JPS5816951B2 - Treatment method for recycled waste liquid in ion exchange treatment - Google Patents
Treatment method for recycled waste liquid in ion exchange treatmentInfo
- Publication number
- JPS5816951B2 JPS5816951B2 JP51143758A JP14375876A JPS5816951B2 JP S5816951 B2 JPS5816951 B2 JP S5816951B2 JP 51143758 A JP51143758 A JP 51143758A JP 14375876 A JP14375876 A JP 14375876A JP S5816951 B2 JPS5816951 B2 JP S5816951B2
- Authority
- JP
- Japan
- Prior art keywords
- waste liquid
- ion exchange
- recycled waste
- ammonia
- exchange treatment
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
- 239000007788 liquid Substances 0.000 title claims description 22
- 239000002699 waste material Substances 0.000 title claims description 16
- 238000000034 method Methods 0.000 title claims description 15
- 238000005342 ion exchange Methods 0.000 title claims description 8
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 36
- 229910021529 ammonia Inorganic materials 0.000 claims description 18
- 229910021536 Zeolite Inorganic materials 0.000 claims description 9
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 9
- 239000010457 zeolite Substances 0.000 claims description 9
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 8
- 239000002244 precipitate Substances 0.000 claims description 8
- 229910052500 inorganic mineral Inorganic materials 0.000 claims description 6
- 239000011707 mineral Substances 0.000 claims description 6
- 230000001172 regenerating effect Effects 0.000 claims description 5
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 4
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 claims description 3
- 239000000347 magnesium hydroxide Substances 0.000 claims description 3
- 229910001862 magnesium hydroxide Inorganic materials 0.000 claims description 3
- 150000003016 phosphoric acids Chemical class 0.000 claims description 3
- 230000007935 neutral effect Effects 0.000 claims description 2
- 159000000003 magnesium salts Chemical class 0.000 claims 2
- 229910019142 PO4 Inorganic materials 0.000 claims 1
- 239000000395 magnesium oxide Substances 0.000 claims 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical class [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims 1
- 230000003647 oxidation Effects 0.000 claims 1
- 238000007254 oxidation reaction Methods 0.000 claims 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims 1
- 239000010452 phosphate Substances 0.000 claims 1
- 235000010755 mineral Nutrition 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 4
- 239000003337 fertilizer Substances 0.000 description 3
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- MXZRMHIULZDAKC-UHFFFAOYSA-L ammonium magnesium phosphate Chemical compound [NH4+].[Mg+2].[O-]P([O-])([O-])=O MXZRMHIULZDAKC-UHFFFAOYSA-L 0.000 description 2
- 229910001629 magnesium chloride Inorganic materials 0.000 description 2
- 230000008929 regeneration Effects 0.000 description 2
- 238000011069 regeneration method Methods 0.000 description 2
- 239000010802 sludge Substances 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 229910052567 struvite Inorganic materials 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- ZSLUVFAKFWKJRC-IGMARMGPSA-N 232Th Chemical compound [232Th] ZSLUVFAKFWKJRC-IGMARMGPSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 229910052776 Thorium Inorganic materials 0.000 description 1
- 238000003915 air pollution Methods 0.000 description 1
- XKMRRTOUMJRJIA-UHFFFAOYSA-N ammonia nh3 Chemical compound N.N XKMRRTOUMJRJIA-UHFFFAOYSA-N 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- 238000010612 desalination reaction Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 1
- 235000019341 magnesium sulphate Nutrition 0.000 description 1
- 159000000001 potassium salts Chemical class 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000012492 regenerant Substances 0.000 description 1
- 239000013535 sea water Substances 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 239000001488 sodium phosphate Substances 0.000 description 1
- 229910000162 sodium phosphate Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 1
Landscapes
- Water Treatment By Sorption (AREA)
- Removal Of Specific Substances (AREA)
Description
【発明の詳細な説明】
本発明は、アンモニアを吸着したゼオライト系鉱物を再
生する際に発生する再生廃液中よりアンモニアを除去す
る方法に関するものである。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for removing ammonia from a regeneration waste liquid generated when regenerating zeolite minerals that have adsorbed ammonia.
従来、水中のアンモニアを除去する方法として、生物学
的脱窒素性、アンモニアストリッピング法、ブレークポ
イントクロリネーション法、イオン交換吸着法等が知ら
れている。Conventionally, biological denitrification, an ammonia stripping method, a breakpoint chlorination method, an ion exchange adsorption method, and the like are known as methods for removing ammonia from water.
イオン交換吸着法は、天然ゼオライトやクリップティラ
イト（Ｃ１ｉｎｏ−ｐｔｉｌｉｔｅ）等のゼオライト系
鉱物を用いてアンモニアを選択的に除去するもので、そ
の除去反応は、例えばナトリウム型ゼオライトの場合、
Ｚｅｏｌ ｉ ｔｅ−Ｎａ＋＋Ｎ）ｆ４”４１：Ｚｅｏ
ｌｉｔｅ −ＮＨ４＋＋Ｎａ＋
のイオン交換であることが知られている。The ion exchange adsorption method selectively removes ammonia using zeolite minerals such as natural zeolite and cliptilite. -Na++N) f4”41:Zeo
It is known that this is an ion exchange of lite -NH4++Na+.
