JPH06285368A - Regenerating method of zeolite for removing ammonia - Google Patents
Regenerating method of zeolite for removing ammoniaInfo
- Publication number
- JPH06285368A JPH06285368A JP24058492A JP24058492A JPH06285368A JP H06285368 A JPH06285368 A JP H06285368A JP 24058492 A JP24058492 A JP 24058492A JP 24058492 A JP24058492 A JP 24058492A JP H06285368 A JPH06285368 A JP H06285368A
- Authority
- JP
- Japan
- Prior art keywords
- zeolite
- regenerant
- regenerated
- sodium
- sodium hydroxide
- 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.)
- Pending
Links
Landscapes
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は水からアンモニア性窒素
を選択的に吸着除去したゼオライトの再生方法に関する
ものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for regenerating zeolite by selectively removing ammoniacal nitrogen from water by adsorption.
【０００２】[0002]
【従来の技術】従来、水からアンモニアを除去する方法
として（ａ）塩素処理方法（ｂ）硝化菌を用いた生物学
的処理方法（ｃ）エアーストリッピング法（ｄ）スチー
ムストリッピング法および（ｅ）ゼオライトによるイオ
ン交換法がある。2. Description of the Related Art Conventionally, as a method for removing ammonia from water, (a) chlorine treatment method (b) biological treatment method using nitrifying bacteria (c) air stripping method (d) steam stripping method and ( e) There is an ion exchange method using zeolite.
【０００３】この内、（ａ）の方法はトリハロメタン生
成の問題や管理の困難さ、アンモニア濃度の高いときの
経費高等の問題があり、（ｂ）の方法は低水温時の除去
効果の悪さや、除去施設のための広い敷地面積を必要と
し、また、（ｃ）の方法は水中アンモニア濃度が低い場
合に効率が悪く、かつ、季節による除去率の変動が大き
い欠点があり、（ｄ）の方法は下水処理水程度のアンモ
ニア濃度では経費高となる欠点があった。Of these, the method (a) has problems such as trihalomethane formation and difficulty of management, and high cost when the ammonia concentration is high, and the method (b) has poor removal effect at low water temperature. , Requires a large site area for the removal facility, and the method (c) is inefficient when the concentration of ammonia in the water is low, and the removal rate varies greatly depending on the season. The method has a drawback that the cost is high when the ammonia concentration is about the same as the sewage treatment water.
【０００４】このため、除去速度が速く、水温の変化に
対しても効果が安定し、装置の運転方法が簡単でかつ、
除去材としてのゼオライトが比較的安価であることから
（ｅ）のゼオライトによるイオン交換法が近年用いられ
るようになっている。Therefore, the removal speed is high, the effect is stable against changes in water temperature, the operation method of the device is simple, and
Since zeolite as a removing material is relatively inexpensive, the ion exchange method using zeolite (e) has been used in recent years.
【０００５】従来、ゼオライトの再生剤として食塩、塩
化カリウム等が用いられ、また、水酸化ナトリウムや塩
化カルシウム等も単独或いは食塩や塩化カリウム等と併
用して用いられ、それなりの再生効果を上げている。Conventionally, sodium chloride, potassium chloride, etc. have been used as a regenerating agent for zeolite, and sodium hydroxide, calcium chloride, etc. have also been used alone or in combination with sodium chloride, potassium chloride, etc. to enhance their regenerating effect. There is.
【０００６】[0006]
【発明が解決しようとする課題】しかしながら、従来の
ゼオライトの再生方法は、被再生ゼオライトより分離濃
縮された再生廃液中のアンモニアの処分に問題点があ
り、再生廃液中よりアンモニアを除去するために、アル
カリ性廃液のストリッピング法、生物処理等が研究され
ているが、二次公害を生じたり、低温時の効果の悪さや
その他の障害により設備の運転管理等にも種々支障があ
る。However, the conventional method for regenerating zeolite has a problem in the disposal of ammonia in the regenerated waste liquid separated and concentrated from the regenerated zeolite, and in order to remove the ammonia from the regenerated waste liquid. The alkaline waste liquid stripping method, biological treatment, etc. have been studied, but there are various obstacles to the operation management of equipment due to secondary pollution, poor effect at low temperature and other obstacles.
