JP2003251375A - Treatment method for organic wastewater - Google Patents
Treatment method for organic wastewaterInfo
- Publication number
- JP2003251375A JP2003251375A JP2002051698A JP2002051698A JP2003251375A JP 2003251375 A JP2003251375 A JP 2003251375A JP 2002051698 A JP2002051698 A JP 2002051698A JP 2002051698 A JP2002051698 A JP 2002051698A JP 2003251375 A JP2003251375 A JP 2003251375A
- Authority
- JP
- Japan
- Prior art keywords
- organic wastewater
- inorganic carrier
- granular inorganic
- organic
- catalyst
- 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
- 238000000034 method Methods 0.000 title claims abstract description 34
- 239000002351 wastewater Substances 0.000 title claims abstract description 29
- 239000000460 chlorine Substances 0.000 claims abstract description 33
- 229910052801 chlorine Inorganic materials 0.000 claims abstract description 33
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims abstract description 31
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 28
- 239000003054 catalyst Substances 0.000 claims abstract description 25
- 239000002245 particle Substances 0.000 claims abstract description 23
- 239000002957 persistent organic pollutant Substances 0.000 claims abstract description 22
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000005708 Sodium hypochlorite Substances 0.000 claims abstract description 12
- 229910021536 Zeolite Inorganic materials 0.000 claims description 18
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 18
- 239000010457 zeolite Substances 0.000 claims description 18
- JYIBXUUINYLWLR-UHFFFAOYSA-N aluminum;calcium;potassium;silicon;sodium;trihydrate Chemical group O.O.O.[Na].[Al].[Si].[K].[Ca] JYIBXUUINYLWLR-UHFFFAOYSA-N 0.000 claims description 4
- 229910001603 clinoptilolite Inorganic materials 0.000 claims description 4
- 229910052680 mordenite Inorganic materials 0.000 claims description 3
- 229910000428 cobalt oxide Inorganic materials 0.000 claims description 2
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 claims description 2
- 229910000480 nickel oxide Inorganic materials 0.000 claims description 2
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical group [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 claims description 2
- 238000000354 decomposition reaction Methods 0.000 abstract description 16
- 230000003197 catalytic effect Effects 0.000 abstract description 13
- 230000003647 oxidation Effects 0.000 abstract description 11
- 238000007254 oxidation reaction Methods 0.000 abstract description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 23
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 10
- 229910052759 nickel Inorganic materials 0.000 description 7
- 239000010815 organic waste Substances 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 4
- -1 nickel peroxide Chemical class 0.000 description 4
- 229910021642 ultra pure water Inorganic materials 0.000 description 4
- 239000012498 ultrapure water Substances 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000006864 oxidative decomposition reaction Methods 0.000 description 3
- 230000001590 oxidative effect Effects 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 125000001309 chloro group Chemical group Cl* 0.000 description 2
- 239000010800 human waste Substances 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- UPWOEMHINGJHOB-UHFFFAOYSA-N oxo(oxocobaltiooxy)cobalt Chemical compound O=[Co]O[Co]=O UPWOEMHINGJHOB-UHFFFAOYSA-N 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 1
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 description 1
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 1
- 241000080590 Niso Species 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 230000010534 mechanism of action Effects 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 1
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 1
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 1
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 239000010802 sludge Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
Landscapes
- Treatment Of Water By Oxidation Or Reduction (AREA)
- Catalysts (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、有機性排水中の有
機汚濁成分を酸化分解する方法に係り、詳しくは、有機
性排水中を、塩素剤の存在下に、粒状無機担体に触媒活
性成分を担持させてなる触媒と接触させることにより、
該有機性排水中の有機汚濁成分を酸化分解する有機性排
水の処理方法に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for oxidatively decomposing organic pollutants in organic wastewater, and more specifically, to a catalytically active component in a granular inorganic carrier in organic wastewater in the presence of a chlorine agent. By contacting with a catalyst supporting
The present invention relates to a method for treating organic wastewater by oxidizing and decomposing organic pollutants in the organic wastewater.
