JP3891189B2 - Method for treating boron-containing water - Google Patents
Method for treating boron-containing water Download PDFInfo
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- JP3891189B2 JP3891189B2 JP2004147626A JP2004147626A JP3891189B2 JP 3891189 B2 JP3891189 B2 JP 3891189B2 JP 2004147626 A JP2004147626 A JP 2004147626A JP 2004147626 A JP2004147626 A JP 2004147626A JP 3891189 B2 JP3891189 B2 JP 3891189B2
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- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 title claims description 95
- 229910052796 boron Inorganic materials 0.000 title claims description 95
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims description 79
- 238000000034 method Methods 0.000 title claims description 40
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 148
- 239000000377 silicon dioxide Substances 0.000 claims description 72
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 41
- 239000011574 phosphorus Substances 0.000 claims description 41
- 229910052698 phosphorus Inorganic materials 0.000 claims description 41
- 229910052761 rare earth metal Inorganic materials 0.000 claims description 36
- 239000008187 granular material Substances 0.000 claims description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 13
- 238000003672 processing method Methods 0.000 claims description 6
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 5
- 229910052782 aluminium Inorganic materials 0.000 claims description 5
- 238000001556 precipitation Methods 0.000 claims description 5
- 239000010802 sludge Substances 0.000 claims description 4
- 238000005345 coagulation Methods 0.000 claims description 3
- 230000015271 coagulation Effects 0.000 claims description 3
- 238000001914 filtration Methods 0.000 claims description 3
- 239000000701 coagulant Substances 0.000 claims description 2
- 238000001179 sorption measurement Methods 0.000 description 38
- 239000007864 aqueous solution Substances 0.000 description 24
- 239000002253 acid Substances 0.000 description 17
- 239000003513 alkali Substances 0.000 description 15
- 235000018936 Vitellaria paradoxa Nutrition 0.000 description 13
- 230000008929 regeneration Effects 0.000 description 13
- 238000011069 regeneration method Methods 0.000 description 13
- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Inorganic materials [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- 239000000243 solution Substances 0.000 description 11
- 239000002351 wastewater Substances 0.000 description 11
- 230000008569 process Effects 0.000 description 10
- 230000002776 aggregation Effects 0.000 description 9
- 238000005469 granulation Methods 0.000 description 8
- 230000003179 granulation Effects 0.000 description 8
- 229920005989 resin Polymers 0.000 description 8
- 239000011347 resin Substances 0.000 description 8
- 238000004220 aggregation Methods 0.000 description 7
- FPWJLQXCGHQXLL-UHFFFAOYSA-N [P].OP(O)(O)=O Chemical compound [P].OP(O)(O)=O FPWJLQXCGHQXLL-UHFFFAOYSA-N 0.000 description 6
- 238000005189 flocculation Methods 0.000 description 6
- 150000002910 rare earth metals Chemical class 0.000 description 6
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 5
- 239000011575 calcium Substances 0.000 description 5
- 238000003795 desorption Methods 0.000 description 5
- 230000016615 flocculation Effects 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 238000000926 separation method Methods 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 239000011260 aqueous acid Substances 0.000 description 4
- 238000006477 desulfuration reaction Methods 0.000 description 4
- 230000023556 desulfurization Effects 0.000 description 4
- 229910052684 Cerium Inorganic materials 0.000 description 3
- 229910019142 PO4 Inorganic materials 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 239000012670 alkaline solution Substances 0.000 description 3
- 239000003990 capacitor Substances 0.000 description 3
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 3
- -1 cerium increases Chemical class 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 3
- 239000010452 phosphate Substances 0.000 description 3
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 229920000219 Ethylene vinyl alcohol Polymers 0.000 description 2
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 2
- 229910004298 SiO 2 Inorganic materials 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 238000005054 agglomeration Methods 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 159000000007 calcium salts Chemical class 0.000 description 2
- 239000000969 carrier Substances 0.000 description 2
- UNJPQTDTZAKTFK-UHFFFAOYSA-K cerium(iii) hydroxide Chemical compound [OH-].[OH-].[OH-].[Ce+3] UNJPQTDTZAKTFK-UHFFFAOYSA-K 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000010828 elution Methods 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000003002 pH adjusting agent Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 229910052692 Dysprosium Inorganic materials 0.000 description 1
- 229910052691 Erbium Inorganic materials 0.000 description 1
- 229910052693 Europium Inorganic materials 0.000 description 1
- 229910052688 Gadolinium Inorganic materials 0.000 description 1
- 229910052689 Holmium Inorganic materials 0.000 description 1
- 239000005909 Kieselgur Substances 0.000 description 1