【０００７】本発明は斯様な状況のもとに、被再生ゼオ
ライトを効率的に再生し、また、再生廃液の処理上にお
いても問題のない再生方法を提供し、延いては、廃液中
からのアンモニアの除去操作を効率的かつ経済的に行な
える再生方法を提供することを目的として創案したもの
である。Under such circumstances, the present invention provides a method for efficiently regenerating zeolite to be regenerated, and a regeneration method which does not cause any problem in the treatment of regenerated waste liquid. The present invention was devised for the purpose of providing a regeneration method capable of efficiently and economically removing the ammonia.
【０００８】[0008]
【課題を解決するための手段】次亜塩素酸ナトリウム単
独若しくはこれらと食塩、塩化カリウムとの水溶液中に
水酸化ナトリウムを加えて再生剤となし、この再生剤に
よってアンモニウムイオンを吸着したゼオライトを再生
する。[Means for Solving the Problems] Sodium hypochlorite alone or an aqueous solution of sodium chloride and potassium chloride is added with sodium hydroxide to form a regenerant, and the zeolite adsorbing ammonium ions is regenerated by the regenerant. To do.
【０００９】或いは、次亜塩素酸ナトリウム又は次亜塩
素酸カルシウム単独若しくはこれらと食塩、塩化カリウ
ム或いは塩化カルシウムとの水溶液によってゼオライト
を再生し、再生廃液中に水酸化ナトリウムを添加混合す
る。Alternatively, the zeolite is regenerated with sodium hypochlorite or calcium hypochlorite alone or an aqueous solution of these with sodium chloride, potassium chloride or calcium chloride, and sodium hydroxide is added and mixed into the regenerated waste liquid.
【００１０】[0010]
【作用】水溶液中のナトリウムイオン又はカルシウムイ
オンによりアンモニウムイオンが置換され、次式のよう
に被再生ゼオライトがナトリウム又はカルシウム型に再
生されるとともに、脱着されたアンモニウムイオンが分
解される。The ammonium ion is replaced by sodium ion or calcium ion in the aqueous solution, the regenerated zeolite is regenerated into sodium or calcium type as shown in the following formula, and the desorbed ammonium ion is decomposed.
【００１１】[0011]
【化１】 [Chemical 1]
【００１２】しかしながら、上式に見られる通り、脱
着したアンモニウムイオンが分解する際塩酸が生じ、再
生廃液のｐＨが低下する。塩素剤を加えてアンモニウム
イオンを分解するとき、ｐＨの低下によってその分解が
遅くなることはすでに知られているところであるが、水
酸化ナトリウムの添加により、再生廃液中の酸を中和
し、アンモニウムイオンの分解を促進することができ
る。However, as seen in the above equation, hydrochloric acid is generated when the desorbed ammonium ions are decomposed, and the pH of the waste liquid for regeneration is lowered. It is already known that when a chlorine agent is added to decompose ammonium ions, the decomposition is slowed by lowering the pH, but the addition of sodium hydroxide neutralizes the acid in the regenerated waste liquid and The decomposition of ions can be promoted.
【００１３】[0013]
【実施例１】図１は本発明に係るアンモニア除去用ゼオ
ライトの再生方法を実施した装置例の略示図である。Example 1 FIG. 1 is a schematic view of an example of an apparatus for carrying out a method for regenerating ammonia-removing zeolite according to the present invention.
【００１４】図中、１は中間部に５ｌ（リットル）の天
然産ゼオライトの一種であるクリノプチロライト（有効
径０．５１ｍｍ、均等係数１．６６、見掛け比重０．９
３、以下ゼオライトと称する）ａを層高６３７ｍｍにな
るように充填したアクリル製樹脂塔（内径１００ｍｍ、
高さ１５００ｍｍ）である。In the figure, 1 is clinoptilolite (effective diameter 0.51 mm, uniform coefficient 1.66, apparent specific gravity 0.9) which is a kind of naturally occurring zeolite of 5 l (liter) in the middle part.
3. Acrylic resin tower (inner diameter 100 mm, filled with a) to be 637 mm in bed height
The height is 1500 mm).
【００１５】この樹脂塔１の上部を切替弁２、流量計３
および流量調整弁４を順次介して第一注入口５に連通さ
せ、前記の第一切替弁２は第一排液口６に連通させてあ
る。The upper part of the resin tower 1 is provided with a switching valve 2 and a flow meter 3
The flow rate adjusting valve 4 and the first inlet 5 are communicated with each other, and the first switching valve 2 is communicated with the first drainage port 6.
【００１６】また、樹脂塔１の下部は第二切替弁７を介
して第二注入口８と第二排液口９に連通させてある。The lower part of the resin tower 1 is connected to the second inlet 8 and the second drain 9 via the second switching valve 7.
