JP2008036573A - Adsorbent for adsorbing ammonium ion selectively - Google Patents
Adsorbent for adsorbing ammonium ion selectively Download PDFInfo
- Publication number
- JP2008036573A JP2008036573A JP2006216730A JP2006216730A JP2008036573A JP 2008036573 A JP2008036573 A JP 2008036573A JP 2006216730 A JP2006216730 A JP 2006216730A JP 2006216730 A JP2006216730 A JP 2006216730A JP 2008036573 A JP2008036573 A JP 2008036573A
- Authority
- JP
- Japan
- Prior art keywords
- ammonium ion
- adsorbent
- ammonium
- acid
- ions
- 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.)
- Granted
Links
Images
Abstract
Description
本発明は、アンモニウムイオン選択的吸着剤に関する。また、この吸着剤を利用したアンモニウムイオンを含む生活排水や工業排水などの排水の処理方法に関する。さらに本発明は、アンモニウムイオン選択的吸着剤の製造方法に関する。 The present invention relates to an ammonium ion selective adsorbent. Further, the present invention relates to a method for treating wastewater such as domestic wastewater and industrial wastewater containing ammonium ions using the adsorbent. Furthermore, this invention relates to the manufacturing method of an ammonium ion selective adsorption agent.
生活排水や工業排水には、１価の陽イオンとして、ナトリウムイオン、カリウムイオン、アンモニウムイオンなどが含有されているが、それらの排出基準は水質汚濁防止法によって定められている。例えば、環境省令第２１号における水質汚濁防止法の省令においては、アンモニア性窒素に０．４を乗じたもの、亜硝酸性窒素及び硝酸性窒素の合計が１００ｍｇ／Ｌと、窒素に関しての排出基準が定められている。排水中のアンモニア性窒素は、電解法により除去することが可能であるが、エネルギーコストが高いという欠点がある。 Domestic wastewater and industrial wastewater contain sodium ions, potassium ions, ammonium ions, etc. as monovalent cations, and their discharge standards are determined by the Water Pollution Control Law. For example, in the ministerial ordinance of the Water Pollution Control Act in Ordinance No. 21 of the Environment, the emission standard for nitrogen is 100 mg / L of ammonia nitrogen multiplied by 0.4, and the total of nitrite nitrogen and nitrate nitrogen is 100 mg / L. Is stipulated. Ammonia nitrogen in the waste water can be removed by an electrolytic method, but has a disadvantage of high energy cost.
下記表１に示されるように、ゼオライト系化合物が、アンモニウムイオンを吸着できることが知られている。 As shown in Table 1 below, it is known that zeolitic compounds can adsorb ammonium ions.
本発明の主な目的は、アンモニウムイオンを選択的に吸着することが可能な吸着剤を提供することであり、さらには、この吸着剤を利用した生活排水や工業排水などの排水の処理方法を提供することである。 The main object of the present invention is to provide an adsorbent capable of selectively adsorbing ammonium ions, and further, a method for treating wastewater such as domestic wastewater and industrial wastewater using the adsorbent. Is to provide.
本発明者は、上記した目的を達成すべく鋭意研究を重ねた結果、特定の複合酸化物がアンモニウムイオンに対して選択的吸着性を示すことを見出した。該吸着剤は、ナトリウムイオンおよびカリウムイオンよりもアンモニウムイオンに高い親和性を有し、アンモニウムイオンを選択的に吸着除去することができる。 As a result of intensive studies to achieve the above-described object, the present inventor has found that a specific composite oxide exhibits selective adsorptivity with respect to ammonium ions. The adsorbent has higher affinity for ammonium ions than sodium ions and potassium ions, and can selectively adsorb and remove ammonium ions.
本発明は、以下のアンモニウムイオン選択的吸着剤、排水処理方法及びアンモニウムイオン選択的吸着剤の製造方法を提供するものである。
1. 下記一般式（１）：
HCa2Ｎｂ3Ｏ10・ｎＨ2Ｏ （１）
（式中、ｎは、０≦ｎ≦４を満たす数である。）で表される化合物を有効成分とするアンモニウムイオン選択的吸着剤。
2. ｎが1.0から2.0の範囲内にある、項１に記載のアンモニウムイオン選択的吸着剤。
3. アンモニウムイオンを含有する排水に、請求項１または２に記載の吸着剤を接触させてアンモニウムイオンを選択的に吸着することを特徴とする排水処理方法。
4. 排水中のアンモニウムイオン濃度が１０ｍｇ/Ｌ以下である、項３に記載の方法。
5. アルカリ金属炭酸塩、炭酸カルシウム、Nb2O5をアルカリ金属：Ca:Nb=1:2:3(モル比)の比率で混合し、900〜1,100℃で焼成し、焼成物を粉砕後さらに900〜1,100℃で焼成し、酸処理を行うことを特徴とする、項1または2に記載のアンモニウム選択的吸着剤の製造方法。
The present invention provides the following ammonium ion selective adsorbent, waste water treatment method, and ammonium ion selective adsorbent production method.
