JP6047880B2 - Ion exchange membrane filling method - Google Patents
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Description
本発明は、イオン交換膜の利用方法、詳しくはイオン交換膜を固定床に充填して利用する際、イオン交換膜の圧密化を防止できる充填方法に関する。 The present invention relates to a method for using an ion exchange membrane, and more particularly to a filling method that can prevent the ion exchange membrane from being consolidated when the ion exchange membrane is used by filling a fixed bed.
イオン交換膜は、化学工業、鉄鋼、機械、自動車、電気・電子工業、医薬、農薬など、様々な産業における水処理分野で利用され、特に、電気透析やイオン交換膜法食塩電解などの隔膜としての使用量は多い。近年、電気自動車の燃料電池の隔膜材料等としてフッ素系イオン交換膜の研究開発が進められており、今後その使用量の大幅な伸びが予想されている。 Ion exchange membranes are used in water treatment fields in various industries such as chemical industry, steel, machinery, automobiles, electrical / electronic industry, medicine, agricultural chemicals, etc., especially as diaphragms for electrodialysis and salt exchange electrolysis using ion exchange membrane method. The amount of use is large. In recent years, research and development of fluorine-based ion exchange membranes have been promoted as a membrane material for fuel cells of electric vehicles, and the use amount is expected to increase significantly in the future.
さらなる用途拡大のため、シート状のイオン交換膜をロール状に成形して固定床に充填し、イオン交換基を利用する方法が考えられる。しかしながら、イオン交換膜の厚みは薄く、その強度が弱いため、固定床に充填すると膜同士が重なったり、固定床の底部で液流れを塞いだりすることがあるため、実用化には至っていない。 In order to further expand the applications, a method of forming a sheet-like ion exchange membrane into a roll shape, filling the fixed bed, and utilizing ion exchange groups can be considered. However, since the thickness of the ion exchange membrane is thin and its strength is weak, if the fixed bed is filled, the membranes may overlap each other or the liquid flow may be blocked at the bottom of the fixed bed, so that it has not been put into practical use.
別法として、イオン交換膜を裁断して、固定床に充填して利用する方法が考えられる。その場合、イオン交換膜は厚みが薄く、強度が弱いため、イオン交換膜のみを充填するとイオン交換膜が圧密化し、液抵抗がアップし、さらに進むと液が流れなくなるため、実用化が困難であった。その対策として、イオン交換膜に過酸化ニッケルを担持した触媒を例として、イオン交換膜をポールリング充填物に絡めて固定化し、流出するイオン交換膜は、デミスターで捕捉する方法が開示されている（例えば、特許文献１参照）。この方法によりイオン交換膜を担体とした触媒を固定化できるものの、この方法で長期間使用すると、ゆっくりではあるが触媒がポールリング充填物から分離し、触媒の偏析が生じ、圧密化が起こり始めるといった課題を抱えていた。 As another method, a method of cutting an ion exchange membrane and filling a fixed bed for use can be considered. In that case, since the ion exchange membrane is thin and weak in strength, if only the ion exchange membrane is filled, the ion exchange membrane becomes consolidated, the liquid resistance increases, and the liquid does not flow when further progressing. there were. As a countermeasure, a method in which a nickel peroxide is supported on an ion exchange membrane is used as an example, and the ion exchange membrane is entangled with a pole ring filler and fixed, and the outflowing ion exchange membrane is captured by a demister. (For example, refer to Patent Document 1). Although this method can immobilize a catalyst using an ion exchange membrane as a carrier, when used in this method for a long period of time, the catalyst is slowly separated from the pole ring packing, causing segregation of the catalyst, and consolidation begins to occur. There was a problem such as.
これらイオン交換膜は、その製造工程から端材が発生したり、あるいは使用中に破損したり、さらには長期間使用し、イオン交換基が残存した使用済みの膜として大量に廃棄されている（これらを総称して「廃イオン交換膜」という）。通常、廃イオン交換膜が、炭化水素系であれば焼却処分される。また、フッ素系イオン交換膜であれば、焼却するとフッ化水素ガスが発生し、焼却炉の炉材を劣化させたり、環境への負荷が大きいため、埋め立て処分される。しかしながら、いずれのイオン交換膜も高価なものであり、経済面から、そして資源の有効利用といった側面から、再利用できる技術の開発が望まれていた。 These ion exchange membranes have scraps generated from the manufacturing process, or are broken during use, and are used for a long time, and are discarded in large quantities as used membranes in which ion exchange groups remain ( These are collectively referred to as “waste ion exchange membranes”). Usually, if the waste ion exchange membrane is hydrocarbon-based, it is incinerated. In addition, in the case of a fluorine-based ion exchange membrane, when incinerated, hydrogen fluoride gas is generated, which deteriorates the furnace material of the incinerator and places a large burden on the environment. However, all of the ion exchange membranes are expensive, and it has been desired to develop a reusable technique from the viewpoints of economy and effective use of resources.
