoride is contained, adding an aluminum compound in advance to decompose borofluoride into boric acid and fluoride, and then adding calcium salt to fix the fluorine (See, for example, Patent Document 2).
しかしながら、これらの方法は、ケイフッ化物の製造に関して、操作の手順、原料化合物の選定、原料化合物の量、原料化合物の投入方法等、工業的製法として必要な条件については検討されていない。
したがって、これらの方法で回収したケイフッ化ナトリウムは、廃水の処理過程でフッ素を除去するための方法において発生した産業廃棄物であって、かなり純度が低く工業用薬品としての価値は極めて低い。
However, these methods have not been examined for the conditions necessary for industrial production, such as operation procedures, selection of raw material compounds, amount of raw material compounds, input method of raw material compounds, etc. with respect to the production of silicofluoride.
Therefore, sodium silicofluoride recovered by these methods is an industrial waste generated in a method for removing fluorine in the treatment process of wastewater, and has a very low purity and extremely low value as an industrial chemical.
本発明は、半導体製造産業、液晶製造産業、及び太陽電池製造産業等の産業から排出されるフッ素系廃液に含まれる、或いはフッ素系廃液の処理過程で発生するケイフッ化水素酸を原料として、工業薬品として有用なケイフッ化ナトリウムを製造する方法を提供することを目的とするものである。 The present invention is based on hydrofluoric acid contained in fluorine waste liquid discharged from industries such as semiconductor manufacturing industry, liquid crystal manufacturing industry, and solar cell manufacturing industry, or generated in the process of processing fluorine waste liquid. It aims at providing the method of manufacturing sodium silicofluoride useful as a chemical | medical agent.
フッ素系廃液に含まれるケイフッ化水素酸については、例えば、特許文献２に記載されているように、ケイフッ化水素酸はナトリウム化合物で処理することにより難溶性のケイフッ化ナトリウムとして分離できるが、フッ素系廃液には、消費されなかったフッ化水素酸を多量に含有しているので、ナトリウム化合物で処理したときにフッ化ナトリウムや酸性フッ化ナトリウムが生成するため、この方法では、工業薬品レベルの品位のケイフッ化ナトリウムを製造することは困難である。 As for hydrosilicofluoric acid contained in the fluorine-based waste liquid, for example, as described in Patent Document 2, hydrosilicic acid can be separated as hardly soluble sodium silicofluoride by treatment with a sodium compound. Since the system waste liquid contains a large amount of hydrofluoric acid that has not been consumed, sodium fluoride and sodium acid fluoride are produced when it is treated with a sodium compound. It is difficult to produce high grade sodium fluorosilicate.
したがって、前記特許文献記載の方法はあくまでも廃液中のフッ素を除去するための方法に過ぎず、ケイフッ化ナトリウムを製造する方法には適さない。 Therefore, the method described in the above-mentioned patent document is only a method for removing fluorine in the waste liquid and is not suitable for a method for producing sodium silicofluoride.
本発明者等は、鋭意研究の結果、フッ素系廃液に含まれる、或いはフッ素系廃液の処理過程で発生するケイフッ化水素酸を原料として、工業用薬品として有用なケイフッ化ナトリウムを製造する方法を見出した。すなわち、フッ素系廃液に含まれる、或いはフッ素系廃液の処理過程で発生するケイフッ化水素酸を原料として、工業用薬品レベルの品位のケイフッ化ナトリウムを製造するための、操作の手順、原料化合物の選定、原料化合物の量、原料化合物の投入方法について種々検討し、工業的に確立し得る方法を完成するに至った。 As a result of intensive research, the present inventors have developed a method for producing sodium silicofluoride useful as an industrial chemical, using hydrosilicofluoric acid contained in the fluorine-based waste liquid or generated in the treatment process of the fluorine-based waste liquid as a raw material. I found it. That is, an operation procedure for producing sodium silicofluoride of a grade of industrial chemicals using hydrosilicofluoric acid contained in a fluorine-based waste liquid or generated in the process of treating a fluorine-based waste liquid as a raw material, Various studies were made on selection, the amount of raw material compound, and the method of charging the raw material compound, and a method that can be established industrially has been completed.