【０００２】[0002]
【従来の技術】従来、し尿処理水等の有機汚濁成分を含
む有機性着色汚水の処理方法としては、生物学的処理方
法や活性炭吸着法、オゾン酸化法、塩素酸化法、フェン
トン法、触媒酸化法などが知られており、既に実用化さ
れている。このうち、触媒酸化法は、次亜塩素酸ナトリ
ウムやオゾン等の酸化剤と、ゼオライトやアルミナ等の
担体に過酸化ニッケルや過酸化コバルトを担持した触媒
とを組み合わせて、有機性排水中の有機汚濁成分を接触
酸化分解するものであり（特公昭５８−８３０７号公
報）、生物学的処理法等に比べて省スペースであり、再
生等のメンテナンス頻度も少なく、しかも塩素酸化法等
に比べて分解効率が高く、汚泥発生の問題もないといっ
た利点を有する。2. Description of the Related Art Conventionally, as a method for treating organic colored wastewater containing organic pollutants such as treated human waste water, biological treatment method, activated carbon adsorption method, ozone oxidation method, chlorine oxidation method, Fenton method, catalytic oxidation method. The law is known and has already been put to practical use. Among them, the catalytic oxidation method is a combination of an oxidizing agent such as sodium hypochlorite or ozone and a catalyst in which nickel peroxide or cobalt peroxide is supported on a carrier such as zeolite or alumina, and the organic matter in the organic waste water is combined. It is a method for catalytically oxidizing and decomposing polluted components (Japanese Patent Publication No. 58-8307), which saves space compared to biological treatment methods and the like, requires less maintenance frequency such as regeneration, and is more efficient than chlorine oxidation method and the like. It has the advantages of high decomposition efficiency and no sludge generation problem.
【０００３】[0003]
【発明が解決しようとする課題】しかしながら、触媒酸
化法では、触媒表面上において、次亜塩素酸ナトリウム
等の塩素剤の一部が自己分解反応を起こし、有機汚濁成
分の酸化分解に使用されることなく消失してしまう。こ
のため、有機性排水中の有機汚濁成分の酸化分解に必要
な理論量よりも過剰に塩素剤を添加する必要があり、処
理コストが高くつくという問題があった。However, in the catalytic oxidation method, a part of the chlorine agent such as sodium hypochlorite causes a self-decomposition reaction on the surface of the catalyst and is used for the oxidative decomposition of organic pollutant components. It disappears without any notice. Therefore, it is necessary to add the chlorine agent in excess of the theoretical amount required for the oxidative decomposition of the organic pollutant component in the organic waste water, which causes a problem of high treatment cost.
【０００４】本発明は上記従来の問題点を解決し、触媒
酸化法による有機性排水の処理において、次亜塩素酸ナ
トリウム等の塩素剤を有機汚濁成分の分解に有効に作用
させることにより、少ない塩素剤添加量で有機汚濁成分
を効率的に酸化分解する方法を提供することを目的とす
る。The present invention solves the above-mentioned conventional problems, and in the treatment of organic waste water by the catalytic oxidation method, the chlorine agent such as sodium hypochlorite effectively acts on the decomposition of organic pollutant components, thereby reducing It is an object of the present invention to provide a method for efficiently oxidizing and decomposing organic pollutant components with the addition amount of a chlorine agent.
【０００５】[0005]
【課題を解決するための手段】本発明の有機性排水の処
理方法は、有機性排水中を、塩素剤の存在下に、粒状無
機担体に触媒活性成分を担持させてなる触媒と接触させ
ることにより、該有機性排水中の有機汚濁成分を酸化分
解する有機性排水の処理方法において、該触媒の粒状無
機担体として、平均粒径０．５ｍｍ以下の粒状無機担体
を用いることを特徴とする。According to the method for treating organic wastewater of the present invention, the organic wastewater is contacted with a catalyst comprising a granular inorganic carrier carrying a catalytically active component in the presence of a chlorine agent. Thus, in the method for treating organic wastewater in which the organic pollutant component in the organic wastewater is oxidatively decomposed, a granular inorganic carrier having an average particle diameter of 0.5 mm or less is used as the granular inorganic carrier of the catalyst.