【００１７】そして、この装置において、アンモニウム
イオンを含む原水を第一注入口５を通じて空間速度７で
樹脂塔１内に流し、樹脂塔１のゼオライトに約２５．５
ｇのアンモニウムイオンを吸着させ前処理を行った。In this apparatus, raw water containing ammonium ions is caused to flow through the first inlet 5 into the resin tower 1 at a space velocity of 7 and the zeolite in the resin tower 1 is filled with about 25.5.
Pretreatment was performed by adsorbing g of ammonium ions.
【００１８】前処理した前記のゼオライトを次の条件で
再生した。The above pretreated zeolite was regenerated under the following conditions.
【００１９】再生条件 逆 洗 ：３０ｍ／ｈｒ×１０ｍｉｎ（分） 再生剤量 ：食塩３６０ｇ、次亜塩素酸ナトリウム液
１．４５リットル（有効塩素９．５％、遊離アルカリ
０．６６％、比重１．１９）を水道水に溶解して１０リ
ットルとしたもの。 通 薬 ：上向流 空間速度 ５ 押 出 ：上向流 空間速度 ５（水量２５リット
ル） 洗 浄 ：下向流 空間速度 ７×３０ｍｉｎ（分） 再生廃液の量は３５リットル、ｐＨは１．５であった。Regeneration conditions Backwash: 30 m / hr × 10 min (min) Regenerator amount: 360 g of salt, 1.45 l of sodium hypochlorite solution (9.5% available chlorine, 0.66% free alkali, specific gravity 1) .19) dissolved in tap water to 10 liters. Penetration: Upflow space velocity 5 Extrusion: Upflow space velocity 5 (25 liters of water) Washing: Downflow space velocity 7 × 30 min (min) Recycled waste liquid volume is 35 liters, pH is 1.5 Met.
【００２０】なお、再生廃液は、通薬および押出し水量
の和の３５リットルとし、洗浄廃水は加えていない。The reclaimed waste liquid is 35 liters, which is the sum of the amount of the replenishing agent and the amount of the extruded water, and no washing waste water is added.
【００２１】[0021]
【実施例２】実施例１で再生したゼオライト塔にアンモ
ニウムイオン１５０ｍｇ／ｌ（リットル）を含む原水を
空間速度７で通水し、処理水中のアンモニウムイオンが
１５ｍｇ／ｌ（リットル）に達した時点で再水を打切り
貫流点とした。[Example 2] Raw water containing ammonium ions of 150 mg / l (liter) was passed through the zeolite tower regenerated in Example 1 at a space velocity of 7 and the ammonium ions in the treated water reached 15 mg / l (liter). Then the re-water was cut off and the once-through point was set.
【００２２】処理水中へ漏洩した量を差し引いて補正し
たゼオライト５リットルのアンモニウムイオン吸着量は
約２６ｇである。The ammonium ion adsorption amount of 5 liters of zeolite corrected by subtracting the amount leaked into the treated water is about 26 g.
【００２３】この貫流点に達したゼオライトを再生剤液
の組成のみ次のように変え、他の条件は実施例１と同様
の条件で再生した。The zeolite that reached this flow-through point was regenerated under the same conditions as in Example 1 except that the composition of the regenerant liquid was changed as follows.
【００２４】再生剤液：食塩２９０ｇ、水酸化ナトリウ
ム４８ｇ（９７％）、次亜塩素酸ナトリウム液１．４５
リットル（有効塩素９．５％、遊離アルカリ０．６６
％、比重１．１９）を水道水に溶解して１０リットルと
したもの。Regenerating agent solution: 290 g of salt, 48 g of sodium hydroxide (97%), sodium hypochlorite solution of 1.45
Liter (effective chlorine 9.5%, free alkali 0.66
%, Specific gravity 1.19) dissolved in tap water to make 10 liters.
【００２５】再生廃液の量は３５リットルで、その分析
値は下記の通りであり、アンモニウムイオンは検出され
なかった。ただし、分析値は押出し終了後４時間後のも
のである。The amount of the recycled waste liquid was 35 liters, and the analytical values were as follows, and ammonium ion was not detected. However, the analysis value is after 4 hours from the end of extrusion.