本発明は、フッ素系廃液に含まれる、或いはフッ素系廃液に含まれるフッ化水素を酸化珪素化合物と反応させる過程で発生するケイフッ化水素酸をナトリウム化合物と反応させることによって、ケイフッ化ナトリウムを製造する方法に関するものである。 The present invention produces sodium silicofluoride by reacting hydrofluoric acid contained in fluorine waste liquid or in the process of reacting hydrogen fluoride contained in fluorine waste liquid with a silicon oxide compound with a sodium compound. It is about how to do.
以下に、本発明について、詳細に説明する。 The present invention is described in detail below.
フッ素系廃液中に含まれるケイフッ化水素酸は、ナトリウム化合物と反応させケイフッ化ナトリウムとすることができるが、フッ化水素酸が共存する場合、ケイフッ化ナトリウムを製造する過程で、ナトリウム化合物と反応し、フッ化ナトリウムや酸性フッ化ナトリウムが生成するのでケイフッ化ナトリウムの純度が低減する。したがって、フッ化水素酸は酸化ケイ素化合物と反応させてケイフッ化水素酸に変換しておかなければならない。使用する酸化ケイ素化合物としては、二酸化ケイ素、一酸化ケイ素、及びケイ酸ナトリウムを挙げることができる。 Hydrofluorosilicic acid contained in the fluorine-based waste liquid can be reacted with a sodium compound to form sodium silicofluoride, but when hydrofluoric acid coexists, it reacts with the sodium compound in the process of producing sodium silicofluoride. In addition, since sodium fluoride and sodium acid fluoride are produced, the purity of sodium silicofluoride is reduced. Therefore, hydrofluoric acid must be converted to silicohydrofluoric acid by reacting with the silicon oxide compound. Examples of the silicon oxide compound used include silicon dioxide, silicon monoxide, and sodium silicate.
そして、本発明の目的であるケイフッ化ナトリウムを製造するためには、反応させる酸化ケイ素化合物のケイ素のモル数がフッ化水素酸のモル数に対して０．２０から０．３３倍であればよい。 And in order to manufacture the sodium silicofluoride which is the object of the present invention, if the number of moles of silicon of the silicon oxide compound to be reacted is 0.20 to 0.33 times the number of moles of hydrofluoric acid Good.
これは、酸化ケイ素化合物として二酸化ケイ素の一例である式（１）に示す酸化ケイ素化合物とフッ化水素酸の反応において、酸化ケイ素化合物を過剰にして化学平衡をケイフッ化水素酸の生成方向へ促進させるためである。 This is an example of silicon dioxide as a silicon oxide compound. In the reaction of the silicon oxide compound shown in Formula (1) with hydrofluoric acid, the silicon oxide compound is excessive to promote the chemical equilibrium toward the production of silicofluoric acid. This is to make it happen.
なお、酸化ケイ素化合物のケイ素のモル数が、フッ化水素酸のモル数に対して、０．２０倍以下であると、フッ化水素酸を完全にケイフッ化水素酸に変換できない。０．３３倍以上の場合は経済的でない。 Note that when the number of moles of silicon in the silicon oxide compound is 0.20 times or less with respect to the number of moles of hydrofluoric acid, hydrofluoric acid cannot be completely converted to silicofluoric acid. If it is 0.33 times or more, it is not economical.
実際には、合成槽中において廃液を攪拌しながら、酸化ケイ素化合物を添加していき、フッ化水素酸を酸化ケイ素化合物と反応させてケイフッ化水素酸とし、過剰の酸化ケイ素化合物はろ過して除去する。 In practice, while stirring the waste liquid in the synthesis tank, the silicon oxide compound is added, hydrofluoric acid is reacted with the silicon oxide compound to form silicohydrofluoric acid, and the excess silicon oxide compound is filtered. Remove.