【０００６】本発明者は、触媒酸化法における次亜塩素
酸ナトリウム等の塩素剤の自己分解を防止すべく鋭意検
討を重ねた結果、平均粒径０．５ｍｍ以下の粒状無機担
体を用いることにより、有機汚濁成分の分解効率が向上
するだけでなく、次亜塩素酸ナトリウム等の塩素剤を有
機汚濁成分の分解に有効に作用させることが可能となる
ことを見出した。The present inventor has conducted extensive studies to prevent self-decomposition of a chlorine agent such as sodium hypochlorite in the catalytic oxidation method, and as a result, by using a granular inorganic carrier having an average particle size of 0.5 mm or less, It has been found that not only the efficiency of decomposing organic pollutants is improved, but also a chlorine agent such as sodium hypochlorite can effectively act on the decomposition of organic pollutants.
【０００７】触媒の担体として平均粒径０．５ｍｍ以下
の粒状無機担体を用いることによる本発明の作用機構の
詳細は明らかではないが、平均粒径０．５ｍｍ以下で比
表面積が大幅にふえた粒状無機担体を用いることにより
担体表面に担持された触媒量が増加し、その結果触媒活
性が高められ、この高い触媒活性で有機汚濁成分の分解
が促進される。一方、塩素剤の自己分解は、主に担体の
細孔中で行われると考えられるが、平均粒径が小さいと
比表面積に比べ、細孔容量が小さいので塩素剤が自己分
解する度合が少なくなり、有機汚濁成分と優先的に反応
するようになることによるものと推定される。Although the details of the mechanism of action of the present invention by using a granular inorganic carrier having an average particle size of 0.5 mm or less as a catalyst carrier are not clear, the specific surface area is significantly increased at an average particle size of 0.5 mm or less. By using the granular inorganic carrier, the amount of the catalyst supported on the surface of the carrier increases, and as a result, the catalytic activity is enhanced, and the decomposition of the organic pollutant component is promoted by this high catalytic activity. On the other hand, the self-decomposition of the chlorine agent is considered to be carried out mainly in the pores of the carrier, but when the average particle size is small, the pore volume is smaller than the specific surface area, so the degree of self-decomposition of the chlorine agent is small. It is presumed that this is due to the preferential reaction with organic pollutants.
【０００８】本発明において、粒状無機担体としては、
クリノプチロライト系天然ゼオライト及び／又はモルデ
ナイト系天然ゼオライトが好ましく、塩素剤としては次
亜塩素酸ナトリウムが、また、触媒活性成分としては過
酸化ニッケルが好ましい。In the present invention, as the granular inorganic carrier,
Clinoptilolite type natural zeolite and / or mordenite type natural zeolite are preferable, sodium hypochlorite is preferable as the chlorine agent, and nickel peroxide is preferable as the catalytically active component.
【０００９】[0009]
【発明の実施の形態】以下に本発明の有機性排水の処理
方法の実施の形態を詳細に説明する。BEST MODE FOR CARRYING OUT THE INVENTION Embodiments of the method for treating organic waste water according to the present invention will be described in detail below.
【００１０】まず、本発明で用いる触媒について説明す
る。First, the catalyst used in the present invention will be described.
【００１１】本発明においては、触媒酸化法における触
媒の粒状無機担体として、平均粒径０．５ｍｍ以下の粒
状無機担体を用いる。後述の実施例及び比較例の結果か
らも明らかなように、平均粒径は小さい程有機汚濁成分
の分解効率、次亜塩素酸ナトリウム等の塩素剤の利用効
率は高くなる傾向にあるが、過度に平均粒径の小さい粒
状無機担体は、取り扱い性や価格の面で好ましくないこ
とから、平均粒径０．０５〜０．５ｍｍ、特に０．１〜
０．４ｍｍの粒状無機担体を用いることが好ましい。In the present invention, a granular inorganic carrier having an average particle diameter of 0.5 mm or less is used as the granular inorganic carrier of the catalyst in the catalytic oxidation method. As is clear from the results of Examples and Comparative Examples described below, the smaller the average particle size, the higher the decomposition efficiency of organic pollutant components, the higher the utilization efficiency of chlorine agents such as sodium hypochlorite, but excessive. Since the granular inorganic carrier having a small average particle size is not preferable in terms of handleability and price, the average particle size is 0.05 to 0.5 mm, particularly 0.1 to 0.5 mm.
It is preferable to use a 0.4 mm granular inorganic carrier.