1. The following general formula (1):
HCa 2 Nb 3 O 10 · nH 2 O (1)
(In the formula, n is a number satisfying 0 ≦ n ≦ 4) An ammonium ion selective adsorbent containing a compound represented by the following formula as an active ingredient.
2. The ammonium ion selective adsorbent according to Item 1, wherein n is in the range of 1.0 to 2.0.
3. A wastewater treatment method comprising selectively adsorbing ammonium ions by bringing the adsorbent according to claim 1 into contact with wastewater containing ammonium ions.
4. The method according to item 3, wherein the ammonium ion concentration in the waste water is 10 mg / L or less.
5. Alkali metal carbonate, calcium carbonate and Nb 2 O 5 are mixed at a ratio of alkali metal: Ca: Nb = 1: 2: 3 (molar ratio) and fired at 900-1100 ° C. Item 3. The method for producing an ammonium selective adsorbent according to Item 1 or 2, further comprising calcining at 900 to 1,100 ° C and performing an acid treatment.
本発明によれば、アルカリ金属イオンに対しアンモニウムイオンを選択的に吸着可能なアンモニウムイオン吸着剤を提供することができる。 According to the present invention, an ammonium ion adsorbent capable of selectively adsorbing ammonium ions to alkali metal ions can be provided.
吸着剤
本発明のアンモニウムイオン選択的吸着剤は、下記式（１）で表される複合酸化物を有効成分とする。
HCa2Ｎｂ3Ｏ10・ｎＨ2Ｏ （１）
（式中、ｎは、０≦ｎ≦４を満たす数である。）。
Adsorbent The ammonium ion selective adsorbent of the present invention contains a composite oxide represented by the following formula (1) as an active ingredient.
HCa 2 Nb 3 O 10 · nH 2 O (1)
(In the formula, n is a number satisfying 0 ≦ n ≦ 4).
ｎは、４以下、好ましくは３以下、より好ましくは1〜２、特に1.4〜１.6である。 n is 4 or less, preferably 3 or less, more preferably 1 to 2, particularly 1.4 to 1.6.
上記式（１）で表される化合物は、下記の方法に従って製造することができる。 The compound represented by the above formula (1) can be produced according to the following method.
好ましい製造法のスキームの一例を図1に示す。図1に示されるように、炭酸カリウム、炭酸カルシウム、Nb2O5をK:Ca:Nb = 1:2:3(モル比)になるように混合し、粉砕する。炭酸カリウムの代わりに炭酸ナトリウム、炭酸リチウムなどの他のアルカリ金属炭酸塩、あるいはアルカリ金属炭酸水素塩（NaHCO3, KHCO3, LiHCO3など）、アルカリ金属酢酸塩などのアルカリ金属有機酸塩を使用することもできる。また、炭酸カルシウムに代えてＣａ（ＯＨ）２，ＣａＣｌ２，ＣａＢｒ２，Ｃａ（ＮＯ３）２，ＣａＯまたはＣａＨＣＯ３、酢酸カルシウムなどの有機酸のカルシウム塩を使用することもできる。 An example of a preferred production scheme is shown in FIG. As shown in FIG. 1, potassium carbonate, calcium carbonate, and Nb 2 O 5 are mixed and pulverized so that K: Ca: Nb = 1: 2: 3 (molar ratio). Instead of potassium carbonate, use other alkali metal carbonates such as sodium carbonate and lithium carbonate, or alkali metal organic acid salts such as alkali metal bicarbonates (such as NaHCO 3 , KHCO 3 , LiHCO 3 ), and alkali metal acetates. You can also In addition, calcium salts of organic acids such as Ca (OH) 2 , CaCl 2 , CaBr 2 , Ca (NO 3 ) 2 , CaO or CaHCO 3 , and calcium acetate can be used instead of calcium carbonate.