次に、前記の方法で調整した液にナトリウム化合物を添加し、ケイフッ化ナトリウムを合成する。ナトリウム化合物としては、水酸化ナトリウム、炭酸ナトリウム、及び炭酸水素ナトリウムが使用できる。ナトリウム化合物の添加方法は、固体の状態で投入してもよいが、適当な濃度の水溶液にして添加する方が、反応を制御しやすい。 Next, a sodium compound is added to the liquid prepared by the above method to synthesize sodium fluorosilicate. As the sodium compound, sodium hydroxide, sodium carbonate, and sodium hydrogen carbonate can be used. The sodium compound may be added in a solid state, but the reaction can be easily controlled by adding an aqueous solution having an appropriate concentration.
廃液とナトリウム化合物の投入は、全量を一度に行ってもよいが、ケイフッ化ナトリウムの析出と分離を何回かに分けながら段階的に行ってもよい。また、ナトリウム化合物の投入量は、フッ素系廃液には、塩酸やホウフッ化水素のような他の種類の酸も含まれている場合もあり、ケイフッ化ナトリウムを収率よく回収するためには、ケイフッ化水素酸のモル数に対し、２．１０から３．３０倍が最適である。 The waste liquid and the sodium compound may be added all at once, or may be performed step by step while separating and separating sodium silicofluoride several times. In addition, the amount of sodium compound input may include other types of acids such as hydrochloric acid and borofluoride in the fluorine-based waste liquid. In order to recover sodium silicofluoride in a high yield, The optimum is 2.10 to 3.30 times the number of moles of hydrofluoric acid.
また、ナトリウム化合物の投入量は、ナトリウム化合物に含まれるナトリウムのモル数でケイフッ化水素酸のモル数に対し、２．１０〜３.３０倍投入する。これは、本発明の目的であるケイフッ化ナトリウムを得るためには、式（２）で示す反応についてナトリウム化合物を過剰に添加することで、ケイフッ化ナトリウムが生成される方へ促進させるためである。ナトリウム化合物添加量がケイフッ化水素酸のモル数に対し２．１０倍を下回ると、ケイフッ化水素酸をケイフッ化ナトリウムとして完全に回収できない。また、３.３０倍を上回ることは、経済的でない。 The sodium compound is added in an amount of 2.10 to 3.30 times the number of moles of sodium hydrofluoric acid in terms of the number of moles of sodium contained in the sodium compound. This is because in order to obtain sodium silicofluoride which is the object of the present invention, the sodium compound is excessively added to the reaction represented by the formula (2) to promote sodium silicofluoride to be produced. . If the amount of sodium compound added is less than 2.10 times the number of moles of silicofluoric acid, the hydrosilicofluoric acid cannot be completely recovered as sodium silicofluoride. Moreover, exceeding 3.30 times is not economical.
なお、ナトリウム化合物は、廃液中にホウフッ化水素酸が含まれる場合、ホウフッ化ナトリウムを生成させるが、投入量がそれに含まれるナトリウムのモル数でケイフッ化水素酸のモル数に対し、２．１０〜３.３０倍であれば、十分溶解し結晶となって析出はしない。 The sodium compound generates sodium borofluoride when the waste liquid contains borohydrofluoric acid. However, the amount of sodium compound contained in the waste liquid is 2.10 with respect to the number of moles of sodium hydrofluoric acid. If it is -3.30 time, it melt | dissolves sufficiently and becomes a crystal | crystallization and does not precipitate.
ケイフッ化ナトリウムを合成するとき、反応温度を３５〜７０℃の間で調整すると、３５℃未満の場合と比較してケイフッ化ナトリウムの高純度で大きな結晶が得られるので、ケイフッ化ナトリウムを遠心分離機等のろ過器で反応液と分離する作業が円滑になり、工業的製法としてより有利になる。また、反応温度が７０℃以上になると、反応液からケイフッ化水素酸が蒸発することや熱エネルギーを過剰に加えることになり、現実的ではない。さらに反応温度の調整は、反応装置を加熱して制御してもよいが、ナトリウム化合物の水溶液を反応温度が３５〜７０℃になるように予め加熱して投入すると、より結晶が大きく成長するので有利である。 When synthesizing sodium silicofluoride, if the reaction temperature is adjusted between 35 and 70 ° C., large crystals of sodium silicofluoride with high purity can be obtained compared to the case of less than 35 ° C. The operation of separating the reaction solution with a filter such as a machine becomes smooth, which is more advantageous as an industrial production method. On the other hand, when the reaction temperature is 70 ° C. or higher, the hydrofluoric acid is evaporated from the reaction solution or excessive heat energy is added, which is not realistic. Further, the reaction temperature may be adjusted by heating the reaction apparatus, but if an aqueous solution of sodium compound is previously heated and added so that the reaction temperature is 35 to 70 ° C., crystals grow larger. It is advantageous.