- 229910052765 Lutetium Inorganic materials 0.000 description 1
- 229910052779 Neodymium Inorganic materials 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 229910052777 Praseodymium Inorganic materials 0.000 description 1
- 229910052773 Promethium Inorganic materials 0.000 description 1
- 229910052772 Samarium Inorganic materials 0.000 description 1
- 229910052771 Terbium Inorganic materials 0.000 description 1
- 229910052775 Thulium Inorganic materials 0.000 description 1
- 229910052769 Ytterbium Inorganic materials 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 238000010306 acid treatment Methods 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 150000001639 boron compounds Chemical class 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000012461 cellulose resin Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 229910052878 cordierite Inorganic materials 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- JSKIRARMQDRGJZ-UHFFFAOYSA-N dimagnesium dioxido-bis[(1-oxido-3-oxo-2,4,6,8,9-pentaoxa-1,3-disila-5,7-dialuminabicyclo[3.3.1]nonan-7-yl)oxy]silane Chemical compound [Mg++].[Mg++].[O-][Si]([O-])(O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2)O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2 JSKIRARMQDRGJZ-UHFFFAOYSA-N 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- KBQHZAAAGSGFKK-UHFFFAOYSA-N dysprosium atom Chemical compound [Dy] KBQHZAAAGSGFKK-UHFFFAOYSA-N 0.000 description 1
- 238000009713 electroplating Methods 0.000 description 1
- UYAHIZSMUZPPFV-UHFFFAOYSA-N erbium Chemical compound [Er] UYAHIZSMUZPPFV-UHFFFAOYSA-N 0.000 description 1
- OGPBJKLSAFTDLK-UHFFFAOYSA-N europium atom Chemical compound [Eu] OGPBJKLSAFTDLK-UHFFFAOYSA-N 0.000 description 1
- UIWYJDYFSGRHKR-UHFFFAOYSA-N gadolinium atom Chemical compound [Gd] UIWYJDYFSGRHKR-UHFFFAOYSA-N 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- KJZYNXUDTRRSPN-UHFFFAOYSA-N holmium atom Chemical compound [Ho] KJZYNXUDTRRSPN-UHFFFAOYSA-N 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 1
- OHSVLFRHMCKCQY-UHFFFAOYSA-N lutetium atom Chemical compound [Lu] OHSVLFRHMCKCQY-UHFFFAOYSA-N 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- 238000005374 membrane filtration Methods 0.000 description 1
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 229920002492 poly(sulfone) Polymers 0.000 description 1
- 229920002239 polyacrylonitrile Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- PUDIUYLPXJFUGB-UHFFFAOYSA-N praseodymium atom Chemical compound [Pr] PUDIUYLPXJFUGB-UHFFFAOYSA-N 0.000 description 1
- VQMWBBYLQSCNPO-UHFFFAOYSA-N promethium atom Chemical compound [Pm] VQMWBBYLQSCNPO-UHFFFAOYSA-N 0.000 description 1
- 229910001404 rare earth metal oxide Inorganic materials 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000012492 regenerant Substances 0.000 description 1
- 230000001172 regenerating effect Effects 0.000 description 1
- KZUNJOHGWZRPMI-UHFFFAOYSA-N samarium atom Chemical compound [Sm] KZUNJOHGWZRPMI-UHFFFAOYSA-N 0.000 description 1
- 238000009287 sand filtration Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 229910052706 scandium Inorganic materials 0.000 description 1
- SIXSYDAISGFNSX-UHFFFAOYSA-N scandium atom Chemical compound [Sc] SIXSYDAISGFNSX-UHFFFAOYSA-N 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 230000009897 systematic effect Effects 0.000 description 1
- GZCRRIHWUXGPOV-UHFFFAOYSA-N terbium atom Chemical compound [Tb] GZCRRIHWUXGPOV-UHFFFAOYSA-N 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 238000004056 waste incineration Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- NAWDYIZEMPQZHO-UHFFFAOYSA-N ytterbium Chemical compound [Yb] NAWDYIZEMPQZHO-UHFFFAOYSA-N 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
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- Water Treatment By Sorption (AREA)
- Separation Of Suspended Particles By Flocculating Agents (AREA)
Description
本発明は、ホウ素含有水の処理方法に関する。詳しくは、本発明は、希土類元素の水酸化物を担持した造粒体を用いて、シリカを含むホウ素含有水中のホウ素を吸着除去するホウ素含有水の処理方法において、該造粒体のホウ素吸着性能の低下を防止して安定かつ効率的な処理を行う方法に関する。 The present invention relates to a method for treating boron-containing water. Specifically, the present invention uses granular material carrying the hydroxide of the rare earth elements, in the processing method of the boron-containing water for adsorbing and removing boron in the boron-containing water containing by silica, boron granulation body The present invention relates to a method for performing stable and efficient treatment by preventing a decrease in adsorption performance.
ホウ素化合物は、医薬品、化粧品、石けん、電気メッキなどの種々の用途に使用されるため、これらの製造工程などから発生する排水にはホウ素が含まれている。また、ごみ焼却場の洗煙排水等にもホウ素が含まれている場合がある。このようなホウ素含有水の処理方法として、希土類元素の水酸化物を担持した造粒体にホウ素を吸着させる処理方法が知られており、ホウ素を吸着した造粒体をアルカリ水溶液を用いて処理することによりホウ素を脱着させて再生する方法が提案されている（特開２００４−５００６９号公報）。また、処理を継続することにより、該造粒体にＣａ（ＯＨ）２，Ｍｇ（ＣＨ）２といったスケール成分が蓄積することにより、ホウ素吸着性能が低下するため、これを酸で除去して再生する方法も提案されている（特開２００４−５７８７０号公報）。
特開２００４−５７８７０号公報では、Ｃａ（ＯＨ）２，Ｍｇ（ＣＨ）２といったスケール成分による性能低下を防止するために、酸による再生工程を行うが、酸による再生では、造粒体からセリウム等の希土類の溶出の問題があり、これにより造粒体が劣化する。 In Japanese Patent Application Laid-Open No. 2004-57870, a regeneration step with an acid is performed in order to prevent performance degradation due to scale components such as Ca (OH) 2 and Mg (CH) 2. There is a problem of elution of rare earths such as this, and this causes deterioration of the granulated body.
