JPH05115777A - Adsorbent for fluorine ion - Google Patents
Adsorbent for fluorine ionInfo
- Publication number
- JPH05115777A JPH05115777A JP3313712A JP31371291A JPH05115777A JP H05115777 A JPH05115777 A JP H05115777A JP 3313712 A JP3313712 A JP 3313712A JP 31371291 A JP31371291 A JP 31371291A JP H05115777 A JPH05115777 A JP H05115777A
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- JP
- Japan
- Prior art keywords
- adsorbent
- fluorine
- resin
- ion exchange
- zirconium
- 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.)
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- Removal Of Specific Substances (AREA)
- Water Treatment By Sorption (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は，産業排水及び環境水に
含有するフツ素イオンを効率良く除去することのできる
フツ素イオン吸着剤に関するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a fluorine ion adsorbent capable of efficiently removing fluorine ions contained in industrial wastewater and environmental water.
【０００２】[0002]
【従来の技術】近年、わが国におけるフツ素使用量は年
々増加する傾向にあり、電子部品や金属加工分野で金属
表面処理及び洗浄用として多く利用されている。フツ素
含有水は人体、生物の生態系に異常を及ぼすことが知ら
れており、地域により飲料水で０．８ｐｐｍ以下、産業
排水では１〜１０ｐｐｍに規制されている。これらの産
業から排出されるフツ素含有廃液は通常Ｃａ塩による凝
集沈澱処理が行われる。しかし、凝集沈澱処理後のフツ
素濃度は１５ｐｐｍ前後と高く、規制値をクリヤーする
ためには、更に高度な処理を行う必要がある。2. Description of the Related Art In recent years, the amount of fluorine used in Japan tends to increase year by year, and it is widely used for metal surface treatment and cleaning in the field of electronic parts and metal processing. Fluorine-containing water is known to cause abnormalities in human and biological ecosystems, and drinking water regulates 0.8 ppm or less and industrial wastewater regulates 1 to 10 ppm depending on the region. The fluorine-containing waste liquid discharged from these industries is usually subjected to coagulation and precipitation treatment with Ca salt. However, the fluorine concentration after the coagulation-precipitation treatment is as high as around 15 ppm, and it is necessary to perform a more advanced treatment in order to clear the regulation value.
【０００３】この処理法として吸着剤を利用する方法が
提案されており、フツ素イオン吸着剤として、樹脂母体
に金属水和物を担持させたもの又はイオン交換樹脂に金
属を吸着させたものが良く用いられている。A method utilizing an adsorbent has been proposed as this treatment method. As a fluorine ion adsorbent, a resin matrix in which a metal hydrate is supported or an ion exchange resin in which a metal is adsorbed is used. It is often used.
【０００４】この中で、強酸性イオン交換樹脂にジルコ
ニウムイオンを吸着させ、ジルコニウムスルホネートと
したフツ素吸着剤が知られている。例えば、「分析化
学」Ｖｏｌ．２９、１０６〜１０９頁（１９８０）に記
載されている吸着剤は強酸性イオン交換樹脂に、ジルコ
ニウムを吸着せしめ環境水の低濃度フツ素イオンの濃縮
分析に利用されている。Among these, there is known a fluorine adsorbent which is made into zirconium sulfonate by adsorbing zirconium ions on a strongly acidic ion exchange resin. For example, “Analytical Chemistry” Vol. 29, pp. 106-109 (1980), the adsorbent is used for concentration analysis of low-concentration fluorine ions by adsorbing zirconium on a strongly acidic ion exchange resin.
【０００５】このジルコニウムスルホネートを吸着させ
た吸着剤は低濃度域のフツ素イオンを良く吸着し、分析
化学の分野では有効な手段である。しかし、産業排水或
いは環境水のフツ素を大量処理する場合、ランニングコ
スト、イニシヤルコストが問題となつてくる。The adsorbent which has adsorbed zirconium sulfonate adsorbs fluorine ions in a low concentration region well, and is an effective means in the field of analytical chemistry. However, when a large amount of fluorine is treated in industrial wastewater or environmental water, running cost and initial cost become problems.