本発明は、前記従来法の種々の問題点を解決できる、効果的、効率的なイオン交換膜の充填方法、即ち、イオン交換膜を簡便な方法で、固定床に充填して利用できる方法を提供することにある。 The present invention provides an effective and efficient method of filling an ion exchange membrane that can solve various problems of the conventional method, that is, a method that can be used by filling an ion exchange membrane into a fixed bed by a simple method. It is to provide.
本発明者らは、イオン交換膜を固定床に充填する方法について鋭意検討した結果、イオン交換膜を適切なサイズに裁断した後、デミスターに絡め、固定床に充填することで、イオン交換膜のイオン交換基を有効に利用できることを見出し、本発明を完成するに至った。 As a result of earnestly examining the method for filling the fixed bed with the ion exchange membrane, the inventors cut the ion exchange membrane to an appropriate size, entangled with the demister, and filled the fixed bed, The present inventors have found that ion exchange groups can be used effectively and have completed the present invention.
即ち本発明は、
［１］イオン交換膜を固定床に充填して利用する方法において、イオン交換膜を１〜２０ｍｍの大きさに裁断した後、デミスターに絡めて充填することを特徴とするイオン交換膜の充填方法。
That is, the present invention
[1] A method of filling an ion exchange membrane in a fixed bed, wherein the ion exchange membrane is cut into a size of 1 to 20 mm and then entangled with a demister and filled. .
［２］イオン交換膜が、廃イオン交換膜であることを特徴とする［１］に記載のイオン交換膜の充填方法。 [2] The ion exchange membrane filling method according to [1], wherein the ion exchange membrane is a waste ion exchange membrane.
［３］イオン交換膜のイオン交換容量が０．３ｍｅｑ／ｇ以上であることを特徴とする［１］または［２］に記載のイオン交換膜の充填方法。 [3] The ion exchange membrane filling method according to [1] or [2], wherein the ion exchange capacity of the ion exchange membrane is 0.3 meq / g or more.
［４］イオン交換膜がフッ素系高分子陽イオン交換膜であることを特徴とする［１］〜［３］に記載のイオン交換膜の充填方法。 [4] The ion exchange membrane filling method according to any one of [1] to [3], wherein the ion exchange membrane is a fluorine-based polymer cation exchange membrane.
［５］イオン交換膜にマンガン、周期表１Ｂ族元素および周期表８族元素から選ばれる少なくとも１種の金属酸化物類が担持されていることを特徴とする［１］〜［４］に記載のイオン交換膜の充填方法。
に関するものである。
[5] At least one metal oxide selected from manganese, periodic table group 1B element and periodic table group 8 element is supported on the ion exchange membrane. Filling method of ion exchange membrane.
It is about.
以下、本発明について詳細に説明する。 Hereinafter, the present invention will be described in detail.