また、希土類元素の含水酸化物を担持した造粒体を用いたホウ素含有水の処理方法にあっては、Ｃａ（ＯＨ）２，Ｍｇ（ＣＨ）２といったスケール成分の除去を行っても、処理を継続することによりホウ素吸着性能が低下する場合があり、特にリンやシリカを含むホウ素含有水にあっては、その他のホウ素吸着性能低下要因があることが推定された。即ち、ホウ素含有水のうち、脱硫排水ではシリカが、また、アルミ電解コンデンサ製造排水のような排水ではリンが含有されている。通常、脱硫排水や電解コンデンサ製造排水では、フッ素処理あるいは高濃度のリン酸性リン除去のために、カルシウム塩による凝集沈殿処理が行われている。しかしながら、このような処理を行っても、脱硫排水ではシリカが、アルミ電解コンデンサ製造排水では低濃度のリン酸性リンが、なお更に残留する。 Further, in the method for treating boron-containing water using a granule carrying a rare earth element hydrated oxide, the treatment can be performed even if scale components such as Ca (OH) 2 and Mg (CH) 2 are removed. It is estimated that there are other factors that lower boron adsorption performance, particularly in boron-containing water containing phosphorus and silica. That is, among the boron-containing water, silica is contained in the desulfurization waste water, and phosphorus is contained in the waste water such as the aluminum electrolytic capacitor manufacturing waste water. Usually, desulfurization waste water and electrolytic capacitor production waste water are subjected to a coagulation precipitation treatment with a calcium salt in order to remove fluorine or remove high-concentration phosphoric acid phosphorus. However, even if such treatment is performed, silica remains in the desulfurization effluent, and low concentration phosphoric acid phosphorus remains in the aluminum electrolytic capacitor manufacturing effluent.
従って、本発明は、希土類元素の含水酸化物を担持した造粒体を用いて、シリカ、或いはシリカ及びリンを含むホウ素含有水中のホウ素を吸着除去するに当たり、造粒体のホウ素吸着性能の低下を防止して安定かつ効率的な処理を行うことができるホウ素含有水の処理方法を提供することを目的とする。 Accordingly, the present invention uses granular material carrying the hydrous oxide of a rare earth element, shea silica, or Upon for adsorbing and removing boron in the boron-containing water containing silica and phosphorus, granules of boron adsorption performance of It is an object of the present invention to provide a method for treating boron-containing water that can prevent a decrease and perform a stable and efficient treatment.
本発明（請求項１）のホウ素含有水の処理方法は、シリカを含むホウ素含有水を、希土類元素の含水酸化物を担持した造粒体と接触させてホウ素を吸着除去するホウ素含有水の処理方法において、該ホウ素含有水中のシリカを予め除去した後、前記造粒体と接触させることを特徴とする。
請求項２のホウ素含有水の処理方法は、請求項１において、シリカを含むホウ素含有水がリンも含み、該ホウ素含有水中のシリカを除去する際に、シリカとともにリンも除去することを特徴とする。
Processing method of the boron-containing water of the present invention (claim 1) is a boron-containing water containing by silica is contacted with granules carrying the hydrous oxide of a rare earth element of boron-containing water for adsorbing and removing boron in the processing method, after prior removal by silica of the boron-containing water, wherein the contacting with the granules.
The method for treating boron-containing water according to
即ち、本発明者らの研究により、被処理水中のリン（ＰＯ４−Ｐ）やシリカ（ＳｉＯ２）は、希土類元素の含水酸化物を担持した造粒体のホウ素吸着性能低下の原因物質であることが判明した。なお、本発明においては含水酸化物は含水・酸化物も含水酸化物も両方含んでいる。 That is, according to the study by the present inventors, phosphorus (PO 4 -P) and silica (SiO 2 ) in the water to be treated are causative substances that cause a decrease in the boron adsorption performance of the granule carrying a rare earth element hydrous oxide. It turned out to be. In the present invention, the hydrous oxide includes both hydrous oxides and hydrous oxides.
被処理水中のリンやシリカは、特開２００４−５００６９号公報に記載されるようなアルカリによる再生では脱着し得ず、造粒体に蓄積されていく。仮りにシリカを酸洗浄により除去しようとすると、７．５ｇ−ＨＣｌ／Ｌ（ｐＨ１以下）の強酸を用いる必要があり、この場合には、セリウム等の希土類の溶出量が多くなり、それによる性能低下を引き起こす。一方、リンは８０ｇ−ＮａＯＨ／Ｌというような強アルカリであれば、８０％程度の脱着効果を得ることができるが、通常のアルカリによる再生に用いる２０ｇ−ＮａＯＨ／Ｌ程度のアルカリでは脱着し得ない。また、強アルカリで再生を行った場合には、リン（ＰＯ４−Ｐ）が回収結晶中に混入するため、これを分離するための工程が必要となる。 Phosphorus and silica in the water to be treated cannot be desorbed by regeneration with alkali as described in JP-A No. 2004-50069 and accumulate in the granulated body. If an attempt is made to remove silica by acid cleaning, it is necessary to use a strong acid of 7.5 g-HCl / L (pH 1 or less). In this case, the amount of elution of rare earth such as cerium increases, and the performance due to this Causes a drop. On the other hand, if phosphorus is a strong alkali such as 80 g-NaOH / L, a desorption effect of about 80% can be obtained, but it can be desorbed with an alkali of about 20 g-NaOH / L used for regeneration with ordinary alkali. Absent. In addition, when regeneration is performed with a strong alkali, phosphorus (PO 4 -P) is mixed into the recovered crystal, and thus a step for separating it is necessary.
このようなことから、本発明者らは、被処理水中のリン、シリカは、これを予め除去し、造粒体への吸着自体を未然に防ぐことが、リンやシリカによる造粒体のホウ素吸着性能低下の防止のために有効であることを見出し、本発明に到達した。 For this reason, the present inventors removed phosphorus and silica in the water to be treated in advance, and previously prevented adsorption to the granulated body itself. The inventors have found that it is effective for preventing a decrease in adsorption performance and have reached the present invention.