【０００６】この吸着剤は、粒径が７０μｍ〜１５０μ
ｍと非常に小さく、大量処理を行う場合、通水抵抗（樹
脂塔内圧力損失）が大きいという問題があつた。また、
表面積が０．１ｍ2 未満のゲル型イオン交換樹脂を利用
しているため、吸着速度が遅く、高いＢＴＣ（カラム法
での破過点交換量）が得られないという問題があつた。This adsorbent has a particle size of 70 μm to 150 μm.
It is very small as m, and there is a problem that water resistance (pressure loss in the resin tower) is large when a large amount of treatment is performed. Also,
Since a gel-type ion exchange resin having a surface area of less than 0.1 m 2 is used, there is a problem that the adsorption rate is slow and a high BTC (breakthrough point exchange amount in the column method) cannot be obtained.
【０００７】さらに特開昭５１−９８６８８号公報に
は、カチオン交換樹脂（すなわち、強酸性イオン交換樹
脂）にトリウム、ジルコニウム、チタニウムなどの金属
イオンを吸着させたフツ素イオン吸着剤が開示されてい
る。Further, Japanese Unexamined Patent Publication (Kokai) No. 51-98688 discloses a fluorine ion adsorbent obtained by adsorbing a metal ion such as thorium, zirconium or titanium on a cation exchange resin (that is, a strongly acidic ion exchange resin). There is.
【０００８】しかしながら、この吸着剤は、カチオン交
換樹脂としてゲル型の樹脂を使用しているため、上記吸
着剤と同じように吸着速度が遅いという問題があつた。However, since this adsorbent uses a gel-type resin as the cation exchange resin, there is a problem that the adsorbing rate is slow like the above adsorbents.
【０００９】[0009]
【発明が解決しようとする課題】本発明は、このような
従来技術の欠点を解消し、吸着速度が速く、圧力損失の
小さいフツ素イオン吸着剤を提供することを目的とする
ものである。SUMMARY OF THE INVENTION An object of the present invention is to solve the above-mentioned drawbacks of the prior art and to provide a fluorine ion adsorbent having a high adsorption rate and a small pressure loss.
【００１０】[0010]
【課題を解決するための手段】本発明者らは、上述のご
とき課題を解決すべく鋭意検討を行つた結果、水中のフ
ツ素イオンを効率良く除去する吸着剤としてジルコニウ
ムスルホネート又はセリウムスルホネートをイオン交換
基として有し、かつ樹脂の粒径が２５０μｍ〜６５０μ
ｍで、比表面積が０．１ｍ2 ／ｇ以上である吸着剤が利
用でき、この吸着剤が吸着速度が速く、圧力損失の小さ
いフツ素イオン吸着剤であるを見出し、本発明に到達し
た。Means for Solving the Problems As a result of intensive studies to solve the above problems, the present inventors have found that zirconium sulfonate or cerium sulfonate can be used as an adsorbent for efficiently removing fluorine ions in water. It has an exchange group and the particle size of the resin is 250 μm to 650 μm
The inventors have found that an adsorbent having a specific surface area of 0.1 m 2 / g or more can be used, and that the adsorbent is a fluorine ion adsorbent having a high adsorption rate and a small pressure loss, and has reached the present invention.
【００１１】すなわち、本発明は、ジルコニウムスルホ
ネート及びセリウムスルホネートから選ばれる１種又は
２種のイオン交換基を有し、かつ粒径が２５０μｍ〜６
５０μｍで、比表面積が０．１ｍ2 ／ｇ以上有してなる
フツ素イオン吸着剤を要旨とするものである。That is, the present invention has one or two kinds of ion exchange groups selected from zirconium sulfonate and cerium sulfonate and has a particle size of 250 μm to 6 μm.
The gist is a fluorine ion adsorbent having a specific surface area of 50 m and a specific surface area of 0.1 m 2 / g or more.
【００１２】本発明の吸着剤は、ジルコニウムスルホネ
ート及びセリウムスルホネートから選ばれる１種又は２
種のイオン交換基を有しおり、このイオン交換基を得る
ためには、例えば、スルホン酸基を有する強酸性イオン
交換樹脂にジルコニウム溶液単独、セリウム溶液単独、
或いはジルコニウム、セリウム混合溶液を接触させるこ
とにより得られる。このとき、接触させる方法として
は、カラム式、バッチ式のどちらの方法でもよい。The adsorbent of the present invention is one or two selected from zirconium sulfonate and cerium sulfonate.