また、酸化ニオブ（Nb2O5）に代えて、オキシ塩化ニオブ、窒化ニオブ、炭化ニオブを用いることもできる。 Further, niobium oxychloride, niobium nitride, or niobium carbide can be used instead of niobium oxide (Nb 2 O 5 ).
これらの混合物を粉砕後、焼成を行う。焼成は、1分当たり3〜20℃程度の速度で800〜1,300℃程度、好ましくは900〜1,100℃程度の温度まで昇温し、該温度で30分〜24時間程度、好ましくは1〜10時間焼成する。例えば、1200〜1,300℃の温度で２４時間焼成した場合であっても、10％前後の原料が残ることが本発明者の実験から明らかになった（Ｘ線回折のデータで確認）。原料を完全に消失させるためには、高温で長時間焼成するのは効率的ではなく、２段階で焼成するのが好ましい。すなわち、800〜1,300℃程度の温度まで昇温後、いったん室温程度まで冷却して焼成物を粉砕し、再度800〜1,300℃程度の温度で1〜15時間程度焼成する２段階の焼成を行うことにより、原料を完全に消失させ得ることが明らかになった。 The mixture is pulverized and fired. Firing is performed at a rate of about 3 to 20 ° C. per minute to a temperature of about 800 to 1,300 ° C., preferably about 900 to 1,100 ° C., and the temperature is about 30 minutes to 24 hours, preferably 1 to 10 hours. Bake. For example, even when baking was performed at a temperature of 1200 to 1,300 ° C. for 24 hours, it was clarified from the experiment of the present inventors that about 10% of the raw material remains (confirmed by X-ray diffraction data). In order to completely eliminate the raw material, firing at a high temperature for a long time is not efficient, and firing in two stages is preferable. That is, after heating up to a temperature of about 800 to 1,300 ° C., cooling to room temperature once, pulverizing the fired product, and performing a two-step firing again at a temperature of about 800 to 1,300 ° C. for about 1 to 15 hours. Thus, it was revealed that the raw material can be completely disappeared.
2段階焼成した焼成物（ＫＣａ２Ｎｂ３Ｏ１０）を必要に応じて粉砕して粉末状とし、酸処理を行う。なお、Ｋ２ＣＯ３に代えて他のアルカリ金属炭酸塩などを使用した場合にも、焼成物中のアルカリ金属は、酸処理により除去される。酸処理に使用される酸としては、塩酸、臭化水素酸、ヨウ化水素酸、硝酸、硫酸、燐酸、過塩素酸などの無機酸、メタンスルホン酸、トリクロル酢酸などの有機酸が挙げられ、好ましくは塩酸、硝酸が挙げられる。酸は焼成物に対し通常過剰量使用される。酸処理の温度は室温から100℃程度の温度で行うことができる。酸処理は、焼成物を酸水溶液の中に入れて撹拌後、ろ過して行ってもよく、焼成物をカラムに充填して酸水溶液を流して行ってもよい。酸水溶液で処理後、脱イオン水で洗浄液が中性になるまで洗浄し、風乾/加熱乾燥し、目的とする式(1)のアンモニウムイオン選択的吸着剤を得ることができる。得られたアンモニウムイオン選択的吸着剤の含水量は、乾燥の条件に依存するが、十分に乾燥した場合には、式(1)のｎは1〜2程度、特に1.4〜1.6程度になる。 The fired product (KCa 2 Nb 3 O 10 ) fired in two stages is pulverized as necessary to form a powder, and then acid-treated. Instead of K 2 CO 3 even when using such other alkali metal carbonates, alkali metal in the calcined product, is removed by acid treatment. Examples of the acid used for the acid treatment include inorganic acids such as hydrochloric acid, hydrobromic acid, hydroiodic acid, nitric acid, sulfuric acid, phosphoric acid and perchloric acid, and organic acids such as methanesulfonic acid and trichloroacetic acid. Preferably, hydrochloric acid and nitric acid are used. The acid is usually used in an excess amount relative to the fired product. The acid treatment can be performed at room temperature to about 100 ° C. The acid treatment may be performed by putting the fired product in an acid aqueous solution and stirring, followed by filtration, or by filling the column with the fired product and flowing the acid aqueous solution. After the treatment with an acid aqueous solution, washing with deionized water is carried out until the washing solution becomes neutral, followed by air drying / heating drying to obtain the target ammonium ion selective adsorbent of the formula (1). The water content of the obtained ammonium ion selective adsorbent depends on the drying conditions, but when sufficiently dried, n in formula (1) is about 1 to 2, particularly about 1.4 to 1.6.