【００２６】ｐＨ ８．１ 残留塩素 ２１０ｍｇ／ｌ（リットル） アンモニウムイオン ０ 上記実施例のように、ゼオライトの再生剤として次亜塩
素酸ナトリウム単独若しくはこれらと食塩、塩化カリウ
ムなどの１種或いは数種の水溶液を用いるとき再生廃液
のｐＨは低下するが、このｐＨの低下は、水酸化ナトリ
ウムを再生剤に加えることによって抑えることができ
る。また、再生廃液のｐＨは逆洗廃水、洗浄廃水を再生
廃液に加えるときは、その量および廃水中の酸消費量の
多少によっても変わってくる。PH 8.1 Residual chlorine 210 mg / l (liter) Ammonium ion 0 As in the above example, as a regenerator of zeolite, sodium hypochlorite alone or with one or several kinds of sodium chloride, potassium chloride and the like. Although the pH of the waste liquid for regeneration is lowered when the aqueous solution is used, this decrease in pH can be suppressed by adding sodium hydroxide to the regenerant. Further, the pH of the reclaimed waste liquid varies depending on the amount of backwashing wastewater and the amount of acid consumption in the wastewater when the wash wastewater is added to the reclaimed wastewater.
【００２７】また、再生剤中に水酸化ナトリウムを加え
ず、再生廃液中に水酸化ナトリウムを直接添加混合する
ことによってもｐＨを中性付近とし、アンモニウムイオ
ンの分解を促進することができる。Further, by adding sodium hydroxide directly to the waste liquid for regeneration without adding sodium hydroxide to the regenerant, the pH can be made close to neutral and the decomposition of ammonium ion can be promoted.
【００２８】なお、本発明でいう再生剤中、次亜塩素酸
ナトリウム等に食塩、塩化カリウム或いは塩化カルシウ
ムを加えたものは、これら各物質を主要剤とするという
意味であって、これら各物質に再生剤として例えば、炭
酸ナトリウム等用いることのできる物質、又は、再生剤
としての効果のない物質を加えたものでも良い。In the regenerant of the present invention, sodium hypochlorite and the like to which sodium chloride, potassium chloride or calcium chloride is added means that each of these substances is the main agent. A substance that can be used as a regenerant, such as sodium carbonate, or a substance that does not have an effect as a regenerant may be added.
【００２９】[0029]
【発明の効果】本発明は前記の通りの構成であるからゼ
オライトを再生できるばかりでなく、廃液中のアンモニ
ウムイオンの分解を促進し、廃液の管理が容易な再生方
法を提供できる。EFFECTS OF THE INVENTION Since the present invention has the above-mentioned constitution, it can provide not only the regeneration method of the zeolite but also the regeneration method in which the decomposition of ammonium ion in the waste liquid is promoted and the waste liquid is easily managed.
【図１】本発明方法を実施した装置の略示図。FIG. 1 is a schematic view of an apparatus for carrying out the method of the present invention.
Claims (2)
化ナトリウムを単独若しくはこれらに食塩、塩化カリウ
ムを加えて再生剤となし、この再生剤によってアンモニ
ウムイオンを吸着したゼオライトを再生することを特徴
とするアンモニア除去用ゼオライトの再生方法。1. A regenerating agent comprising sodium hydroxide alone or sodium chloride or potassium chloride in an aqueous solution of sodium hypochlorite to regenerate the zeolite having adsorbed ammonium ions. A method for regenerating zeolite for removing ammonia.