Having a kind of ion exchange group, in order to obtain this ion exchange group, for example, a zirconium solution alone to a strongly acidic ion exchange resin having a sulfonic acid group, cerium solution alone,
Alternatively, it can be obtained by contacting a mixed solution of zirconium and cerium. At this time, the method of contact may be either a column method or a batch method.
【００１３】また、このときのジルコニウム溶液、セリ
ウム溶液の濃度は特に限定されないが、低濃度で行うと
液量が多くなるとともに時間も要するので、１Ｍ程度の
溶液が好ましい。The concentration of the zirconium solution or the cerium solution at this time is not particularly limited, but if it is carried out at a low concentration, the liquid amount becomes large and it takes time, so a solution of about 1 M is preferable.
【００１４】本発明に用いられるスルホン酸基を有する
イオン交換樹脂としては、スルホン酸基を有するもので
あればアクリル系、フエノール系、スチレン系、ビニル
系、エポキシ系等いかなるものでもよいが、特にスチレ
ン系、フエノール系が好ましい。The ion exchange resin having a sulfonic acid group used in the present invention may be any one such as an acrylic resin, a phenol resin, a styrene resin, a vinyl resin or an epoxy resin as long as it has a sulfonic acid group. Styrene type and phenol type are preferable.
【００１５】また、スルホン酸基を有するイオン交換樹
脂の形状としては、不定形状、球状、針状等いかなる形
状でもよいが、操作面から見て特に球状が好ましい。こ
れらのスルホン酸基を有するイオン交換樹脂は数社から
市販されており、その市販品を利用すればよい。The ion exchange resin having a sulfonic acid group may have any shape such as an irregular shape, a spherical shape, or a needle shape, but a spherical shape is particularly preferable from the viewpoint of operation. Ion exchange resins having these sulfonic acid groups are commercially available from several companies, and the commercially available products may be used.
【００１６】本発明の吸着剤は、粒径が２５０μｍ〜６
５０μｍであることが必要である。粒径が２５０μｍ未
満になると、吸着速度が遅くなり、また、粒径が６５０
μｍを超えると、圧力損失が大きくなるので好ましくな
い。本発明における粒径が２５０μｍ〜６５０μｍと
は、湿式分級操作において、この範囲に入る粒子容積が
７０Vol ％以上有することをいう。The adsorbent of the present invention has a particle size of 250 μm to 6 μm.
It must be 50 μm. If the particle size is less than 250 μm, the adsorption rate becomes slower and the particle size becomes 650
If it exceeds μm, the pressure loss increases, which is not preferable. The particle size of 250 μm to 650 μm in the present invention means that the volume of particles falling within this range is 70 vol% or more in the wet classification operation.
【００１７】この湿式分級操作を行うには、まず、目開
き６５０μｍのフルイ及び２５０μｍのフルイと水を張
つたバツトを準備し、６５０μｍのフルイを半分程度水
につけ、樹脂１００ｍｌをフルイ中に入れ、上下及び回
転運動をフルイに与え小粒をバツト中に落とし、次にバ
ツト中の小粒を集め、２５０μｍのフルイで同様の操作
を行い、それぞれの体積を測ることによつて行うことが
できる。In order to carry out this wet classification operation, first, prepare a sieve with an opening of 650 μm and a sieve with a 250 μm sieve and a water-tight butt, soak the 650 μm sieve in about half of the water, and put 100 ml of resin in the sieve. Upward and downward and rotary motions are applied to the sieve to drop the small particles into the butt, then the small particles in the butt are collected, the same operation is performed with a 250 μm sieve, and each volume is measured.
【００１８】本発明の吸着剤は、比表面積が０．１ｍ2
／ｇ以上有していることが必要である。比表面積が０．
１ｍ2 ／ｇ未満、すなわち，ゲル型であると、吸着速度
が遅くなるので好ましくない。本発明において比表面積
を測定するには，例えば、ＢＥＴ法（測定装置ベルソー
プ２８、日本ベル株製）にて測定することができる。The adsorbent of the present invention has a specific surface area of 0.1 m 2.