本発明の式(1)のアンモニウムイオン選択的吸着剤は、層状ペロブスカイト構造を有する(図2)。該構造の吸着剤において、カリウムイオンが酸処理によりプロトンに交換され、これがアンモニウムイオンを含む排水と接触することでプロトンと交換されることで、アンモニウムイオンを選択的に吸着することができる。アンモニウムイオンを吸着した吸着剤は、酸処理することにより、プロトン型のアンモニウムイオン選択的吸着剤に再生することもでき、該アンモニウムイオン選択的吸着剤を必要に応じて減圧下ないし窒素、アルゴンなどの不活性ガス下(酸素を除くため)に加熱することによりアンモニアを除去し、プロトン型のアンモニウムイオン選択的吸着剤を再生し得る。 The ammonium ion selective adsorbent of the formula (1) of the present invention has a layered perovskite structure (FIG. 2). In the adsorbent having such a structure, potassium ions are exchanged with protons by acid treatment, and when these ions are exchanged with protons by coming into contact with wastewater containing ammonium ions, ammonium ions can be selectively adsorbed. The adsorbent having adsorbed ammonium ions can be regenerated into a proton-type ammonium ion-selective adsorbent by acid treatment, and the ammonium ion-selective adsorbent is reduced under reduced pressure or nitrogen, argon, etc. as necessary. The ammonia can be removed by heating under an inert gas (to remove oxygen) to regenerate the proton-type ammonium ion selective adsorbent.
以下、実施例を挙げて本発明を更に詳細に説明する。
実施例１
図1に示すスキームに従って、２段階の焼成処理を行い、さらに酸処理を行って、本発明のアンモニウムイオン選択的吸着剤を得た。酸処理の６Ｎ-HClに代えて、硝酸、水酸化ナトリウムで処理したアンモニウムイオン選択的吸着剤を各々得た。これら3種類のアンモニウムイオン選択的吸着剤に関し、Ｎａ＋，Ｋ＋，ＮＨ４ ＋に対する選択係数（Ｋｄ値）を求めた。測定条件は、以下の通りである。
吸着剤重量=0.20g, 処理液の体積.=20 mL, Ｎａ＋，Ｋ＋またはＮＨ４ ＋の濃度= 1 mmol, pH=2.2, 接触時間= 3日
結果を表2〜表4に示す。
Hereinafter, the present invention will be described in more detail with reference to examples.
Example 1
According to the scheme shown in FIG. 1, two-stage baking treatment was performed, and acid treatment was further performed to obtain the ammonium ion selective adsorbent of the present invention. Instead of acid-treated 6N HCl, ammonium ion selective adsorbents treated with nitric acid and sodium hydroxide were obtained. For these three types of ammonium ion selective adsorbents, selectivity coefficients (Kd values) for Na + , K + , and NH 4 + were determined. The measurement conditions are as follows.
Adsorbent weight = 0.20 g, treatment liquid volume = 20 mL, Na + , K + or NH 4 + concentration = 1 mmol, pH = 2.2, contact time = 3 days The results are shown in Tables 2-4.
表２、３に示されるように、酸処理の条件によって、アンモニウムイオンに対する選択性が変化する。また、表４の結果から、酸処理によりアルカリ金属イオンをプロトンに置換する工程は必要であることが明らかである。 As shown in Tables 2 and 3, the selectivity for ammonium ions varies depending on the acid treatment conditions. Also, from the results in Table 4, it is clear that a step for replacing alkali metal ions with protons by acid treatment is necessary.