以上の発明によって製造したケイフッ化ナトリウムは、遠心ろ過機のようなろ過機で分離した後、乾燥して製品とする。 The sodium silicofluoride produced by the above invention is separated by a filter such as a centrifugal filter and then dried to obtain a product.
請求項１記載の発明によれば、半導体製造産業、液晶製造産業、及び太陽電池製造産業等の産業から排出されるフッ素系廃液に含まれる、或いはフッ素系廃液の処理過程で発生するケイフッ化水素酸を原料として、工業用薬品であるケイフッ化ナトリウムを製造することができ、地球環境保護及び限られた資源の有効利用に益するところ大である。 According to the first aspect of the present invention, hydrogen silicofluoride contained in a fluorine-based waste liquid discharged from industries such as the semiconductor manufacturing industry, the liquid crystal manufacturing industry, and the solar cell manufacturing industry, or generated during the treatment of the fluorine-based waste liquid. Using acid as a raw material, it is possible to produce sodium silicofluoride, which is an industrial chemical, which is great for the protection of the global environment and the effective use of limited resources.
請求項２記載の発明によれば、廃液に含まれるフッ化水素酸を、酸化ケイ素化合物である二酸化ケイ素、一酸化ケイ素、ケイ酸ナトリウムとのいずれかと反応させ、予めケイフッ化水素酸に変換することで、ケイフッ化水素酸を製造することができる。 According to the invention described in claim 2, hydrofluoric acid contained in the waste liquid is reacted with any one of silicon dioxide, silicon monoxide, and sodium silicate, which is a silicon oxide compound, and converted into silicohydrofluoric acid in advance. Thus, silicohydrofluoric acid can be produced.
請求項３記載の発明によれば、廃液に含まれるフッ化水素酸と酸化ケイ素化合物である二酸化ケイ素、一酸化ケイ素、ケイ酸ナトリウムのいずれかを、酸化ケイ素化合物のケイ素のモル数がフッ化水素酸のモル数に対して０．２０から０．３３倍で反応させることで、ケイフッ化水素酸を製造することができる。 According to the third aspect of the present invention, any one of hydrofluoric acid and silicon oxide compound silicon dioxide, silicon monoxide, and sodium silicate contained in the waste liquid is fluorinated. By reacting with 0.20 to 0.33 times the number of moles of hydroacid, hydrofluoric acid can be produced.
請求項４記載の発明によれば、ナトリウム化合物である水酸化ナトリウム、炭酸ナトリウム、炭酸水素ナトリウムのいずれかを、ケイフッ化水素酸のモル数の２．１０から３．３０倍で反応させることでケイフッ化ナトリウムの製造ができる。 According to invention of Claim 4, any one of sodium hydroxide which is a sodium compound, sodium carbonate, and sodium hydrogencarbonate is made to react by 2.10 to 3.30 times the mole number of silicofluoric acid. Sodium silicofluoride can be produced.
請求項５の発明によれば、反応温度を３５〜７０℃の間で調整するか、あるいは、ナトリウム化合物の水溶液をあらかじめ加熱して投入して反応温度が３５〜７０℃になるように調整することにより、ケイフッ化ナトリウムの製造を可能にすることができる。 According to the invention of claim 5, the reaction temperature is adjusted between 35 and 70 ° C., or an aqueous solution of sodium compound is previously heated and adjusted so that the reaction temperature becomes 35 to 70 ° C. This makes it possible to produce sodium silicofluoride.
以下に、本発明の実施例を詳細に説明するが、本発明はこれらの実施例のみに限定されるものではない。 Examples of the present invention will be described in detail below, but the present invention is not limited to these examples.