/ G or more is necessary. Specific surface area is 0.
If it is less than 1 m 2 / g, that is, if it is a gel type, the adsorption rate becomes slow, which is not preferable. In the present invention, the specific surface area can be measured by, for example, the BET method (measuring device Bellthorpe 28, manufactured by Nippon Bell Co., Ltd.).
【００１９】本発明の吸着剤は、従来の吸着剤と同様に
フツ素含有水と接触させることによつて、フツ素イオン
を効率よく除去することができる。接触させる方法とし
ては、カラム式、バッチ式のどちらの方法でもよいが、
吸着速度が速いので、カラム式で行う方が有利である。The adsorbent of the present invention can efficiently remove fluorine ions by bringing it into contact with fluorine-containing water like conventional adsorbents. The method of contacting may be either a column method or a batch method,
Since the adsorption rate is high, it is advantageous to use the column method.
【００２０】本発明の吸着剤は、従来の吸着剤と同様に
アルカリ剤（水酸化ナトリウム、水酸化カリウム）でフ
ツ素イオンを溶離することができるとともに鉱酸（塩
酸、硫酸、硝酸）で再生して再使用することができる。The adsorbent of the present invention is capable of eluting fluorine ions with an alkaline agent (sodium hydroxide, potassium hydroxide) and regenerated with a mineral acid (hydrochloric acid, sulfuric acid, nitric acid) like conventional adsorbents. And can be reused.
【００２１】[0021]
次に、本発明を実施例により具体的に説明する。 実施例１ 市販スチレン系マクロポ−ラス型強酸性イオン交換樹脂
（架橋度８％、比表面積５ｍ2/ｇ、イオン交換量１．７
５ｍｅｑ／ｍｌ、末端Ｈ型）を水中で湿式分級操作を行
い、２５０μｍ〜６５０μｍの範囲８０％、６５０μｍ
以上２０％の樹脂を得た。この樹脂１リツトルを三角フ
ラスコにとり、その中にオキシ塩化ジルコニウム溶液
（Ｚｒ−１４０ｇ／ｌ）２リツトルを投入し、４８時間
攪拌を行つた。Next, the present invention will be specifically described with reference to examples. Example 1 Commercially available styrene-based macroporous type strongly acidic ion exchange resin (crosslinking degree 8%, specific surface area 5 m 2 / g, ion exchange amount 1.7)
5 meq / ml, terminal H type) is subjected to a wet classification operation in water to give a range of 250 μm to 650 μm 80%, 650 μm
Thus, 20% of resin was obtained. This resin (1 liter) was placed in an Erlenmeyer flask, and 2 liters of the zirconium oxychloride solution (Zr-140 g / l) was charged therein, and the mixture was stirred for 48 hours.
【００２２】攪拌した後、樹脂をイオン交換水で充分水
洗し、１Ｎ−ＮａＯＨ２リツトルを入れ、２時間攪拌
し、再度充分に水洗を行い、０．５Ｎ−ＨＣｌ３リツト
ルを入れ、２時間攪伴を続けた後、充分に水洗を行い、
ジルコニウムスルホネート樹脂（粒径が２５０μｍ〜６
５０μｍで、比表面積が４．６ｍ2/ｇの吸着剤）を得
た。After stirring, the resin was thoroughly washed with ion-exchanged water, 2 liters of 1N-NaOH was added, and the mixture was stirred for 2 hours, washed again with sufficient water, 3 liters of 0.5N-HCl was added, and the mixture was stirred for 2 hours. After continuing, wash thoroughly with water,
Zirconium sulfonate resin (particle size 250 μm-6
An adsorbent having a specific surface area of 50 μm and a specific surface area of 4.6 m 2 / g was obtained.