また、酸処理の前後での金属酸化物のＸ線回折パターンを図３に示す。図３の結果から、本発明のアンモニウムイオン選択的吸着剤は、層状ペロブスカイト構造を有することが明らかである。
実施例２
実施例１で得られたアンモニウムイオン選択的吸着剤（HCa2Nb3O10×1.5H2O、塩酸処理）について、アンモニウムイオンの吸着の理論量に対する実際の吸着量(●)およびアンモニウムイオンの取り込み量（○）を以下の条件で測定した。
吸着剤の重量= 0.25g, アンモニウムイオン水溶液の体積.=500 mL、アンモニウムイオンの濃度= 9.0 mg/L, pH=3.0。サンプリング時間は、２，４，６，８，２４，４８および７２時間である。結果を図4に示す。図4の縦軸の左側は理論量に対する実際の吸着量を示し、縦軸の右側はアンモニウムイオンの実際の取り込み量を示す。図4に示されるように、本発明の吸着剤は、短時間で十分なアンモニウムイオンの吸着を示す。
実施例3
実施例１で得られたアンモニウムイオン吸着剤（HCa2Nb3O10×1.5H2O、塩酸処理）について、アンモニウムイオンの除去率を以下の条件で求めた。
吸着剤の重量= 0.05g, アンモニウムイオン水溶液の体積.=100 mL、pH=3.0、接触時間=1日間。初期濃度は、１，２，４，６，８，１０，１５，２０，２５（ｍｇ-ＮＨ４ +/Ｌ）であった。結果を図5に示す。図５に示されるように、本発明の吸着剤は、10ｍｇ-ＮＨ４ +/Ｌ以下の低濃度で極めて有効にアンモニウムイオンを吸着することができる。
Further, X-ray diffraction patterns of the metal oxide before and after the acid treatment are shown in FIG. From the results shown in FIG. 3, it is clear that the ammonium ion selective adsorbent of the present invention has a layered perovskite structure.
Example 2
For the ammonium ion selective adsorbent (HCa 2 Nb 3 O 10 × 1.5H 2 O, treated with hydrochloric acid) obtained in Example 1, the actual adsorption amount (●) and ammonium ion The amount of uptake (◯) was measured under the following conditions.
Weight of adsorbent = 0.25 g, volume of aqueous ammonium ion solution = 500 mL, concentration of ammonium ion = 9.0 mg / L, pH = 3.0. Sampling times are 2, 4, 6, 8, 24, 48 and 72 hours. The results are shown in FIG. The left side of the vertical axis in FIG. 4 shows the actual amount of adsorption relative to the theoretical amount, and the right side of the vertical axis shows the actual amount of ammonium ions taken up. As shown in FIG. 4, the adsorbent of the present invention exhibits sufficient adsorption of ammonium ions in a short time.
Example 3
For the ammonium ion adsorbent (HCa 2 Nb 3 O 10 × 1.5H 2 O, treated with hydrochloric acid) obtained in Example 1, the removal rate of ammonium ions was determined under the following conditions.
Weight of adsorbent = 0.05g, volume of aqueous ammonium ion solution = 100mL, pH = 3.0, contact time = 1 day. The initial concentration was 1,2,4,6,8,10,15,20,25 (mg-NH 4 + / L). The results are shown in FIG. As shown in FIG. 5, the adsorbent of the present invention can adsorb ammonium ions very effectively at a low concentration of 10 mg-NH 4 + / L or less.
Claims (5)
HCa2Ｎｂ3Ｏ10・ｎＨ2Ｏ （１）
（式中、ｎは、０≦ｎ≦４を満たす数である。）で表される化合物を有効成分とするアンモニウムイオン選択的吸着剤。 The following general formula (1):
HCa 2 Nb 3 O 10 · nH 2 O (1)
(In the formula, n is a number satisfying 0 ≦ n ≦ 4) An ammonium ion selective adsorbent containing a compound represented by the following formula as an active ingredient.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2006216730A JP5024749B2 (en) | 2006-08-09 | 2006-08-09 | Ammonium ion selective adsorbent |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2006216730A JP5024749B2 (en) | 2006-08-09 | 2006-08-09 | Ammonium ion selective adsorbent |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2008036573A true JP2008036573A (en) | 2008-02-21 |
| JP5024749B2 JP5024749B2 (en) | 2012-09-12 |
Family
ID=39172192
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2006216730A Expired - Fee Related JP5024749B2 (en) | 2006-08-09 | 2006-08-09 | Ammonium ion selective adsorbent |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP5024749B2 (en) |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH07275658A (en) * | 1994-04-08 | 1995-10-24 | Mitsubishi Heavy Ind Ltd | Ammonia adsorbing and decomposing method |
| JPH08132075A (en) * | 1994-11-10 | 1996-05-28 | Ishihara Sangyo Kaisha Ltd | Treatment of aqueous solution containing ammonia and/or ammonium ion |
| JP2003205236A (en) * | 2002-01-15 | 2003-07-22 | Japan Science & Technology Corp | Adsorbent comprising layered niobium oxide and hydrocarbon ammonium salt |
| JP2006021132A (en) * | 2004-07-08 | 2006-01-26 | National Institute Of Advanced Industrial & Technology | Ammonium ion adsorbent and ammonium ion removing method |
-
2006