本発明においては、ホウ素吸着処理に先立ち、被処理水中のシリカ、或いはシリカ及びリンを予め除去することにより、シリカ、或いはシリカ及びリンによる造粒体のホウ素吸着性能の低下を確実に防止することができる。 In the present invention, prior to the boron adsorption treatment, shea silica in the water to be treated, or by previously removing silica and phosphorus, shea silica, or securely prevent the decrease in boron adsorption performance of the granule with silica and phosphorus can do.
本発明において、シリカ、或いはシリカ及びリンを除去する処理は凝集処理が好ましく、特にアルミニウムを含む凝集剤を用い、ｐＨ８〜９で行う凝集処理が好ましい。この場合、生成した凝集汚泥は濾過又は沈殿により分離することが好ましい。
In the present invention, shea silica, or a process for removing silica and phosphorus are preferred agglomeration process, in particular using a flocculant containing aluminum, aggregation processing performed in
本発明のホウ素含有水の処理方法によれば、希土類元素の含水酸化物を担持した造粒体を用いてシリカ、或いはシリカ及びリンを含むホウ素含有水中のホウ素を吸着除去するに当たり、シリカ、或いはシリカ及びリンによる造粒体のホウ素吸着性能の低下を防止して、造粒体の再生頻度の低減、造粒体寿命の延長を図り、長期にわたり安定かつ効率的な処理を行うことができる。 According to the processing method of the boron-containing water of the present invention, in sheet silica or adsorbing and removing boron in the boron-containing water containing silica and phosphorus by using a granular material carrying the hydrous oxide of a rare earth element, shea silica Alternatively, it is possible to prevent a decrease in the boron adsorption performance of the granulate by silica and phosphorus , reduce the frequency of granulation regeneration, extend the granule life, and perform stable and efficient treatment over a long period of time. it can.
以下に図面を参照して本発明のホウ素含有水の処理方法の実施の形態を詳細に説明する。 Embodiments of a method for treating boron-containing water according to the present invention will be described below in detail with reference to the drawings.
図１は、本発明のホウ素含有水の処理方法の実施の形態を示す系統図であり、図示の方法においては、シリカ、或いはシリカ及びリンを含むホウ素含有水に凝集剤とｐＨ調整剤を添加して、凝集分離手段１にて凝集処理及び凝集汚泥の分離を行うことにより、シリカ、或いはシリカ及びリンを除去した後、後述の希土類含水酸化物担持樹脂２Ａ等の希土類元素の含水酸化物を担持した造粒体が充填されたホウ素吸着塔２に導入してホウ素を吸着除去する。ホウ素吸着塔２の流出水は処理水として系外へ排出される。
Figure 1 is a system diagram showing an embodiment of treatment method of the boron-containing water of the present invention, in the method shown, shea silica, or the boron-containing water containing silica and phosphorus coagulant and a pH adjusting agent was added, by performing the aggregation treatment and separation of agglomerated sludge in flocculation separation unit 1, shea silica, or after removal of silica and phosphorus, hydrated rare earth element of the rare earth oxide hydroxide carrying resin 2A like below It is introduced into a
シリカ、或いはシリカ及びリンを含むホウ素含有水中のシリカ、或いはシリカ及びリンの除去処理としては特に制限はないが、処理設備が簡素、処理が容易であることから、凝集処理が好適であり、特に凝集剤として、ＰＡＣ（ポリ塩化アルミニウム）、硫酸バンド（硫酸アルミニウム）等のアルミニウム塩系凝集剤を用い、ｐＨ９以上で凝集処理を行うことが好ましい。このｐＨ条件が９を超えるとアルミニウム塩系凝集剤からのアルミニウムの溶解の問題があり好ましくない。 Shi silica, or silica and boron-containing water shea silica containing phosphorus, or is not particularly limited as removal treatment of the silica and phosphorus, process equipment simpler, because the process is easy, the aggregation treatment is preferred In particular, it is preferable to use an aluminum salt-based flocculant such as PAC (polyaluminum chloride) or sulfuric acid band (aluminum sulfate) as the flocculant and perform the flocculant treatment at a pH of 9 or more. If this pH condition exceeds 9, there is a problem of dissolution of aluminum from the aluminum salt flocculant, which is not preferable.
特に、凝集処理時のｐＨ及びアルミニウム塩系凝集剤添加量については、後述の実験例１の結果からも明らかなように、除去対象により好適な条件が異なり、次のような条件とすることが好ましい。従って、凝集処理に先立ち、シリカ、或いはシリカ及びリンを含むホウ素含有水には必要に応じて、酸又はアルカリのｐＨ調整剤を添加して好適ｐＨに調整する。 In particular, the pH and the addition amount of the aluminum salt-based flocculant during the flocculation process are different depending on the object to be removed, as will be apparent from the results of Experimental Example 1 described later. preferable. Therefore, prior to the flocculation treatment, shea silica, or silica and optionally the boron-containing water containing phosphorus, adjusted to a preferred pH by adding a pH adjusting agent in an acid or alkali.