【００２３】実施例２ 市販スチレン系マクロポ−ラス型強酸性イオン交換樹脂
（架橋度１０％、比表面積３０ｍ2/ｇ、イオン交換量２
ｍｅｑ／ｍｌ、末端Ｈ型）を実施例１と同様に湿式分級
操作を行い、２５０μｍ〜６５０μｍ７０％、６５０μ
ｍ以上３０％の樹脂を得た。Example 2 Commercially available styrene-based macroporous type strongly acidic ion exchange resin (degree of crosslinking 10%, specific surface area 30 m 2 / g, ion exchange amount 2
meq / ml, terminal H type) was subjected to a wet classification operation in the same manner as in Example 1 to obtain 250 μm to 650 μm 70%, 650 μm
A resin of m or more and 30% was obtained.
【００２４】その樹脂１リツトルを直径１００ｍｍのカ
ラムに投入し、塩化セリウム溶液（ＣｅIV、４０ｇ／
ｌ）、オキシ塩化ジルコニウム溶液（Ｚｒ７０ｇ／ｌ）
の混合液３リツトルを空塔速度（ＳＶ）０．５(1/hr)に
てカラムに通液した。その後、イオン交換水５リツトル
を同じ通液速度で流し樹脂を水洗し、セリウム−ジルコ
ニウムスルホネート樹脂（粒径が２５０μｍ〜６５０μ
ｍで、比表面積が２９ｍ2/ｇの吸着剤）を得た。1 liter of the resin was put into a column having a diameter of 100 mm, and a cerium chloride solution (CeIV, 40 g /
l), zirconium oxychloride solution (Zr 70 g / l)
3 liters of the mixed solution of was passed through the column at a superficial velocity (SV) of 0.5 (1 / hr). Then, 5 liters of ion-exchanged water was flowed at the same flow rate to wash the resin with cerium-zirconium sulfonate resin (particle size: 250 μm to 650 μm).
m, an adsorbent having a specific surface area of 29 m 2 / g) was obtained.
【００２５】比較例１ 実施例１に用いたイオン交換樹脂（粒径６５０μｍ以上
７０％、６５０μｍ〜２５０μｍ３０％）を湿式分級操
作をせずにそのまま実施例１と同様に処理を行い、ジル
コニウムスルホネート樹脂（吸着剤）を得た。Comparative Example 1 The ion exchange resin (particle size 650 μm or more 70%, 650 μm to 250 μm 30%) used in Example 1 was treated in the same manner as in Example 1 without the wet classification operation, and the zirconium sulfonate resin was used. (Adsorbent) was obtained.
【００２６】比較例２ 市販スチレン系ゲル型強酸性イオン交換樹脂ダウエツク
ス５０ＷＸ−８（架橋度８％、粒径７０μｍ〜１５０μ
ｍ、比表面積０ｍ2/ｇ、ダウケミカル社製）を、そのま
ま実施例１と同様に処理してジルコニウムスルホネート
樹脂（吸着剤）を得た。Comparative Example 2 Commercially available styrene gel type strong acid ion exchange resin Dowex 50WX-8 (crosslinking degree 8%, particle size 70 μm to 150 μm)
m, a specific surface area of 0 m 2 / g, manufactured by Dow Chemical Co., Ltd.) was directly treated in the same manner as in Example 1 to obtain a zirconium sulfonate resin (adsorbent).
【００２７】吸着剤の性能実験 上記の吸着剤（実施例１〜２及び比較例１〜２）を次の
ような性能実験をした。Performance Experiment of Adsorbent The above-mentioned adsorbents (Examples 1-2 and Comparative Examples 1-2) were subjected to the following performance experiments.
【００２８】（１）バツチ式フツ素吸着量 上記の吸着剤（実施例１〜２及び比較例１〜２）１ｍｌ
にフツ素濃度１９０ｍｇ／ｌ、ｐＨ＝３．５の溶液１０
０ｍｌを投入し、２４時間攪拌して吸着させた後の残液
フツ素濃度より静的フツ素吸着量を求めた。その結果を
表１に示す。(1) Batch type fluorine adsorption amount: 1 ml of the above-mentioned adsorbent (Examples 1-2 and Comparative Examples 1-2)
Solution with a fluorine concentration of 190 mg / l and pH = 3.5
The static fluorine adsorption amount was determined from the residual liquid fluorine concentration after the addition of 0 ml and stirring for 24 hours for adsorption. The results are shown in Table 1.