（実施例１）
フッ素系廃液処理工程から得られた、フッ化水素酸５．５０重量％を含む廃液４００ｋｇを原水とし、１ｍ３のポリエチレン容器に取った。これにフッ化水素酸量のモル数の０.２８倍の二酸化ケイ素粉末１８．５ｋｇを投入し攪拌し、二酸化ケイ素を溶解させてフッ化水素を完全にケイフッ化水素酸にした。そして、過剰分の二酸化ケイ素をろ過機で分離した。
ろ過液を分析して確認したところ、フッ化水素酸の濃度は０．０１重量％以下で、ケイフッ化水素酸の濃度は、１８．２重量％であった。
このろ過液４１０ｋｇを１ｍ３の本体が鉄製で内面がポリプロピレンライニングされたジャケット付反応器に計り採り、反応器のジャケットに減圧蒸気を流して液温を４５℃に加熱した。
次に、液を攪拌しながら、炭酸水素ナトリウムの粉末１０３ｋｇ（ケイフッ化水素酸のモル数の２．３０倍）を炭酸ガスの発生を調整しながら、少しずつ添加した。添加終了後、３時間攪拌をした。そのとき、反応熱も発生して、反応温度は５８℃になった。
反応液を１日間放冷した。その後、結晶を遠心ろ過機で分離し後、乾燥させて、ケイフッ化ナトリウム９８．９ｋｇを得た。
その分析結果は、純度９９．５重量％、平均粒子径（ｄ５０）が１１３μｍであった。
Example 1
400 kg of waste liquid containing 5.50% by weight of hydrofluoric acid obtained from the fluorine-based waste liquid treatment step was used as raw water, and taken into a 1 m 3 polyethylene container. To this was added 18.5 kg of silicon dioxide powder 0.28 times the number of moles of hydrofluoric acid, and the mixture was stirred to dissolve the silicon dioxide to completely convert the hydrogen fluoride into silicofluoric acid. And the excess silicon dioxide was isolate | separated with the filter.
When the filtrate was analyzed and confirmed, the concentration of hydrofluoric acid was 0.01% by weight or less, and the concentration of silicohydrofluoric acid was 18.2% by weight.
410 kg of this filtrate was weighed into a reactor with a jacket of 1 m 3 body made of iron and the inner surface of which was lined with polypropylene, and the liquid temperature was heated to 45 ° C. by flowing reduced pressure steam through the jacket of the reactor.
Next, 103 kg of sodium hydrogen carbonate powder (2.30 times the number of moles of silicofluoric acid) was added little by little while adjusting the generation of carbon dioxide gas while stirring the liquid. After completion of the addition, the mixture was stirred for 3 hours. At that time, reaction heat was also generated and the reaction temperature reached 58 ° C.
The reaction was allowed to cool for 1 day. Thereafter, the crystals were separated with a centrifugal filter and then dried to obtain 98.9 kg of sodium silicofluoride.
As a result of the analysis, the purity was 99.5% by weight and the average particle size (d50) was 113 μm.
（実施例２）
フッ素系廃液処理工程から得られた、フッ化水素酸５．７０重量％を含む廃液５００ｋｇを原水とし、１ｍ３のポリエチレン容器に取った。これにフッ化水素酸量のモル数の０.３０倍のニ酸化ケイ素粉末２５．７ｋｇを投入し攪拌し、二酸化ケイ素を溶解させてフッ化水素を完全にケイフッ化水素酸にした。そして、過剰分の二酸化ケイ素をろ過機で分離した。
ろ過液を分析して確認したところ、フッ化水素酸の濃度は０．０１重量％以下で、ケイフッ化水素酸の濃度は、１８．１重量％であった。
この液を攪拌しながら、４５℃に加熱した２０重量％水酸化ナトリウム溶液３１２ｋｇ（ケイフッ化水素酸のモル数の２.３６倍）を８０分かけて滴下し、滴下終了後、４時間攪拌した。そのとき、反応温度は４８℃になった。
反応液を１日間放冷した後、結晶を遠心ろ過機で分離し後、乾燥させて、ケイフッ化ナトリウム１２１ｋｇを得た。
その分析結果は、純度９９．８重量％、平均粒子径（ｄ５０）が６５μｍであった。
(Example 2)
500 kg of waste liquid containing 5.70% by weight of hydrofluoric acid obtained from the fluorine waste liquid treatment step was used as raw water and placed in a 1 m 3 polyethylene container. To this was added 25.7 kg of silicon dioxide powder, 0.30 times the number of moles of hydrofluoric acid, and the mixture was stirred to dissolve silicon dioxide to completely convert hydrogen fluoride to silicofluoric acid. And the excess silicon dioxide was isolate | separated with the filter.