シリカを除去する場合：ｐＨ８〜９、アルミニウム塩系凝集剤添加量５ｍｇ／Ｌ以上（Ａｌ２Ｏ３として）、例えば５〜２０ｍｇ／Ｌ
シリカ及びリン酸性リンを除去する場合：ｐＨ８〜９、アルミニウム塩系凝集剤添加量５ｍｇ／Ｌ以上（Ａｌ２Ｏ３として）、例えば５〜２０ｍｇ／Ｌ
なお、シリカとリンとが共存する場合は、上記ｐＨ条件でもシリカとの共沈でリン酸性リンが析出してくるものと推定される。
When removing silica: pH 8-9, aluminum salt-based flocculant addition amount 5 mg / L or more (as Al 2 O 3 ), for example, 5-20 mg / L
When removing by silica and phosphorus acid phosphate: pH 8-9, (as Al 2 O 3) aluminum salt flocculant addition amount 5 mg / L or more, for example 5 to 20 mg / L
In addition, when silica and phosphorus coexist, it is presumed that phosphoric acid phosphorus is precipitated by coprecipitation with silica even under the above pH conditions.
凝集汚泥を固液分離する方法としては特に制限はないが、砂濾過、膜濾過等の濾過手段や沈殿分離手段が好ましい。 A method for solid-liquid separation of the coagulated sludge is not particularly limited, but a filtration means such as sand filtration and membrane filtration and a precipitation separation means are preferable.
このようにしてシリカ、或いはシリカ及びリンが除去されたシリカ・リン除去処理水は、次いで希土類元素の含水酸化物を担持した造粒体によるホウ素の吸着除去処理に供される。 Shi silica Thus, or silica and silica and phosphorus removal process water which phosphorus is removed is then subjected to adsorption removal treatment of boron granulating compound carrying hydrous oxide of a rare earth element.
本発明においては、希土類元素の含水酸化物を担持した造粒体のシリカ、或いはシリカ及びリンによるホウ素吸着性能の低下を確実に防止するために、ホウ素吸着処理に供されるシリカ・リン除去処理水は、シリカ（ＳｉＯ２）濃度１．５ｍｇ／Ｌ以下、リン酸性リン（ＰＯ４−Ｐ）濃度１ｍｇ／Ｌ以下にまで、シリカ、或いはシリカ及びリンが高度に除去されたものであることが好ましい。 In the present invention, shea Rica granulated compound carrying hydrous oxide of a rare earth element, or a decrease in the boron adsorption performance with silica and phosphorus in order to reliably prevent, silica and phosphorus removal to be subjected to the boron adsorption treatment treated water, a silica (SiO 2) concentration of 1.5 mg / L or less, to less than the phosphorus acidic phosphate (PO 4 -P) concentration 1 mg / L, is shea silica, or those silica and phosphorus is highly removed It is preferable.
本発明方法に用いる希土類元素の含水酸化物を担持した造粒体の製造方法に特に制限はなく、例えば、希土類元素の塩の水溶液を担体に付着させ、アルカリ水溶液で処理し、担体上に不溶性の希土類元素の水酸化物を沈着、乾燥させることにより、製造することができる（乾燥の程度によって酸化物と水酸化物両方が含まれるので本発明ではあわせて水酸化物という。）。希土類元素の水酸化物としては、スカンジウム、イットリウム、ランタン、セリウム、プラセオジム、ネオジム、プロメチウム、サマリウム、ユウロピウム、ガドリニウム、テルビウム、ジスプロシウム、ホルミウム、エルビウム、ツリウム、イッテルビウム、ルテチウムの水酸化物を挙げることができる。これらの中で、セリウムの水酸化物を特に好適に用いることができる。 There is no particular limitation on the method for producing a granule carrying a rare earth element hydrous oxide used in the method of the present invention. For example, an aqueous solution of a salt of a rare earth element is attached to a carrier, treated with an alkaline aqueous solution, and insoluble on the carrier. It can be produced by depositing and drying a rare earth element hydroxide (in the present invention, both oxide and hydroxide are included depending on the degree of drying). Examples of rare earth element hydroxides include scandium, yttrium, lanthanum, cerium, praseodymium, neodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, and lutetium. it can. Of these, cerium hydroxide can be particularly preferably used.
希土類元素の水酸化物を担持する担体についても特に制限はなく、例えば、マグネシア、アルミナ、チタニア、シリカ、シリカ−アルミナ、ジルコニア、ゼオライト、活性炭、ケイソウ土、コージェライトなどの無機系担体、ポリアミド、セルロース系樹脂、ポリスルホン、ポリアクリロニトリル、ポリ塩化ビニル、エチレン−ビニルアルコール共重合体などの有機系担体を挙げることができ、その平均粒径は接触効率、取り扱い性の面から０．５〜５ｍｍ程度であることが好ましく、また、担体への希土類元素の水酸化物の担持量は担体に対する希土類元素換算の割合で０．１〜１ｋｇ−希土類元素／Ｌ−担体程度、好ましくは０．４〜０．５ｋｇ−希土類元素／Ｌ−担体とすることが好ましい。 There is no particular limitation on the carrier supporting the rare earth element hydroxide, for example, magnesia, alumina, titania, silica, silica-alumina, zirconia, zeolite, activated carbon, diatomaceous earth, cordierite and other inorganic carriers, polyamide, Organic carriers such as cellulose resin, polysulfone, polyacrylonitrile, polyvinyl chloride, and ethylene-vinyl alcohol copolymer can be listed, and the average particle size is about 0.5 to 5 mm from the viewpoint of contact efficiency and handling The amount of the rare earth element hydroxide supported on the carrier is preferably about 0.1-1 kg-rare earth element / L-carrier, preferably 0.4-0. 0.5 kg-rare earth element / L-support is preferable.
なお、以下において、希土類元素水酸化物を有機系担体に担持してなる造粒体を「希土類含水酸化物担持樹脂」と称す場合がある。 In the following, a granulated body obtained by supporting a rare earth element hydroxide on an organic carrier may be referred to as “rare earth hydroxide-containing resin”.