【００２９】[0029]
【表１】 [Table 1]
【００３０】（２）カラム式フツ素吸着量 上記の吸着剤（実施例１〜２及び比較例１〜２）１０ｍ
ｌを直径７ｍｍのカラムに充填し、フツ素濃度１５ｍｇ
／ｌ、 ＮａＣｌ１ｇ／ｌ、ｐＨ＝３．５に調製された
溶液を空塔速度（ＳＶ＝７1/hr）、下向流で通液し、樹
脂通過液のフツ素濃度が０．８ｐｐｍ点でのカラム吸着
量（ ０．８ｐｐｍＢＴＣ）を求めた。その結果を表２
に示す。(2) Column type fluorine adsorption amount 10 m of the above adsorbent (Examples 1 and 2 and Comparative Examples 1 and 2)
1 was packed in a column with a diameter of 7 mm and the concentration of fluorine was 15 mg.
/ L, NaCl 1 g / l, pH = 3.5, the solution was passed at a superficial velocity (SV = 71 / hr) at a downward flow, and the fluorine concentration of the resin passing liquid was 0.8 ppm. Column adsorption amount (0.8 ppm BTC) was determined. The results are shown in Table 2.
Shown in.
【００３１】[0031]
【表２】 [Table 2]
【００３２】表１及び表２から明らかなように、実施例
１及び２の吸着剤は、０．８ｐｐｍＢＴＣが比較例１及
び２の吸着剤と比べて非常に高い。比較例１及び２の吸
着剤は、静的フツ素吸着量が実施例１及び２の吸着剤と
ほぼ同等であるにもかかわらず、工業的に重要な０．８
ｐｐｍＢＴＣは、極めて低い。このことから、本発明の
吸着剤は、吸着速度が速くフツ素吸着剤として工業的に
利用可能なことが判る。As is clear from Tables 1 and 2, the adsorbents of Examples 1 and 2 have a much higher 0.8 ppm BTC than the adsorbents of Comparative Examples 1 and 2. The adsorbents of Comparative Examples 1 and 2 have an industrially important 0.8% although the static fluorine adsorption amount is almost the same as that of the adsorbents of Examples 1 and 2.
The ppm BTC is extremely low. From this, it is understood that the adsorbent of the present invention has a high adsorption rate and can be industrially used as a fluorine adsorbent.
【００３３】（３）圧力損失の測定 上記の吸着剤（実施例１〜２及び比較例１〜２）１リツ
トルを直径７８ｍｍのカラムに充填し、定量ポンプを用
い２５℃に調整されたイオン交換水を下向流で流し、線
速度（ＬＶ）を変化させ、水柱にて圧力損失を測定し
た。その結果を図１に示す。図１は、圧力損失と線速度
との関係を示した図であり、縦軸に樹脂（吸着剤）高１
ｍ当りの圧力損失（水柱で表す）を、横軸に線速度（Ｌ
Ｖ）を示しており、図中の１は実施例１及び２を、図中
の２は比較例１を、図中の３は比較例２を、それぞれ示
している。(3) Measurement of pressure loss A column having a diameter of 78 mm was packed with 1 liter of the adsorbent (Examples 1 and 2 and Comparative Examples 1 and 2), and ion exchange was performed at 25 ° C. using a metering pump. Water was made to flow in a downward flow, the linear velocity (LV) was changed, and the pressure loss was measured in a water column. The result is shown in FIG. FIG. 1 is a diagram showing the relationship between the pressure loss and the linear velocity, where the vertical axis indicates the resin (adsorbent) height 1
The pressure loss per m (represented by a water column) is plotted on the horizontal axis as the linear velocity (L
V) is shown, 1 in the figure shows Examples 1 and 2, 2 in the figure shows Comparative Example 1, and 3 in the figure shows Comparative Example 2.
【００３４】（４）逆洗展開率の測定 上記の圧力損失の測定と同様の装置を用い、２５℃に調
整されたイオン交換水を上向流で流し、線速度（ＬＶ）
を変化させ、展開樹脂（吸着剤）体積を測定して逆洗展
開率を求めた。その結果を図２に示す。図２は、逆洗展
開率と線速度との関係を示した図であり、縦軸に逆洗展
開率を、横軸に線速度（ＬＶ）を示しており、図中の１
は実施例１及び２を、図中の２は比較例１を、図中の３
は比較例２を、それぞれ示している。(4) Measurement of backwash expansion rate Using the same device as the above pressure loss measurement, ion-exchanged water adjusted to 25 ° C. was caused to flow in an upward flow to obtain a linear velocity (LV).