【００１２】この粒状無機担体としては、ゼオライト、
アルミナ等を用いることができるが、特にゼオライトが
好ましい。ゼオライトとしては、天然ゼオライト、合成
ゼオライトのいずれでも良いが、硬質で、耐磨耗性に優
れることから、クリノプチロライト系天然ゼオライト、
及び／又はモルデナイト系天然ゼオライトを用いること
が好ましい。As the granular inorganic carrier, zeolite,
Alumina or the like can be used, but zeolite is particularly preferable. As the zeolite, either natural zeolite or synthetic zeolite may be used, but since it is hard and has excellent abrasion resistance, clinoptilolite-based natural zeolite,
And / or mordenite type natural zeolite is preferably used.
【００１３】このような粒状無機担体に担持させる触媒
活性成分としては、ニッケル及び／又はコバルト好まし
くはニッケル酸化物又はコバルト酸化物が挙げられ、特
に過酸化ニッケル又は過酸化コバルトが好ましい。粒状
無機担体に過酸化ニッケルを担持させるには、硫酸ニッ
ケル、硝酸ニッケル、塩化ニッケル等の水溶液に粒状無
機担体を浸漬させるなどして接触させた後、必要に応じ
て洗浄し、その後塩素剤を含むアルカリ溶液で処理して
洗浄すれば良い。Examples of the catalytically active component supported on such a granular inorganic carrier include nickel and / or cobalt, preferably nickel oxide or cobalt oxide, and nickel peroxide or cobalt peroxide is particularly preferable. In order to support nickel peroxide on the granular inorganic carrier, the granular inorganic carrier is contacted by immersing it in an aqueous solution of nickel sulfate, nickel nitrate, nickel chloride, etc., and then washed if necessary, and then a chlorine agent is added. It may be cleaned by treating with an alkaline solution containing it.
【００１４】粒状無機担体への触媒活性成分の担持処理
条件は適宜決定されるが、本発明によれば、平均粒径が
０．５ｍｍ以下という微粒状の粒状無機担体を用いるこ
とにより、触媒活性成分を効率的に担持させることがで
き、触媒活性の高い触媒を調製することができる。Although the conditions for carrying the catalytically active component on the granular inorganic carrier are appropriately determined, according to the present invention, the catalytic activity can be improved by using the fine granular inorganic carrier having an average particle size of 0.5 mm or less. The components can be efficiently supported, and a catalyst having high catalytic activity can be prepared.
【００１５】塩素剤としては、次亜塩素酸ナトリウム、
塩素ガス、電解により発生させた塩素などの遊離塩素を
発生する薬剤、好ましくは次亜塩素酸ナトリウムを用い
ることができる。As the chlorine agent, sodium hypochlorite,
A chlorine gas, an agent that generates free chlorine such as chlorine generated by electrolysis, preferably sodium hypochlorite can be used.
【００１６】本発明では、処理する有機性排水に塩素剤
を添加し、これを前記触媒の充填カラムに通水するか、
触媒を添加して混合するなどして触媒と接触させる。In the present invention, a chlorine agent is added to the organic wastewater to be treated and this is passed through a packed column of the catalyst, or
The catalyst is added and mixed to bring it into contact with the catalyst.
【００１７】本発明では、用いる触媒の粒径が小さいの
でカラムは流動床で通水する方が好ましい。この通水速
度はＬＶ１．５ｍ／ｈｒ以上とする。In the present invention, since the catalyst used has a small particle size, it is preferable to pass water through the column in a fluidized bed. This water flow rate shall be LV 1.5 m / hr or more.
【００１８】有機性排水に添加する塩素剤の添加量は、
有機性排水中の有機汚濁成分量に応じて適宜決定される
が、本発明では、平均粒径０．５ｍｍ以下の粒状無機担
体を用いることにより、塩素剤の使用量を低減すること
ができ、有機性排水中のＣＯＤＭｎに対して塩素換算の
添加量として４〜１０重量倍程度の添加量で十分な分解
効率を得ることができる。The amount of chlorine agent added to the organic wastewater is
The amount of the chlorine agent can be reduced by using a granular inorganic carrier having an average particle size of 0.5 mm or less, though it is appropriately determined according to the amount of organic pollutant components in the organic waste water. Sufficient decomposition efficiency can be obtained by adding chlorine in an amount of about 4 to 10 times by weight with respect to COD Mn in the organic waste water.