本発明の方法に用いるイオン交換膜は、イオン交換基が残存したシート状のものであれば特に限定されない。また、イオン交換膜の種類は、炭化水素系、フッ素系のいずれでも良いが、耐久性などの面からフッ素系イオン交換膜が好ましい。イオン交換膜が、例えば、食塩電解の隔膜や電気透析に使用された後の廃イオン交換膜である場合、不純物で汚染されていることがあるが、不純物は酸やアルカリで洗浄除去後に裁断しても、裁断後に洗浄除去しても構わない。好ましくは、裁断する前に水洗し、裁断した後、酸やアルカリで洗浄する方法である。イオン交換膜は、１〜２０ｍｍの大きさに裁断することを必須とする。１ｍｍよりも小さいと裁断するのに多大な労力が必要なばかりか、イオン交換膜をデミスターに絡めて充填する際、充分に固定化できないことがある。一方、２０ｍｍよりも大きいと膜同士が重なり合って、イオン交換性能が充分に発揮できなくなる。より好ましい裁断幅は２〜２０ｍｍである。裁断する装置は特に限定されない。具体的には、カッター、ハサミ、シュレッダー、シートカッターなどを例示することができる。裁断した後の形状についても特に限定されない。裁断のし易さから、好ましい形状は正方形もしくは長方形である。イオン交換基の濃度は特に限定されないが、濃度が高いほどイオン交換性能を高めることができる。好ましくは０．３ｍｅｑ／ｇ以上であり、より好ましくは０．５ｍｅｑ／ｇ以上である。イオン交換膜は、陽イオン交換膜でも陰イオン交換膜でも、また、両性イオン交換膜であっても良く、イオン交換基の種類も特に限定されない。イオン交換膜は、イオン交換膜単独であっても、イオン交換膜に金属酸化物を担持した複合体であっても構わない。好ましくは、フッ素系高分子陽イオン交換膜に金属酸化物を担持した複合体である。イオン交換膜は裁断した後、デミスターに絡めて充填するが、デミスターの材質は、イオン交換膜を絡めることができれば特に限定されない。強度や耐食性などの面から、好ましい材質は、フッ素樹脂、ポリエチレン、ポリプロピレン、チタン、ステンレスである。また、デミスターの種類は、通常市販されているものであれば特に限定されない。イオン交換膜とデミスターを絡める際、イオン交換膜とデミスターとの比率は、イオン交換膜がデミスターで良く固定化できる比率であれば特に限定されない。イオン交換性能をより発揮できることから、イオン交換膜とデミスターとの重量比は１０対１〜１０対３の範囲が好ましい。イオン交換膜をデミスターで絡めた後、デミスターは適切な大きさに成形し、固定床に充填される。固定床に充填する際、イオン交換膜の充填濃度は特に限定されない。充填濃度が高いほどイオン交換性能をアップさせることができるため好ましいが、高すぎると液抵抗が大きくなり、設備の耐圧性やポンプの揚程（ヘッド）が必要となるなど、設備コストがアップすることがある。イオン交換膜の充填濃度は、１５０〜５００ｇ／Ｌが好ましく、より好ましくは２００〜４００ｇ／Ｌである。 The ion exchange membrane used in the method of the present invention is not particularly limited as long as it is in a sheet form in which ion exchange groups remain. The type of ion exchange membrane may be either hydrocarbon or fluorine, but a fluorine ion exchange membrane is preferred from the standpoint of durability. If the ion exchange membrane is, for example, a salt electrolysis membrane or a waste ion exchange membrane after being used for electrodialysis, it may be contaminated with impurities, but the impurities are cut after washing with acid or alkali. Alternatively, it may be removed by washing after cutting. Preferably, it is a method of washing with water before cutting, and then washing with acid or alkali after cutting. The ion exchange membrane must be cut into a size of 1 to 20 mm. If it is smaller than 1 mm, not only a great amount of labor is required for cutting, but also when the ion exchange membrane is entangled with the demister and filled, it may not be sufficiently fixed. On the other hand, when it is larger than 20 mm, the membranes overlap each other, and the ion exchange performance cannot be sufficiently exhibited. A more preferable cutting width is 2 to 20 mm. The apparatus for cutting is not particularly limited. Specifically, a cutter, scissors, a shredder, a sheet cutter, etc. can be illustrated. The shape after cutting is not particularly limited. In view of ease of cutting, the preferred shape is a square or a rectangle. The concentration of the ion exchange group is not particularly limited, but the higher the concentration, the higher the ion exchange performance. Preferably it is 0.3 meq / g or more, More preferably, it is 0.5 meq / g or more. The ion exchange membrane may be a cation exchange membrane, an anion exchange membrane, or an amphoteric ion exchange membrane, and the type of ion exchange group is not particularly limited. The ion exchange membrane may be an ion exchange membrane alone or a complex in which a metal oxide is supported on the ion exchange membrane. Preferably, it is a composite in which a metal oxide is supported on a fluorine-based polymer cation exchange membrane. The ion exchange membrane is cut and then entangled with the demister and filled, but the material of the demister is not particularly limited as long as the ion exchange membrane can be entangled. From the viewpoint of strength and corrosion resistance, preferred materials are fluororesin, polyethylene, polypropylene, titanium, and stainless steel. Moreover, the kind of demister will not be specifically limited if it is normally marketed. When the ion exchange membrane and the demister are entangled, the ratio of the ion exchange membrane to the demister is not particularly limited as long as the ion exchange membrane can be well immobilized by the demister. Since the ion exchange performance can be further exhibited, the weight ratio of the ion exchange membrane to the demister is preferably in the range of 10: 1 to 10: 3. After the ion exchange membrane is entangled with a demister, the demister is formed into an appropriate size and filled into a fixed bed. When filling the fixed bed, the filling concentration of the ion exchange membrane is not particularly limited. Higher packing concentration is preferable because ion exchange performance can be improved. However, if the concentration is too high, liquid resistance increases, equipment pressure resistance and pump head (head) are required, and equipment costs increase. There is. The filling concentration of the ion exchange membrane is preferably 150 to 500 g / L, more preferably 200 to 400 g / L.