When the filtrate was analyzed and confirmed, the concentration of hydrofluoric acid was 0.01% by weight or less, and the concentration of silicohydrofluoric acid was 18.1% by weight.
While stirring this liquid, 312 kg of a 20 wt% sodium hydroxide solution heated to 45 ° C. (2.36 times the number of moles of silicofluoric acid) was added dropwise over 80 minutes, and the mixture was stirred for 4 hours after completion of the addition. . At that time, the reaction temperature reached 48 ° C.
After the reaction solution was allowed to cool for 1 day, the crystals were separated by a centrifugal filter and then dried to obtain 121 kg of sodium silicofluoride.
As a result of the analysis, the purity was 99.8% by weight and the average particle size (d50) was 65 μm.
（実施例３）
フッ素系廃液処理工程から得られた、フッ化水素酸３．２０重量％を含む廃液３３０ｋｇを原水とし、１ｍ３のポリエチレン容器に取った。これにフッ化水素酸量のモル数の０.２５倍の二酸化ケイ素粉末７．９１ｋｇを投入し攪拌し、二酸化ケイ素を溶解させてフッ化水素を完全にケイフッ化水素酸にした。そして、過剰分の二酸化ケイ素をろ過機で分離した。
ろ過液を分析して確認したところ、フッ化水素酸の濃度は０．０１重量％以下で、ケイフッ化水素酸の濃度は、１４．３重量％であった。
この液を攪拌しながら、７０℃に加熱した２０重量％塩化ナトリウム溶液２５０ｋｇ（ケイフッ化水素酸のモル数の２．５６倍）を５０分かけて滴下し、滴下終了後、３時間攪拌した。そのとき、反応熱も発生して、反応温度は５５℃になった。
反応液を１日間放冷した。その後、結晶を遠心ろ過機で分離し、乾燥させて、ケイフッ化ナトリウム６４．５ｋｇを得た。
その分析結果は、純度９９．７重量％、平均粒子径（ｄ５０）が１０１μｍであった。
(Example 3)
330 kg of waste liquid containing 3.20% by weight of hydrofluoric acid obtained from the fluorine waste liquid treatment step was used as raw water and placed in a 1 m 3 polyethylene container. To this, 7.91 kg of silicon dioxide powder of 0.25 times the number of moles of hydrofluoric acid was added and stirred to dissolve the silicon dioxide to completely convert the hydrogen fluoride into silicohydrofluoric acid. And the excess silicon dioxide was isolate | separated with the filter.
When the filtrate was analyzed and confirmed, the concentration of hydrofluoric acid was 0.01% by weight or less, and the concentration of silicohydrofluoric acid was 14.3% by weight.
While stirring this solution, 250 kg of a 20 wt% sodium chloride solution heated to 70 ° C. (2.56 times the number of moles of silicofluoric acid) was added dropwise over 50 minutes, and the mixture was stirred for 3 hours after completion of the addition. At that time, reaction heat was also generated and the reaction temperature reached 55 ° C.
The reaction was allowed to cool for 1 day. Thereafter, the crystals were separated with a centrifugal filter and dried to obtain 64.5 kg of sodium silicofluoride.
As a result of the analysis, the purity was 99.7% by weight and the average particle size (d50) was 101 μm.