本発明方法において、シリカ・リン除去処理水を希土類元素の水酸化物を担持した造粒体と接触させる方法に特に制限はなく、例えば、図１に示す如く、該造粒体を充填したホウ素吸着塔２にシリカ・リン除去処理水を通水して接触させることができる。造粒体を充填したホウ素吸着塔の数に特に制限はなく、例えば、ホウ素吸着塔１基のみを使用しても、複数基のホウ素吸着塔を直列につなぎ、最初の塔が飽和したとき、最初の塔を系列からはずし、再生済みの塔を最終段に付け加えるいわゆるメリーゴーラウンド方式とすることもできる。また、ホウ素吸着塔を２基並列に設け、ホウ素の吸着除去処理と再生処理とを交互に行うように通水を切り換えることもできる。ホウ素吸着塔１基のみを使用する場合は、塔から流出する処理水のホウ素濃度が所定の排水基準に達したときに、後述の方法で再生工程に移行する。メリーゴーラウンド方式の場合は、最初の塔の流出水のホウ素濃度が入口濃度に等しくなったとき、最初の塔を塔列から外して、再生工程に移行する。
In the method of the present invention, there is no particular limitation on the method of bringing the silica / phosphorus-removed treated water into contact with the granule supporting the rare earth element hydroxide. For example, as shown in FIG. The
本発明方法において、シリカ・リン除去処理水は、ｐＨを３〜１２、特に４〜１０に調整して希土類元素の水酸化物を担持した造粒体と接触させることが好ましい。希土類元素の含水酸化物を担持した造粒体と接触させるシリカ・リン除去処理水のｐＨが３未満であったり、ｐＨが１２を超えると、吸着量が低下するおそれがある。従って、シリカ・リン除去処理水は、ホウ素吸着処理に先立ち、必要に応じてｐＨ調整を行っても良い。 In the method of the present invention, the silica / phosphorus-removed treated water is preferably brought into contact with a granule carrying a rare earth element hydroxide by adjusting the pH to 3 to 12, particularly 4 to 10. If the pH of the silica / phosphorus-removed water to be brought into contact with the granule carrying a rare earth element-containing hydrous oxide is less than 3, or if the pH exceeds 12, the adsorption amount may decrease. Accordingly, the silica / phosphorus removal treated water may be adjusted in pH as necessary prior to the boron adsorption treatment.
ホウ素吸着処理に用いた、希土類元素の含水酸化物を担持した造粒体は、アルカリ水溶液と接触させてホウ素を脱着させることにより再生処理する。 The granule carrying the rare earth element hydrated oxide used in the boron adsorption treatment is regenerated by bringing it into contact with an alkaline aqueous solution to desorb boron.
ホウ素の脱着に用いるアルカリ水溶液に特に制限はなく、例えば、水酸化ナトリウム、水酸化カリウムなどの水溶液を挙げることができる。これらの中で、水酸化ナトリウム水溶液を好適に用いることができる。アルカリ水溶液の濃度に特に制限はないが、０．１〜２モル／Ｌであることが好ましく、０．３〜１モル／Ｌであることがより好ましい。アルカリ水溶液の濃度が０．１モル／Ｌ未満であると、必要なアルカリ水溶液の量が過大になるとともに、ホウ素が十分に脱着しないおそれがある。アルカリ水溶液の濃度が２モル／Ｌを超えても、脱着効率が向上せず、希土類元素の水酸化物を担持した造粒体が劣化するおそれがある。 There is no restriction | limiting in particular in aqueous alkali solution used for the desorption of boron, For example, aqueous solution, such as sodium hydroxide and potassium hydroxide, can be mentioned. Among these, an aqueous sodium hydroxide solution can be suitably used. Although there is no restriction | limiting in particular in the density | concentration of aqueous alkali solution, it is preferable that it is 0.1-2 mol / L, and it is more preferable that it is 0.3-1 mol / L. If the concentration of the aqueous alkaline solution is less than 0.1 mol / L, the amount of the required aqueous alkaline solution becomes excessive, and boron may not be sufficiently desorbed. Even if the concentration of the aqueous alkali solution exceeds 2 mol / L, the desorption efficiency is not improved, and the granule carrying the rare earth element hydroxide may be deteriorated.
アルカリ水溶液と造粒体との接触方法には特に制限はなく、前述の希土類元素の含水酸化物を担持した造粒体を充填したホウ素吸着塔であれば、図１に示す如く、このホウ素吸着塔２に再生剤としてのアルカリ水溶液を通水して再生を行えば良い。なお、アルカリ水溶液の通水の前後で必要に応じて水による洗浄を行っても良い。
The method for contacting the alkaline aqueous solution with the granulated body is not particularly limited. If the boron adsorption tower is filled with the above-mentioned granulated body supporting the hydrated oxide of the rare earth element, as shown in FIG. The regeneration may be performed by passing an aqueous alkali solution as a regenerant through the
なお、本発明においても、特開２００４−５７８７０号公報に記載されるように、上記アルカリ水溶液による再生の前又は後で造粒体を酸水溶液で処理してＣａ（ＯＨ）２，Ｍｇ（ＣＨ）２といったスケール成分により低下したホウ素吸着性能の回復処理を行っても良い。 In the present invention, as described in JP-A-2004-57870, the granulated product is treated with an acid aqueous solution before or after regeneration with the alkaline aqueous solution, and Ca (OH) 2 , Mg (CH ) You may perform the recovery process of the boron adsorption | suction performance reduced with scale components, such as 2 .