このように、固定床に充填されたイオン交換膜は、イオン交換性能を利用して超純水の製造や、廃水の脱塩や、水溶液からのカチオン成分、アニオン成分の除去などの用途に使用することができる。また、イオン交換基を利用して固体酸触媒としても利用することができる。さらには、イオン交換膜に金属酸化物を担持した複合体の場合、次亜塩素酸塩の分解触媒や、次亜塩素酸塩によるＣＯＤ成分（化学的酸素要求量）を除去する触媒として利用することができる。 In this way, ion exchange membranes packed in a fixed bed are used for applications such as ultrapure water production, wastewater desalination, and removal of cation and anion components from aqueous solutions using ion exchange performance. can do. Moreover, it can utilize also as a solid acid catalyst using an ion exchange group. Furthermore, in the case of a composite having a metal oxide supported on an ion exchange membrane, it is used as a catalyst for decomposing hypochlorite and a catalyst for removing COD components (chemical oxygen demand) due to hypochlorite. be able to.
金属酸化物としては、二酸化マンガン、酸化銅、酸化銀、酸化鉄、酸化コバルト、酸化ニッケル等を挙げることができる。 Examples of the metal oxide include manganese dioxide, copper oxide, silver oxide, iron oxide, cobalt oxide, nickel oxide and the like.
本発明の方法によれば、以下のような効果が達成される。 According to the method of the present invention, the following effects are achieved.
・これまで不可能であったシート状のイオン交換膜を固定床に充填して、イオン交換基を利用できる。 -It is possible to use ion exchange groups by filling a fixed bed with a sheet-like ion exchange membrane that has been impossible until now.
・イオン交換樹脂の代わりに廃イオン交換膜を使用することで、イオン交換体のコストを大幅に削減できる。 -The cost of ion exchangers can be greatly reduced by using waste ion exchange membranes instead of ion exchange resins.
・廃イオン交換膜をリサイクル利用することで、資源の有効活用ができる。 -Resources can be effectively used by recycling waste ion exchange membranes.
・廃棄物量の削減、焼却処理コストの低減、環境負荷の低減につながる。 ・ Reducing waste, reducing incineration costs, and reducing environmental impact.
・廃イオン交換膜の埋め立て処分場の確保が不要となる。 -It is not necessary to secure a landfill site for waste ion exchange membranes.
・簡易な方法で廃イオン交換膜を再利用できるので、廃イオン交換膜の発生源でも容易に実施できる。 -Since the waste ion exchange membrane can be reused by a simple method, it can be easily implemented even at the source of the waste ion exchange membrane.
以下、本発明を実施例により説明するが、本発明はこれら実施例にのみ限定されるものではない。 EXAMPLES Hereinafter, although an Example demonstrates this invention, this invention is not limited only to these Examples.
なお、本発明におけるイオン交換膜中の総イオン交換容量（ｍｅｑ／ｇ）とは、イオン交換膜を１１０℃で４時間乾燥させて求めたイオン交換膜の乾燥重量に対する、イオン交換基の濃度のことである。 The total ion exchange capacity (meq / g) in the ion exchange membrane in the present invention is the concentration of ion exchange groups relative to the dry weight of the ion exchange membrane obtained by drying the ion exchange membrane at 110 ° C. for 4 hours. That is.