（比較例）
フッ素系廃液処理工程から得られた、フッ化水素酸３．２０重量％を含む廃液３３０ｋｇを原水とし、１ｍ３のポリエチレン容器に取った。これにフッ化水素酸量のモル数の０.１７倍の二酸化ケイ素粉末６．３７ｋｇを投入し攪拌し、二酸化ケイ素を溶解させてフッ化水素を完全にケイフッ化水素酸にした。そして、過剰分の二酸化ケイ素をろ過機で分離した。
ろ過液を分析して確認したところ、フッ化水素酸の濃度は１．３０重量％で、ケイフッ化水素酸の濃度は、１３．５重量％であった。
この液を攪拌しながら、室温の２０重量％塩化ナトリウム溶液１８８ｋｇ（ケイフッ化水素酸のモル数の２．０４倍）を５０分かけて滴下し、滴下終了後、３時間攪拌した。そのとき、反応熱が発生したが、反応温度は２６℃になった。
反応液を１日間放冷した後、実施例３のときの３．５倍の時間をかけて結晶を遠心ろ過機で分離した後、乾燥させて、ケイフッ化ナトリウム５２．７ｋｇを得た。
その分析結果は、純度８６．７重量％、平均粒子径（ｄ５０）が１３．５μｍであった。さらに、Ｘ線回折分析で調査したところ、ケイフッ化ナトリウムの他に、フッ化ナトリウム及び酸性フッ化ナトリウムが含まれており、工業用薬品として要求される品位を大きく下回ることが判明した。
(Comparative example)
330 kg of waste liquid containing 3.20% by weight of hydrofluoric acid obtained from the fluorine waste liquid treatment step was used as raw water and placed in a 1 m 3 polyethylene container. To this, 6.37 kg of silicon dioxide powder of 0.17 times the number of moles of hydrofluoric acid was added and stirred to dissolve the silicon dioxide so that the hydrogen fluoride was completely converted to silicofluoric acid. And the excess silicon dioxide was isolate | separated with the filter.
When the filtrate was analyzed and confirmed, the concentration of hydrofluoric acid was 1.30% by weight and the concentration of silicohydrofluoric acid was 13.5% by weight.
While stirring this solution, 188 kg of a 20 wt% sodium chloride solution at room temperature (2.04 times the number of moles of hydrofluoric acid) was added dropwise over 50 minutes, and the mixture was stirred for 3 hours after completion of the addition. At that time, heat of reaction was generated, but the reaction temperature became 26 ° C.
After the reaction solution was allowed to cool for 1 day, the crystals were separated by a centrifugal filter over 3.5 times as in Example 3, and then dried to obtain 52.7 kg of sodium silicofluoride.
As a result of the analysis, the purity was 86.7% by weight, and the average particle size (d50) was 13.5 μm. Furthermore, as a result of investigation by X-ray diffraction analysis, it has been found that sodium fluoride and sodium acid fluoride are contained in addition to sodium silicofluoride, which is far below the quality required for industrial chemicals.
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| JP2016203096A (en) * | 2015-04-23 | 2016-12-08 | 株式会社Ｎｓｃ | Method for treating waste liquid containing silicofluoric acid |
| CN106829983A (en) * | 2017-03-31 | 2017-06-13 | 瓮福（集团）有限责任公司 | A kind of preparation method of sodium metasilicate |
| KR20170131688A (en) | 2016-04-01 | 2017-11-29 | 사사키카가쿠야쿠힌 가부시키가이샤 | Alkali metal salt-containing molded article and method for regenerating acidic aqueous solution using the same |
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| JPH05279009A (en) * | 1992-03-31 | 1993-10-26 | Mitsui Toatsu Chem Inc | Sodium silicofluoride composition |
| JP2008189484A (en) * | 2007-02-01 | 2008-08-21 | Morita Kagaku Kogyo Kk | Method and apparatus for separating/recovering acid component from waste liquid containing hydrofluoric acid and silicofluoric acid |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JP2016203096A (en) * | 2015-04-23 | 2016-12-08 | 株式会社Ｎｓｃ | Method for treating waste liquid containing silicofluoric acid |
| KR20170131688A (en) | 2016-04-01 | 2017-11-29 | 사사키카가쿠야쿠힌 가부시키가이샤 | Alkali metal salt-containing molded article and method for regenerating acidic aqueous solution using the same |
| CN106829983A (en) * | 2017-03-31 | 2017-06-13 | 瓮福（集团）有限责任公司 | A kind of preparation method of sodium metasilicate |
| CN106829983B (en) * | 2017-03-31 | 2020-03-27 | 瓮福（集团）有限责任公司 | Preparation method of sodium silicate |
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