【００１９】塩素剤を添加した有機性排水を触媒充填カ
ラムに通水する場合、その通水条件は、塩素剤の添加量
や有機性排水の有機汚濁成分量等によって適宜決定され
る。When the organic wastewater containing the chlorine agent is passed through the catalyst-filled column, the water passage conditions are appropriately determined depending on the amount of the chlorine agent added and the amount of organic pollutants in the organic wastewater.
【００２０】このような本発明の有機性排水の処理方法
は、し尿処理水、その他の着色有機性排水の脱色及びＣ
ＯＤ除去処理に有効であり、塩素剤及び触媒使用量の低
減により、イニシャルコスト、ランニングコストの削減
を図ることができる。Such a method for treating organic wastewater according to the present invention is a method for decolorizing human waste water and other colored organic wastewater, and C
It is effective for OD removal treatment, and the initial cost and running cost can be reduced by reducing the amounts of chlorine agent and catalyst used.
【００２１】[0021]
【実施例】以下に実施例及び比較例を挙げて本発明をよ
り具体的に説明する。EXAMPLES The present invention will be described more specifically with reference to Examples and Comparative Examples below.
【００２２】なお、供試担体としては、クリノプチロラ
イト系天然ゼオライト（イオン交換容量：１６６〜１６
８ｍｅｑ／１００ｇ，ＢＥＴ比表面積：１８ｍ２／ｇ）
を用い、下記Ａ〜Ｅの粒径範囲の５種類のものを用意し
た。
Ａ：０．０８〜０．２２ｍｍφ
Ｂ：０．２２〜０．５０ｍｍφ
Ｃ：０．５０〜 １．０ｍｍφ
Ｄ： １．０〜 ２．０ｍｍφ
Ｅ： ２．０〜 ４．０ｍｍφAs the sample carrier, clinoptilolite natural zeolite (ion exchange capacity: 166 to 16) is used.
8 meq / 100 g, BET specific surface area: 18 m 2 / g)
The following five kinds of particles having particle diameter ranges A to E were prepared. A: 0.08 to 0.22 mmφ B: 0.22 to 0.50 mmφ C: 0.50 to 1.0 mmφ D: 1.0 to 2.0 mmφ E: 2.0 to 4.0 mmφ
【００２３】触媒の調製手順は以下の通りである。
担体をそれぞれ１，０００ｇとり、ＳＳ成分がなく
なるまで洗浄した。
ＮｉＳＯ４・６Ｈ２Ｏ １１２ｇ（２５ｇ−Ｎｉ／
１，０００ｇ−乾燥ゼオライト）を８００ｍＬの超純水
に溶解した。これを水洗したゼオライトに添加し、２０
ｈｒ放置した（担体に対して２．５重量％Ｎｉ添加）
上澄み液を廃棄した。
１，０００ｍＬの超純水で３度ゼオライトを洗浄し
た。
３５ｇのＮａＯＨを５００ｍＬの超純水に溶解し、
４００ｍＬの１０重量％ＮａＣｌＯ溶液を添加し、この
混合溶液中に洗浄後のゼオライトを浸漬して２０ｈｒ放
置した。
ゼオライトをの混合溶液から分離し、洗浄水のｐ
Ｈが１０になるまで超純水で洗浄した。The procedure for preparing the catalyst is as follows. 1,000 g of each carrier was taken and washed until the SS component was eliminated. NiSO 4 · 6H 2 O 112g ( 25g-Ni /
1,000 g-dry zeolite) was dissolved in 800 mL of ultrapure water. Add this to washed zeolite and add 20
The mixture was allowed to stand for hr (2.5 wt% Ni added to the carrier), and the supernatant was discarded. The zeolite was washed 3 times with 1,000 mL of ultrapure water. Dissolve 35 g of NaOH in 500 mL of ultrapure water,
400 mL of 10 wt% NaClO solution was added, and the washed zeolite was immersed in this mixed solution and left for 20 hours. The zeolite is separated from the mixed solution of
It was washed with ultrapure water until H became 10.
【００２４】調整した触媒を別途塩酸で溶解し、ニッケ
ル担持量（ｇ／ｇ−触媒）を測定したところ、Ａ：０．
１３，Ｂ：０．１１，Ｃ：０．１４，Ｄ：０．１１であ
った。The adjusted catalyst was separately dissolved in hydrochloric acid, and the amount of nickel supported (g / g-catalyst) was measured.