実施例１
イオン交換膜法食塩電解の隔膜として使用できるフッ素系イオン交換膜Ｎａｆｉｏｎ９６１（デュポン社製）の総イオン交換容量は０．９ｍｅｑ／ｇであった。これをカッターで５ｍｍ×５ｍｍにカッティングし、５ｗｔ％塩酸水溶液中に一昼夜浸漬した。次に、純水にて塩酸を洗い流し、自然乾燥した。イオン交換膜は乾燥重量で８．５ｋｇであり、これをフッ素樹脂製の巻きタイプのデミスター（後藤商事（株）製）１．５ｋｇを広げた上に分散させ、デミスターをロール状に巻いて、イオン交換膜を絡めて成形した。このロールを内径３００ｍｍ、高さ４００ｍｍの固定床に充填し、超純水製造装置の陽イオン交換樹脂塔の代わりに用いた。固定床下部からＮａイオン濃度７ｍｇ／Ｌの水道水を１５Ｌ／時間の速度で通液し、イオン交換処理を実施した。その結果、１日後の処理水中のＮａイオン濃度は、０．１ｍｇ／Ｌの検出下限以下と良好な結果が得られた。３１日間に亘って、水道水の処理を継続したところ、イオン交換膜は圧密化することなく、安定した連続処理が可能で、処理水中のＮａイオン濃度は、検出下限以下で良好であった。
Example 1
The total ion exchange capacity of a fluorine-based ion exchange membrane Nafion 961 (manufactured by DuPont) that can be used as a diaphragm for salt electrolysis with an ion exchange membrane method was 0.9 meq / g. This was cut to 5 mm × 5 mm with a cutter, and immersed in a 5 wt% hydrochloric acid aqueous solution all day and night. Next, hydrochloric acid was washed away with pure water and air dried. The ion exchange membrane has a dry weight of 8.5 kg, and this is dispersed on a fluorine resin wound type demister (Goto Shoji Co., Ltd.) 1.5 kg spread, and the demister is wound into a roll, Molded with an ion exchange membrane. This roll was filled in a fixed bed having an inner diameter of 300 mm and a height of 400 mm, and used instead of the cation exchange resin tower of the ultrapure water production apparatus. Ion exchange treatment was carried out by passing tap water having a Na ion concentration of 7 mg / L from the lower part of the fixed bed at a rate of 15 L / hour. As a result, the Na ion concentration in the treated water after 1 day was less than the detection lower limit of 0.1 mg / L, and good results were obtained. When the treatment of tap water was continued for 31 days, the ion exchange membrane could be stably treated without being consolidated, and the Na ion concentration in the treated water was good below the lower limit of detection.
実施例２
イオン交換膜法食塩電解の隔膜として使用したフッ素系廃イオン交換膜Ｎａｆｉｏｎ９６１（デュポン社製）の総イオン交換容量は０．８ｍｅｑ／ｇであった。これをカッターで５ｍｍ×５ｍｍにカッティングし、５ｗｔ％塩酸水溶液中に一昼夜浸漬し、沈着物を洗浄除去した。次に、純水にて塩酸を洗い流し、自然乾燥した。廃イオン交換膜は乾燥重量で８．５ｋｇであり、これをフッ素樹脂製の巻きタイプのデミスター（後藤商事（株）製）１．５ｋｇを広げた上に分散させ、デミスターをロール状に巻いて、廃イオン交換膜を絡めて成形した。このロールを内径３００ｍｍ、高さ４００ｍｍの固定床に充填し、超純水製造装置の陽イオン交換樹脂塔の代わりに用いた。固定床下部からＮａイオン濃度７ｍｇ／Ｌの水道水を１５Ｌ／時間の速度で通液し、イオン交換処理を実施した。その結果、１日後の処理水中のＮａイオン濃度は、０．１ｍｇ／Ｌの検出下限以下と良好な結果が得られた。３１日間に亘って、水道水の処理を継続したところ、廃イオン交換膜は圧密化することなく、安定した連続処理が可能で、処理水中のＮａイオン濃度は、検出下限以下で良好であった。
Example 2
Ion exchange membrane method The total ion exchange capacity of the fluorine-based waste ion exchange membrane Nafion 961 (manufactured by DuPont) used as a diaphragm for salt electrolysis was 0.8 meq / g. This was cut to 5 mm × 5 mm with a cutter and immersed in a 5 wt% hydrochloric acid aqueous solution for a whole day and night to remove the deposits. Next, hydrochloric acid was washed away with pure water and air dried. The waste ion exchange membrane has a dry weight of 8.5 kg, and this is spread on a fluorinated resin wound type demister (produced by Goto Shoji Co., Ltd.) 1.5 kg. Then, it was formed by entanglement with a waste ion exchange membrane. This roll was filled in a fixed bed having an inner diameter of 300 mm and a height of 400 mm, and used instead of the cation exchange resin tower of the ultrapure water production apparatus. Ion exchange treatment was carried out by passing tap water having a Na ion concentration of 7 mg / L from the lower part of the fixed bed at a rate of 15 L / hour. As a result, the Na ion concentration in the treated water after 1 day was less than the detection lower limit of 0.1 mg / L, and a good result was obtained. When the treatment of tap water was continued for 31 days, the waste ion exchange membrane could be stably treated without being consolidated, and the Na ion concentration in the treated water was good below the lower limit of detection. .