ルシウム単独若しくはこれらと食塩、塩化カリウム或い
は塩化カルシウムとの水溶液を再生剤となし、この再生
剤によってアンモニウムイオンを吸着したゼオライトを
再生すると共に、再生廃液に水酸化ナトリウムを添加す
ることを特徴とするアンモニア除去用ゼオライトの再生
方法。2. Sodium hypochlorite or calcium hypochlorite alone or an aqueous solution of these with sodium chloride, potassium chloride or calcium chloride is used as a regenerant, and this regenerant regenerates zeolite having ammonium ions adsorbed. A method for regenerating zeolite for ammonia removal, characterized in that sodium hydroxide is added to the reclaimed waste liquid.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP24058492A JPH06285368A (en) | 1992-09-09 | 1992-09-09 | Regenerating method of zeolite for removing ammonia |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP24058492A JPH06285368A (en) | 1992-09-09 | 1992-09-09 | Regenerating method of zeolite for removing ammonia |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH06285368A true JPH06285368A (en) | 1994-10-11 |
Family
ID=17061692
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP24058492A Pending JPH06285368A (en) | 1992-09-09 | 1992-09-09 | Regenerating method of zeolite for removing ammonia |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH06285368A (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5853689A (en) * | 1997-02-11 | 1998-12-29 | Klatte; Fred | Method for producing chlorine dioxide by activating an impregnated zeolite crystal mixture, and mixtures for performing such method |
| US5885543A (en) * | 1997-02-11 | 1999-03-23 | Klatte; Fred | Method for producing chlorine dioxide using calcium chloride impregnated zeolite or aqueous calcium chloride |
| WO2005075355A3 (en) * | 2004-02-10 | 2005-10-13 | Kemira Oyj | Process of removal of ammonium from waste water |
| US7347994B2 (en) | 2002-09-13 | 2008-03-25 | Ica Trinova, Llc | Method and composition for attracting arthropods by volatilizing an acid |
| US9382116B2 (en) | 2013-01-10 | 2016-07-05 | Ica Trinova, Llc | Mixtures for producing chlorine dioxide gas in enclosures and methods of making the same |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5037680A (en) * | 1973-08-07 | 1975-04-08 |
-
1992
- 1992-09-09 JP JP24058492A patent/JPH06285368A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5037680A (en) * | 1973-08-07 | 1975-04-08 |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5853689A (en) * | 1997-02-11 | 1998-12-29 | Klatte; Fred | Method for producing chlorine dioxide by activating an impregnated zeolite crystal mixture, and mixtures for performing such method |
| US5885543A (en) * | 1997-02-11 | 1999-03-23 | Klatte; Fred | Method for producing chlorine dioxide using calcium chloride impregnated zeolite or aqueous calcium chloride |
| US7347994B2 (en) | 2002-09-13 | 2008-03-25 | Ica Trinova, Llc | Method and composition for attracting arthropods by volatilizing an acid |
| US7922992B2 (en) | 2002-09-13 | 2011-04-12 | Ica Trinova, Llc | Composition and method for producing carbon dioxide |
| US8709396B2 (en) | 2002-09-13 | 2014-04-29 | Premark Feg L.L.C. | Method and composition for attracting arthropods by volatizing an acid |
| WO2005075355A3 (en) * | 2004-02-10 | 2005-10-13 | Kemira Oyj | Process of removal of ammonium from waste water |
| US9382116B2 (en) | 2013-01-10 | 2016-07-05 | Ica Trinova, Llc | Mixtures for producing chlorine dioxide gas in enclosures and methods of making the same |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US5453201A (en) | Water treatment process | |
| US20020100729A1 (en) | Purification of produced water from coal seam natural gas wells using ion exchange and reverse osmosis | |
| CN101987764A (en) | Method and treatment device for purifying water of micro polluted water source | |
| JP3646900B2 (en) | Apparatus and method for treating boron-containing water | |
| CN112266099A (en) | Mine fluorine-containing wastewater resource utilization system and process | |
| US3985859A (en) | Vacuum stripping of ammonia | |
| JPH06285368A (en) | Regenerating method of zeolite for removing ammonia | |
| Schoeman et al. | An evaluation of the activated alumina process for fluoride removal from drinking-water and some factors influencing its | |
| CN204644026U (en) | A kind of device adopting PhotoelectrochemicalTechnique Technique to remove ammonia nitrogen in water | |
| JP4110604B2 (en) | Fluorine-containing water treatment method | |
| JPH0214794A (en) | Treatment of waste liquid after regeneraton of ion exchange apparatus | |
| JP3727212B2 (en) | Apparatus and method for treating wastewater containing boron | |
| JP2000301005A (en) | Method for reutilizing effluent in regeneration of ion exchange resin | |
| KR200211618Y1 (en) | Unit capable of adsorbing, desorbing and recovering toxic ions using ion exchangers | |
| Pollio et al. | Tertiary treatment of municipal sewage effluents | |
| JPS58174297A (en) | Treatment of waste water from desulfurization of waste gas | |
| RU2808013C1 (en) | Method for purifying groundwater from radon, alpha activity, iron, manganese, hardness salts and carbon dioxide | |
| Tate et al. | Recent developments in direct filtration | |
| JP3261033B2 (en) | Water purification treatment equipment | |
| JPH1080682A (en) | Nitrate nitrogen removing device and water purifier using the same | |
| CA1042575A (en) | Process for regenerating an ion exchange bed | |
| JP2003094051A (en) | Method for regenerating boron selective adsorption resin | |
| CN104891717A (en) | Method and apparatus for removing ammonia nitrogen in water by utilizing photoelectrochemical technology | |
| JP2941988B2 (en) | Removal method of nitrate ion in raw water | |
| Symons et al. | Treatment Processes for Coping With Variation in Raw‐Water Quality |