この場合、使用する酸としては、例えば、塩酸、硝酸、硫酸などを挙げることができる。これらの中で、塩酸は、窒素含有廃液が発生せず、ホウ素吸着塔内で不溶性の塩を生成するおそれもないので、好適に用いることができる。酸水溶液は、ｐＨ１〜５であることが好ましく、ｐＨ１〜３であることがより好ましい。酸水溶液のｐＨが１未満であると、担持している希土類元素の水酸化物が溶出し、造粒体の吸着性能が低下するおそれがある。酸水溶液のｐＨが５を超えると、造粒体の表面のスケールを除去する効果が十分に発現しないおそれがある。 In this case, examples of the acid used include hydrochloric acid, nitric acid, and sulfuric acid. Among these, hydrochloric acid can be suitably used because no nitrogen-containing waste liquid is generated and there is no possibility of forming an insoluble salt in the boron adsorption tower. The acid aqueous solution preferably has a pH of 1 to 5, more preferably a pH of 1 to 3. When the pH of the acid aqueous solution is less than 1, the supported rare earth element hydroxide is eluted, and the adsorbing performance of the granulated material may be lowered. When the pH of the acid aqueous solution exceeds 5, the effect of removing the scale on the surface of the granulated body may not be sufficiently exhibited.
造粒体と酸水溶液との接触方法についても特に制限はなく、例えば、造粒体を充填したホウ素吸着塔に酸水溶液を通水する方法が挙げられる。 There is no restriction | limiting in particular also about the contact method of a granulation body and acid aqueous solution, For example, the method of passing an acid aqueous solution to the boron adsorption tower filled with the granulation body is mentioned.
ホウ素を吸着した造粒体をアルカリ水溶液と接触させる前に、該造粒体を酸水溶液と接触させる場合は、シリカ・リン除去処理水の通水を停止し、造粒体を水で洗浄し、造粒体を酸水溶液と接触させた後、水で洗浄し、次いで造粒体をアルカリ水溶液と接触させてホウ素を脱着し、更に造粒体を水で洗浄して１サイクルの処理を完了する。ホウ素を吸着した造粒体をアルカリ水溶液と接触させた後に、造粒体を酸水溶液と接触させる場合は、シリカ・リン除去処理水の通水を停止し、造粒体を水で洗浄し、造粒体をアルカリ水溶液と接触させてホウ素を脱着した後、水で洗浄し、次いで造粒体を酸水溶液と接触させ、造粒体を水で洗浄し、次いで造粒体をアルカリ水溶液と接触させてＯＨ型に変換し、最後に造粒体を水で洗浄して１サイクルの処理を完了する。酸水溶液による処理後にアルカリ水溶液によるホウ素の脱着を行うと、脱着工程終了時に造粒体がＯＨ型になっているので、工程数が少ないという利点がある。しかし、酸水溶液による処理後において、吸着されているホウ素の一部が脱着するので、ホウ素の回収に重点をおく場合は、脱着工程後に酸処理工程を行うことが好ましい。 Before bringing the granulated body adsorbing boron into contact with the aqueous alkali solution, when the granulated body is brought into contact with the aqueous acid solution, the flow of silica / phosphorus removal water is stopped and the granulated body is washed with water. After the granulated body is contacted with an acid aqueous solution, it is washed with water, and then the granulated body is contacted with an alkaline aqueous solution to desorb boron, and the granulated body is further washed with water to complete one cycle of processing. To do. After contacting the granulated body adsorbed with boron with an aqueous alkaline solution, if the granulated body is contacted with an aqueous acid solution, stop the silica / phosphorus removal treatment water flow, wash the granulated body with water, Contact the granulation with an aqueous alkali solution to desorb boron, then wash with water, then contact the granulation with an aqueous acid solution, wash the granulation with water, and then contact the granulation with an aqueous alkali solution Then, it is converted to OH type, and finally the granulated body is washed with water to complete one cycle of treatment. When boron is desorbed with an alkaline aqueous solution after the treatment with the acid aqueous solution, the granulated body is in the OH type at the end of the desorption step, and thus there is an advantage that the number of steps is small. However, since part of the adsorbed boron is desorbed after the treatment with the acid aqueous solution, it is preferable to perform the acid treatment step after the desorption step when emphasizing the recovery of boron.
なお、用いたアルカリ水溶液及び酸水溶液は、使用後、アルカリ又は酸を添加してｐＨ調整することにより、循環再使用することができる。 In addition, the alkali aqueous solution and acid aqueous solution which were used can be recirculated and reused by adding alkali or an acid and adjusting pH after use.
本発明によれば、予めシリカ、或いはシリカ及びリンを除去することにより、シリカ、或いはシリカ及びリンによる希土類元素の含水酸化物を担持した造粒体のホウ素吸着性能の低下が防止されることにより、上記アルカリ水溶液或いはアルカリ水溶液及び酸水溶液による再生頻度を従来の１／１０程度に低減することができる。 According to the present invention, by removing pre Me shea silica, or silica and phosphorus, shea silica, or reduction of boron adsorption performance of the granulated material with silica and phosphate carrying hydrous oxide of a rare earth element is prevented Thus, the regeneration frequency with the alkaline aqueous solution or the alkaline aqueous solution and the acid aqueous solution can be reduced to about 1/10 of the conventional one.
このような本発明のホウ素含有水の処理方法が適用されるシリカ、或いはシリカ及びリンを含むホウ素含有水としては特に制限はないが、例えば、前述のシリカとホウ素を含む脱硫排水が挙げられる。これらの排水は必要に応じて、フッ素及び高濃度リン除去のためにカルシウム塩による凝集沈殿処理が施された後、本発明による処理に供される。 Such boron is processed method contains water applied Cie Rica present invention, or is not particularly limited as boron-containing water containing silica and phosphorus, for example, include desulfurization waste water containing silica and boron above It is done. These wastewaters are subjected to the treatment according to the present invention after being subjected to a coagulation-precipitation treatment with a calcium salt to remove fluorine and high-concentration phosphorus as required.