実施例３
イオン交換膜法食塩電解の隔膜として使用したフッ素系廃高分子陽イオン交換膜Ｎａｆｉｏｎ９５４（デュポン社製）をよく洗浄した後、１０ｍｍ×１０ｍｍの大きさに切断した。廃イオン交換膜の総イオン交換容量は、０．７５ｍｅｑ／ｇであった。
Example 3
Ion exchange membrane method Fluorine-based waste polymer cation exchange membrane Nafion 954 (manufactured by DuPont) used as a diaphragm for salt electrolysis was thoroughly washed and then cut into a size of 10 mm x 10 mm. The total ion exchange capacity of the waste ion exchange membrane was 0.75 meq / g.
２Ｌビーカーに、ＮｉＣｌ２（２ｍｏｌ／Ｌ）水溶液１．５Ｌおよび上記の切断したフッ素系廃高分子陽イオン交換膜３００ｇ（湿潤状態）を入れ、１時間攪拌しながらイオン交換処理を行った。次に、溶液を抜き出し、新たにＮｉＣｌ２（２ｍｏｌ／Ｌ）水溶液１．５Ｌを入れ、同様に１時間処理し、溶液を抜き出した。 A 2 L beaker was charged with 1.5 L of a NiCl 2 (2 mol / L) aqueous solution and 300 g (wet state) of the cut fluorine-based waste polymer cation exchange membrane, and an ion exchange treatment was performed while stirring for 1 hour. Next, the solution was extracted, and 1.5 L of a NiCl 2 (2 mol / L) aqueous solution was newly added, and similarly treated for 1 hour, and the solution was extracted.
次に、３．０ｗｔ％ＮａＣｌＯ水溶液（ｐＨ１０）１．５Ｌを入れた２Ｌビーカーに、イオン交換処理した前記イオン交換膜を全量入れたところ、ニッケルイオンは黒色の酸化物となった。フッ素系高分子陽イオン交換体の乾燥重量に対するニッケルの担持量は、２．０ｗｔ％であった。また、Ｘ線光電子分光法で複合体表面に付着している金属酸化物類を分析したところ、Ｎｉ２Ｏ３であった。この廃イオン交換膜と酸化ニッケルの複合体２５０ｇをフッ素樹脂製デミスター（後藤商事（株）製）５０ｇの上に分散させ、デミスターと廃イオン交換膜を絡めてロール状に巻いて成形した。このロールを内径５０ｍｍ、高さ４００ｍｍ、内容積０．８Ｌの固定床反応器に充填した。この固定床反応器に、エチレングリコール、エタノールなどをＣＯＤ濃度として５８０ｗｔｐｐｍ含む廃水を連続的に供給して処理した。廃水流量は１．５Ｌ／時間で、同時に酸化剤である次亜塩素酸ナトリウムをＣＯＤに対して重量比で８倍となるように供給した。反応温度は７５℃、反応器入口のｐＨは１０とした。 Next, when the entire amount of the ion exchange membrane subjected to the ion exchange treatment was placed in a 2 L beaker containing 1.5 L of a 3.0 wt% NaClO aqueous solution (pH 10), nickel ions became black oxide. The amount of nickel supported relative to the dry weight of the fluoropolymer cation exchanger was 2.0 wt%. Moreover, when the metal oxides adhering to the composite surface were analyzed by X-ray photoelectron spectroscopy, it was Ni 2 O 3 . 250 g of the composite of the waste ion exchange membrane and nickel oxide was dispersed on 50 g of a fluororesin demister (manufactured by Goto Shoji Co., Ltd.), and the demister and the waste ion exchange membrane were wound to form a roll. This roll was packed in a fixed bed reactor having an inner diameter of 50 mm, a height of 400 mm, and an internal volume of 0.8 L. The fixed bed reactor was treated by continuously supplying waste water containing 580 wtppm of ethylene glycol, ethanol or the like as a COD concentration. The wastewater flow rate was 1.5 L / hour, and at the same time, sodium hypochlorite as an oxidizing agent was supplied so as to be 8 times by weight with respect to COD. The reaction temperature was 75 ° C., and the pH at the reactor inlet was 10.