13, B: 0.11, C: 0.14, D: 0.11.
【００２５】実施例１，２、比較例１〜３
表１に示す粒状無機担体を用いて調製した触媒を各々内
径２５ｍｍφのカラムに５０ｍＬ充填した。このカラム
に、ＣＯＤ源としてモノエタノールアミンを含有する原
水（ｐＨ７．９〜８．１）に、ＮａＣｌＯを添加した
後、通水した。温度は４０℃で通水速度７５０ｍＬ／ｈ
ｒ，ＳＶ：１５ｈｒ−１，ＬＶ：１．５ｍ／ｈｒで通水
を行った。Examples 1 and 2 and Comparative Examples 1 to 3 50 mL of the catalyst prepared by using the granular inorganic carrier shown in Table 1 was packed in each column having an inner diameter of 25 mmφ. To this column, NaClO was added to raw water (pH 7.9 to 8.1) containing monoethanolamine as a COD source, and then water was passed. Temperature is 40 ° C and water flow rate is 750mL / h
Water was passed at r, SV: 15 hr −1 and LV: 1.5 m / hr.
【００２６】この処理における、原水のＣＯＤＭｎ、処
理水のＣＯＤＭｎ及びその分解率と、原水のＮａＣｌＯ
濃度、処理水のＮａＣｌＯ濃度及びその分解率は表１に
示す通りであった。[0026] in this process, raw water COD Mn, and COD Mn and its degradation rate of the treated water, NaClO raw water
The concentration, the concentration of NaClO in the treated water, and the decomposition rate thereof were as shown in Table 1.
【００２７】各例におけるＮａＣｌＯのＣＯＤ分解に対
する有効利用率を調べるために、反応比（ΔＣＯＤ／Δ
ＮａＣｌＯ）として、消費されたＮａＣｌＯ量（原水Ｎ
ａＣｌＯ濃度−処理水ＮａＣｌＯ濃度）に対する除去さ
れたＣＯＤＭｎ量（原水ＣＯＤＭｎ−処理水ＣＯ
ＤＭｎ）の割合を算出し、結果を表１に示すと共に、こ
の反応比と触媒の粒状無機担体の平均粒径との関係を図
１に示した。In order to examine the effective utilization rate of NaClO for COD decomposition in each example, the reaction ratio (ΔCOD / Δ
As NaClO), the amount of NaClO consumed (raw water N
aCOO concentration-treated water NaClO concentration) COD Mn amount removed (raw water COD Mn -treated water CO)
The ratio of D Mn ) was calculated, the results are shown in Table 1, and the relationship between this reaction ratio and the average particle size of the granular inorganic carrier of the catalyst is shown in FIG.
【００２８】[0028]
【表１】 [Table 1]
【００２９】表１及び図１より、粒状無機担体の平均粒
径が小さい程反応比ΔＣＯＤ／ΔＮａＣｌＯが大きく、
単位塩素消費量当たりのＣＯＤ除去量が多いことが分か
る。この傾向は、特に、粒状無機担体の平均粒径が０．
３９ｍｍ以下の場合に顕著であり、また、平均粒径が
０．３９ｍｍ以下の場合には、ＣＯＤＭｎ分解率も格段
に向上しており、平均粒径０．４ｍｍ以下の粒状無機担
体を用いることにより、効率的な接触酸化分解を行うこ
とができることが明らかである。From Table 1 and FIG. 1, the smaller the average particle size of the granular inorganic carrier, the larger the reaction ratio ΔCOD / ΔNaClO,
It can be seen that the COD removal amount per unit chlorine consumption is large. This tendency is especially caused when the average particle size of the granular inorganic carrier is 0.
When the average particle size is 39 mm or less, the COD Mn decomposition rate is remarkably improved when the average particle size is 0.39 mm or less, and a granular inorganic carrier having an average particle size of 0.4 mm or less is used. Thus, it is clear that efficient catalytic oxidative decomposition can be carried out.