本発明のホウ素含有水の処理方法は、１〜２０ｍｇ／Ｌ程度のシリカ、或いは更に０．１〜１０ｍｇ／Ｌ程度のリン酸性リンを含み、１０〜５００ｍｇ／Ｌ程度のホウ素とを含む水に特に有効に適用される。 The method for treating boron-containing water according to the present invention is about water containing about 1 to 20 mg / L of silica, or about 0.1 to 10 mg / L of phosphoric acid phosphorus , and about 10 to 500 mg / L of boron. It is applied particularly effectively.
以下に実験例、実施例及び比較例を挙げて本発明をより具体的に説明する。 Hereinafter, the present invention will be described in more detail with reference to experimental examples, examples and comparative examples.
実験例１
シリカ１２．８ｍｇ／Ｌ、リン酸性リン０．９１ｍｇ／Ｌ、カルシウム１４００ｍｇ／Ｌ、ホウ素２００ｍｇ／Ｌを含む排水２０ｍＬに、ＰＡＣを１０〜１００ｍｇ／Ｌの所定量添加し、ｐＨ５〜９の所定値に調整して、２０分間撹拌後、Ｎｏ．５Ａ濾紙で濾過した。
Experimental example 1
A predetermined amount of 10 to 100 mg / L of PAC is added to 20 mL of waste water containing 12.8 mg / L of silica, 0.91 mg / L of phosphoric acid phosphorus, 1400 mg / L of calcium, and 200 mg / L of boron, and a predetermined value of
この凝集処理におけるＰＡＣ添加量及び調整ｐＨ値と、得られた処理水（濾過水）のシリカ（ＳｉＯ２）濃度、リン（ＰＯ４−Ｐ）濃度との関係を表１及び図２に示した。 And PAC amount and adjusting pH value in the flocculation treatment, silica (SiO 2) concentration of the resulting treated water (filtered water), the relationship between phosphorus (PO 4 -P) concentrations shown in Table 1 and Figure 2 .
表１，図２より、ＰＡＣを用いた凝集処理により、ＳｉＯ２，ＰＯ４−Ｐを効率的に除去することができることが分かる。 From Table 1 and FIG. 2, it can be seen that SiO 2 and PO 4 -P can be efficiently removed by the aggregation treatment using PAC.
実施例１
実験例１で処理したものと同様の水質の排水に、ＰＡＣ１００ｍｇ／Ｌを添加してｐＨ９に調整した後濾過し、その後ｐＨ７に調整したシリカ・リン除去処理水（シリカ濃度１．０ｍｇ／Ｌ、リン酸性リン濃度０．０８ｍｇ／Ｌ、ホウ素濃度２００ｍｇ／Ｌ）を原水として、希土類含水酸化物担持樹脂２０ｍＬを充填したガラスカラムよりなるホウ素吸着塔に下向流にてＳＶ＝３ｈ−１で通水し、塔出口水のホウ素濃度が通水原水ホウ素濃度と同じになるまでの単位希土類含水酸化物担持樹脂量（Ｌ−希土類含水酸化物担持樹脂（Ｒ））当たりの平衡吸着量を調べた。なお、希土類含水酸化物担持樹脂としては、エチレン−ビニルアルコール共重合体にセリウムの水酸化物をセリウムとして０．５ｋｇ−Ｃｅ／Ｌ−担体担持させた造粒体（平均粒径０．７ｍｍ）を用いた。
Example 1
Silica / phosphorus-removed water (silica concentration 1.0 mg / L, silica concentration 1.0 mg / L), adjusted to
通水終了後（平衡吸着量到達後）、通水流量ＳＶ＝３ｈ−１で、純水（３ＢＶ）→２０ｇ−ＮａＯＨ／Ｌ（３ＢＶ）→純水（３ＢＶ）の順で通水して再生した。 After completion of water flow (after reaching the equilibrium adsorption amount), water is regenerated by flowing water in the order of pure water (3 BV) → 20 g-NaOH / L (3 BV) → pure water (3 BV) at a flow rate of SV = 3h −1. did.
このような原水の通水と再生を繰り返し、平衡吸着量の変化を調べ、結果を図３に示した。 Such flow and regeneration of the raw water were repeated, the change in the equilibrium adsorption amount was examined, and the result is shown in FIG.
比較例１
実施例１において、ＰＡＣによる凝集処理を行わなかったこと以外は同様にして、通水と再生を繰り返し、平衡吸着量の変化を調べ、結果を図３に示した。
Comparative Example 1
In Example 1, water passage and regeneration were repeated in the same manner except that the PAC aggregation treatment was not performed, and changes in the equilibrium adsorption amount were examined. The results are shown in FIG.
図３より凝集処理により予めリンとシリカを除去することにより、希土類含水酸化物担持樹脂のホウ素吸着性能の低下が防止されることが分かる。 It can be seen from FIG. 3 that the phosphorus adsorption performance of the rare earth-containing hydrated oxide-supported resin is prevented from being lowered by previously removing phosphorus and silica by agglomeration treatment.
１ 凝集分離手段
２ ホウ素吸着塔
２Ａ 希土類含水酸化物担持樹脂
DESCRIPTION OF SYMBOLS 1 Aggregation separation means 2 Boron adsorption tower 2A Rare earth hydrated oxide carrying resin
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