このようなイオン交換反応による脱塩プロセスでは、常
に再生廃液の処分が問題となるが、ゼオライト系鉱物に
よるアンモニアの除去においても同様で、アンモニアを
吸着したゼオライトをＮａＣ１，ＮａＯＨ，Ｃａ（ＯＨ
）２その他のすトリウム、カルシウムあるいはカリウム
の塩又は水酸化物溶液で再生したときの濃厚なアンモニ
アを含む再生廃液の処分が問題となっていた。In desalination processes using such ion exchange reactions, disposal of the regenerated waste liquid is always a problem, but the same is true for the removal of ammonia using zeolite minerals.
)2 Disposal of regeneration waste liquid containing concentrated ammonia when regenerated with other thorium, calcium or potassium salts or hydroxide solutions has been a problem.
従来、このような再生廃液の処分方法は、廃液中のアン
モニアを空気又は水蒸気で大気中にストリッピングする
方法が一般的であったが、大気中に放出されたアンモニ
アが再び付近の水系に溶解してしまうこと、また大気汚
染上からも極めて不合理な方法があった。Conventionally, the common method for disposing of such recycled waste liquid was to strip the ammonia in the waste liquid into the atmosphere with air or steam, but the ammonia released into the atmosphere could be redissolved in the nearby aqueous system. This was an extremely unreasonable method in terms of air pollution.
本発明は、上記従来の再生廃液の処分法の問題点を解決
し、再生廃液中のアンモニアを有価固形物として回収し
、しかも再生廃液中の反復再利用をも可能にすることを
目的とするものである。The present invention aims to solve the above-mentioned problems of the conventional disposal method for recycled waste liquid, recover ammonia in the recycled waste liquid as valuable solids, and also enable repeated reuse of the recycled waste liquid. It is something.
本発明は、アンモニアを吸着したゼオライト鉱物を上記
Ｎ ａ Ｃｌ、Ｎ ａ ＯＨ、Ｃａ （ＯＨ） ２その
他の水溶液によって再生したときの再生廃液に、硫酸マ
グネシウム、塩化マグネシウム等のマグネシウム水酸化
物、酸化物もしくはマグネシウム塩とリン酸もしくはリ
ン酸塩を添加混和し、生成する沈殿を分離することを特
徴とするもので、また本発明において使用するマグネシ
ウムとしては、海水を使用することもでき、さらに上記
薬品を添加混和することにより沈殿が生成するが、この
場合の液のｐＨは中性以上、好ましくはｐＨ９〜１０で
、生成した沈殿はリン酸マグネシウムアンモン
（’ＮＨ４ＭｇＰＯ４・６Ｈ２０）であり、これを分離
回収して肥料あるいはその原料として有効に利用するこ
とができる。In the present invention, magnesium hydroxide such as magnesium sulfate, magnesium chloride, etc. This method is characterized by adding and mixing phosphoric acid or a phosphoric acid salt with phosphoric acid or a phosphoric acid salt, and separating the formed precipitate.Also, as the magnesium used in the present invention, seawater can also be used, and the above-mentioned A precipitate is formed by adding and mixing chemicals, but in this case the pH of the liquid is above neutral, preferably pH 9 to 10, and the precipitate that is formed is magnesium ammonium phosphate ('NH4MgPO4・6H20), which is It can be separated and recovered and used effectively as fertilizer or its raw material.
さらに、生成沈殿を分離した分離液を、再びアンモニア
を吸着したゼオライト系鉱物の再生剤として反復利用で
きる。Furthermore, the separated liquid obtained by separating the generated precipitate can be repeatedly used as a regenerating agent for zeolite minerals that have adsorbed ammonia.
次に本発明の実施例を示す。Next, examples of the present invention will be shown.
実施例 Ｉ
Ｓ下水処理場の活性汚泥処理水のアンモニア性窒素は１
５．４ ｐｐｍであり、これを径２５１ｎ１ｒｔφ、長
さ１０００ｍｍのカラム内に８×２０メツシユの天然ク
リップティライトを充填したものに、５ｖ−４（１／ｈ
）で通水した結果、クリップティライト充填容量の２５
０倍の原水を通水したときに流出水中のアンモニア濃度
が１．０ｐｐｍ以上となり、リークをおこした時点で通
水を停止した。Example Ammonia nitrogen in activated sludge treated water at IS sewage treatment plant is 1
5.4 ppm, and this was added to a column with a diameter of 251n1rtφ and a length of 1000mm filled with 8 x 20 meshes of natural cliptilite at 5v-4 (1/h).
), the cliptilite filling capacity was 25.
When the ammonia concentration in the outflow water reached 1.0 ppm or more when 0 times the raw water was passed through, and a leak occurred, the water flow was stopped.
次に、このカラムに再生剤として２０係のＮａＣｌ溶液
をクリップティライト１１あたり５１通液したところ、
流出した再生廃液中のアンモニア濃度は
２４００７ｎｖ′ｌ テア−”）だ。Next, when a 20% NaCl solution was passed through this column as a regenerating agent at a rate of 51 per 11 cliptilites.