- 2006-08-09 JP JP2006216730A patent/JP5024749B2/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH07275658A (en) * | 1994-04-08 | 1995-10-24 | Mitsubishi Heavy Ind Ltd | Ammonia adsorbing and decomposing method |
| JPH08132075A (en) * | 1994-11-10 | 1996-05-28 | Ishihara Sangyo Kaisha Ltd | Treatment of aqueous solution containing ammonia and/or ammonium ion |
| JP2003205236A (en) * | 2002-01-15 | 2003-07-22 | Japan Science & Technology Corp | Adsorbent comprising layered niobium oxide and hydrocarbon ammonium salt |
| JP2006021132A (en) * | 2004-07-08 | 2006-01-26 | National Institute Of Advanced Industrial & Technology | Ammonium ion adsorbent and ammonium ion removing method |
Also Published As
| Publication number | Publication date |
|---|---|
| JP5024749B2 (en) | 2012-09-12 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP4126399B2 (en) | Iron oxyhydroxide production method and iron oxyhydroxide adsorbent | |
| JP2013505832A (en) | Adsorbent to remove mercury from flue gas | |
| JP4681384B2 (en) | Arsenic adsorbent manufacturing method and arsenic adsorbent | |
| JP6644805B2 (en) | Anion adsorption method | |
| CN102874805A (en) | Method for preparing porous carbon for wastewater treatment | |
| JP2008505831A (en) | Purification method of nitrogen trifluoride gas using zeolite ion exchanged and impregnated with alkaline earth metal | |
| JP5024749B2 (en) | Ammonium ion selective adsorbent | |
| JP4674854B2 (en) | Wastewater treatment method | |
| JPH0657354B2 (en) | Simultaneous removal method of arsenic and silicon | |
| JP4469948B2 (en) | Ammonium ion adsorbent and method for removing ammonium ion | |
| JP2011200750A (en) | Method for removing halogen-based gas | |
| JP4617476B2 (en) | Method for removing potassium ions | |
| JP2008029985A (en) | Apparatus for regenerating anion adsorbent and method of regenerating anion adsorbent using the same | |
| JP3695845B2 (en) | Water purification material | |
| WO2020213281A1 (en) | Acidic exhaust gas treatment agent, acidic exhaust gas treatment method, and acidic exhaust gas treatment equipment | |
| JP4696017B2 (en) | Treatment method for boron-containing wastewater | |
| JP2007237169A (en) | Adsorbent for treating liquid phase and its manufacturing method | |
| JPWO2006080467A1 (en) | Hydrotalcite-like compound, bromide ion exchanger, and use thereof | |
| JP4072624B2 (en) | Specific alkali metal ion adsorbent and method for producing high purity lithium or high purity cesium | |
| KR101488237B1 (en) | Preparation Process of Dry Adsorbent for Selective Capture of Gaseous Carbon Dioxide | |
| AU2022250148B2 (en) | Lithium-containing solution production method | |
| KR101302597B1 (en) | Zeolite for removal the phosphorous of wastewater and fabricating method for the same | |
| JP2007253155A (en) | Sulfur compound adsorbent and its manufacturing method | |
| JP5279094B2 (en) | Wastewater treatment method | |
| JPH10305224A (en) | Cadmium adsorbent |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20090128 |
|
| A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20100825 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20120124 |
|
| A521 | Written amendment |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20120228 |
|
| TRDD | Decision of grant or rejection written | ||
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20120529 |
|
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20120611 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20150629 Year of fee payment: 3 |
|
| R150 | Certificate of patent or registration of utility model |
Ref document number: 5024749 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R150 Free format text: JAPANESE INTERMEDIATE CODE: R150 |
|
| S533 | Written request for registration of change of name |
Free format text: JAPANESE INTERMEDIATE CODE: R313533 |
|
| R350 | Written notification of registration of transfer |
Free format text: JAPANESE INTERMEDIATE CODE: R350 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| LAPS | Cancellation because of no payment of annual fees |