Was varied and the volume of developed resin (adsorbent) was measured to determine the backwash development rate. The result is shown in FIG. FIG. 2 is a diagram showing the relationship between the backwash development rate and the linear velocity, where the vertical axis shows the backwash development rate and the horizontal axis shows the linear velocity (LV).
Indicates Examples 1 and 2, 2 in the figure represents Comparative Example 1, and 3 in the figure
Shows Comparative Example 2, respectively.
【００３５】図１及び図２に示すように、比較例２の吸
着剤は、圧力損失、逆流展開率が高く、工業的に使用が
困難であるのに対し、実施例１及び２の吸着剤は、工業
的に使用可能である。また、比較例１の吸着剤は、圧力
損失、逆流展開率は問題ないが、前述したようにＢＴＣ
吸着量が低く工業的な利用は困難である。As shown in FIGS. 1 and 2, the adsorbent of Comparative Example 2 has a high pressure loss and a high backflow expansion rate and is industrially difficult to use, whereas the adsorbents of Examples 1 and 2 are difficult to use. Are industrially usable. In addition, the adsorbent of Comparative Example 1 has no problem in pressure loss and backflow expansion rate, but as described above, BTC
The amount of adsorption is low and industrial use is difficult.
【００３６】[0036]
【発明の効果】本発明の吸着剤は、吸着速度が速く、圧
力損失が小さいため、フツ素イオン含有水中のフツ素イ
オンを経済的に効率良く除去することができるとともに
大容量のフツ素イオン含有水を速やかに処理することが
できる。Since the adsorbent of the present invention has a high adsorption rate and a small pressure loss, it can economically and efficiently remove fluorine ions in water containing fluorine ions and has a large capacity. The contained water can be treated promptly.
【図１】本発明の吸着剤における圧力損失と線速度との
関係を示した図である。FIG. 1 is a diagram showing a relationship between pressure loss and linear velocity in an adsorbent of the present invention.
【図２】本発明の吸着剤における逆洗展開率と線速度と
の関係を示した図である。FIG. 2 is a diagram showing a relationship between a backwash development rate and a linear velocity in the adsorbent of the present invention.
１ 実施例１及び２ ２ 比較例１ ３ 比較例２ 1 Examples 1 and 2 2 Comparative example 1 3 Comparative example 2
フロントページの続き (72)発明者 越後 良彰 京都府宇治市宇治小桜23番地 ユニチカ株 式会社中央研究所内Front page continuation (72) Inventor Yoshiaki Echigo 23 Uji Kozakura, Uji City, Kyoto Prefecture Unitika Ltd. Central Research Laboratory
Claims (1)
スルホネートから選ばれる１種又は２種のイオン交換基
を有し、かつ粒径が２５０μｍ〜６５０μｍで、比表面
積が０．１ｍ2 ／ｇ以上有してなるフツ素イオン吸着
剤。1. A foot having one or two ion-exchange groups selected from zirconium sulfonate and cerium sulfonate, having a particle size of 250 μm to 650 μm, and having a specific surface area of 0.1 m 2 / g or more. Elemental ion adsorbent.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP31371291A JP2653591B2 (en) | 1991-10-30 | 1991-10-30 | Fluoride ion adsorbent |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP31371291A JP2653591B2 (en) | 1991-10-30 | 1991-10-30 | Fluoride ion adsorbent |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH05115777A true JPH05115777A (en) | 1993-05-14 |
| JP2653591B2 JP2653591B2 (en) | 1997-09-17 |
Family
ID=18044611
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP31371291A Expired - Lifetime JP2653591B2 (en) | 1991-10-30 | 1991-10-30 | Fluoride ion adsorbent |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2653591B2 (en) |
-
1991
- 1991-10-30 JP JP31371291A patent/JP2653591B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JP2653591B2 (en) | 1997-09-17 |
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