The ammonia concentration in the recycled waste liquid that flowed out was 24,007 nv'l tear'').
この再生廃液に、塩化マグネシウムを
３６００ｒｎＩ？／ｌ（８８Ｍｇ２＋）、リン酸第−ナ
トリウムを１．３％（ａｓＰＯｊ）添加し、ｐＨを９．
５に調整後撹拌混合し、３０分静置後の上澄液のアンモ
ニア濃度は２５０ｍ９／ｌと低濃度となり、これを再び
上記アンモニアを吸着したクリップティライトの再生剤
として反復使用したが、全く問題のないことが認められ
た。Add 3600 rnI of magnesium chloride to this recycled waste liquid. /l (88Mg2+), 1.3% (asPOj) of sodium phosphate was added and the pH was adjusted to 9.
5, the ammonia concentration of the supernatant liquid was as low as 250 m9/l after being left to stand for 30 minutes, and this was repeatedly used as a regenerant for cliptilite that had adsorbed ammonia, but no results were found. It was confirmed that there were no problems.
また、生成した沈殿は、化学分析の結果リン酸マグネシ
ウムアンモンであることか確認され、これは塩基性肥料
として利用可能であることが判明した。Further, the resulting precipitate was confirmed to be magnesium ammonium phosphate as a result of chemical analysis, and it was found that this can be used as a basic fertilizer.
以上述べたように本発明によれは、従来からゼオライト
系鉱物によるアンモニア除去方法の最大の問題点であっ
た再生廃液の処分が完全に確消され、またゼオライトに
よって濃縮されたアンモニアを肥料として利用すること
ができ、さらに最終的に分離された分離液をゼオライト
の再生剤として反復利用でき、環境汚泥をも防止するこ
とができるものである。As described above, the present invention completely eliminates the disposal of recycled waste liquid, which has traditionally been the biggest problem with ammonia removal methods using zeolite minerals, and also makes it possible to utilize ammonia concentrated with zeolite as fertilizer. Furthermore, the final separated liquid can be used repeatedly as a zeolite regenerating agent, and environmental sludge can also be prevented.
Claims (1)
ンモニア性窒素含有廃水中のアンモニア性窒素を除去す
るに際して発生するアンモニア吸着ゼオライト系鉱物の
再生剤による再生廃液に、マグネシウム水酸化物、酸化
物もしくはマグネシウム塩とリン酸もしくはリン酸塩を
添加混和し、生成する沈殿を分離することによって再生
廃液中のアンモニアを除去することを特徴とするイオン
交換処理における再生廃液の処理方法。 ２ 前記マグネシウム水酸化物、酸化物もしくはマグネ
シウム塩とリン酸もしくはリン酸塩を添加混和して沈殿
を生成するに際し、液のｐＨを中性以上、好ましくはｐ
Ｈ９〜１０にする特許請求の範囲第１項記載のイオン交
換処理における再生廃液の処理方法。 ３ 前記生成する沈殿を分離した分離液をゼオライト系
鉱物の再生剤として反復使用する特許請求の範囲第１項
、第２項記載のイオン交換処理における再生廃液の処理
方法。[Scope of Claims] 1. Magnesium hydroxide, oxidation 1. A method for treating recycled waste liquid in ion exchange treatment, characterized in that ammonia in the recycled waste liquid is removed by adding and mixing phosphoric acid or a phosphoric acid salt or a magnesium salt and separating the generated precipitate. 2. When adding and mixing the above magnesium hydroxide, oxide or magnesium salt with phosphoric acid or phosphate to form a precipitate, the pH of the liquid is adjusted to above neutral, preferably at p.
A method for treating regenerated waste liquid in ion exchange treatment according to claim 1, wherein H9 to H10 are obtained. 3. A method for treating recycled waste liquid in ion exchange treatment according to claims 1 and 2, wherein a separated liquid obtained by separating the generated precipitate is repeatedly used as a regenerating agent for zeolite minerals.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP51143758A JPS5816951B2 (en) | 1976-11-30 | 1976-11-30 | Treatment method for recycled waste liquid in ion exchange treatment |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP51143758A JPS5816951B2 (en) | 1976-11-30 | 1976-11-30 | Treatment method for recycled waste liquid in ion exchange treatment |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS5367675A JPS5367675A (en) | 1978-06-16 |
| JPS5816951B2 true JPS5816951B2 (en) | 1983-04-04 |
Family
ID=15346326
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP51143758A Expired JPS5816951B2 (en) | 1976-11-30 | 1976-11-30 | Treatment method for recycled waste liquid in ion exchange treatment |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS5816951B2 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| SE463364B (en) * | 1988-06-03 | 1990-11-12 | Ecocure Ab | PROCEDURES FOR THE REMOVAL OF NAVIGATES FROM RAAVATTEN |
-
1976
- 1976-11-30 JP JP51143758A patent/JPS5816951B2/en not_active Expired
Also Published As
| Publication number | Publication date |
|---|---|
| JPS5367675A (en) | 1978-06-16 |
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