その結果、運転開始から１日後の処理液のＣＯＤ濃度、次亜塩素酸ナトリウム濃度は、各々２ｗｔｐｐｍ、１２ｗｔｐｐｍ、９０日後の処理液のＣＯＤ濃度、次亜塩素酸ナトリウム濃度は、各々５９ｗｔｐｐｍ、１２０ｗｔｐｐｍ、３００日後の処理液のＣＯＤ濃度、次亜塩素酸ナトリウム濃度は、各々１０２ｗｔｐｐｍ、３５０ｗｔｐｐｍであり、この間に触媒の圧密化は見られず、安定した連続運転を実施できた。 As a result, the COD concentration and sodium hypochlorite concentration of the treatment liquid one day after the start of operation are 2 wtppm and 12 wtppm, respectively, and the COD concentration and sodium hypochlorite concentration of the treatment liquid after 90 days are 59 wtppm and 120 wtppm, respectively. The COD concentration and sodium hypochlorite concentration of the treatment liquid after 300 days were 102 wtppm and 350 wtppm, respectively, and no consolidation of the catalyst was observed during this period, and stable continuous operation could be carried out.
比較例１
実施例３と同様に、廃イオン交換膜と酸化ニッケルの複合体を製造した。これと２分割にした１インチのポールリングを絡めて内径５０ｍｍ、高さ４００ｍｍ、内容積０．８Ｌの固定床反応器に充填した。この固定床反応器に、実施例３と同じ廃水を連続的に供給して処理した。廃水流量は１．５Ｌ／時間で、同時に酸化剤である次亜塩素酸ナトリウムをＣＯＤに対して重量比で８倍となるように供給した。反応温度は７５℃、反応器入口のｐＨは１０とした。
Comparative Example 1
As in Example 3, a composite of a waste ion exchange membrane and nickel oxide was produced. This was entangled with a 1-inch pole ring divided into two and packed in a fixed bed reactor having an inner diameter of 50 mm, a height of 400 mm, and an internal volume of 0.8 L. This fixed bed reactor was treated by continuously supplying the same waste water as in Example 3. The wastewater flow rate was 1.5 L / hour, and at the same time, sodium hypochlorite as an oxidizing agent was supplied so as to be 8 times by weight with respect to COD. The reaction temperature was 75 ° C., and the pH at the reactor inlet was 10.
その結果、運転開始から１日後の処理液のＣＯＤ濃度、次亜塩素酸ナトリウム濃度は、各々２ｗｔｐｐｍ、１３ｗｔｐｐｍ、１５０日後の処理液のＣＯＤ濃度、次亜塩素酸ナトリウム濃度は、各々７０ｗｔｐｐｍ、２５０ｗｔｐｐｍであったが、充填した触媒のうち、３５ｇがポールリングから外れて流出したため、連続運転を一時停止し、触媒を充填し直して運転を再開した。 As a result, the COD concentration and sodium hypochlorite concentration of the treatment liquid one day after the start of operation are 2 wtppm and 13 wtppm, respectively, and the COD concentration and sodium hypochlorite concentration of the treatment liquid after 150 days are 70 wtppm and 250 wtppm, respectively. However, 35 g out of the charged catalyst flowed out of the pole ring, so the continuous operation was temporarily stopped, the catalyst was refilled, and the operation was resumed.
本発明によれば、シート状のイオン交換膜を固定床に充填して、有効に利用することができる。 According to the present invention, a sheet-like ion exchange membrane can be filled in a fixed bed and used effectively.
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