【００３０】[0030]
【発明の効果】以上詳述した通り、本発明の有機性排水
の処理方法によれば、触媒酸化法による有機性排水の処
理において、有機汚濁成分の分解効率を高めると共に、
次亜塩素酸ナトリウム等の塩素剤を有機汚濁成分の分解
に有効に作用させることができるため、塩素剤及び触媒
の必要量を低減することができ、有機性排水中の有機汚
濁成分を低コストで効率的に酸化分解することができ
る。As described in detail above, according to the method for treating organic wastewater of the present invention, in the treatment of organic wastewater by the catalytic oxidation method, the decomposition efficiency of organic pollutant components is increased, and
Since chlorine agents such as sodium hypochlorite can effectively act on the decomposition of organic pollutants, the required amount of chlorine agents and catalysts can be reduced, and organic pollutants in organic wastewater can be produced at low cost. Can be efficiently oxidatively decomposed.
【図１】実施例１，２と比較例１〜３で得られた反応比
と粒状無機担体の平均粒径との関係を示すグラフであ
る。FIG. 1 is a graph showing the relationship between the reaction ratios obtained in Examples 1 and 2 and Comparative Examples 1 to 3 and the average particle size of a granular inorganic carrier.
───────────────────────────────────────────────────── フロントページの続き Ｆターム(参考） 4D050 AA12 AB07 BB05 BB06 BC05 BC06 BD03 BD06 4G069 AA03 BA07A BA07B BC67A BC68A BC68B CA05 EA02X EA02Y EB18X EB18Y ZA06A ZA15A ZA15B ZF05A ZF05B ─────────────────────────────────────────────────── ─── Continued front page F term (reference) 4D050 AA12 AB07 BB05 BB06 BC05 BC06 BD03 BD06 4G069 AA03 BA07A BA07B BC67A BC68A BC68B CA05 EA02X EA02Y EB18X EB18Y ZA06A ZA15A ZA15B ZF05A ZF05B
Claims (4)
状無機担体に触媒活性成分を担持させてなる触媒と接触
させることにより、該有機性排水中の有機汚濁成分を酸
化分解する有機性排水の処理方法において、 該触媒の粒状無機担体として、平均粒径０．５ｍｍ以下
の粒状無機担体を用いることを特徴とする有機性排水の
処理方法。1. An organic pollutant component in an organic wastewater is oxidatively decomposed by bringing the organic wastewater into contact with a catalyst obtained by supporting a catalytically active component on a granular inorganic carrier in the presence of a chlorine agent. In the method for treating organic wastewater, a granular inorganic carrier having an average particle diameter of 0.5 mm or less is used as the granular inorganic carrier for the catalyst.
リノプチロライト系天然ゼオライト及び／又はモルデナ
イト系天然ゼオライトであることを特徴とする有機性排
水の処理方法。2. The method for treating organic wastewater according to claim 1, wherein the granular inorganic carrier is clinoptilolite-based natural zeolite and / or mordenite-based natural zeolite.
亜塩素酸ナトリウムであることを特徴とする有機性排水
の処理方法。3. The method for treating organic wastewater according to claim 1, wherein the chlorine agent is sodium hypochlorite.
て、該触媒活性成分がニッケル酸化物又はコバルト酸化
物であることを特徴とする有機性排水の処理方法。4. The method for treating organic wastewater according to claim 1, wherein the catalytically active component is nickel oxide or cobalt oxide.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105879872A (en) * | 2016-04-27 | 2016-08-24 | 河北协同环保科技股份有限公司 | Method for preparing Fenton-like reaction catalyst and application thereof |
| CN106882867A (en) * | 2017-03-29 | 2017-06-23 | 山东本源晶体科技有限公司 | A kind of method of modified graphene catalytic oxidation treatment thiram waste water |
-
2002
- 2002-02-27 JP JP2002051698A patent/JP2003251375A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105879872A (en) * | 2016-04-27 | 2016-08-24 | 河北协同环保科技股份有限公司 | Method for preparing Fenton-like reaction catalyst and application thereof |
| CN105879872B (en) * | 2016-04-27 | 2019-03-15 | 河北协同水处理技术有限公司 | The preparation method and application of class Fenton's reaction catalyst |
| CN106882867A (en) * | 2017-03-29 | 2017-06-23 | 山东本源晶体科技有限公司 | A kind of method of modified graphene catalytic oxidation treatment thiram waste water |
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