JP2011016048A - Method of decoloring and purifying wastewater containing lignin and/or tannin - Google Patents

Method of decoloring and purifying wastewater containing lignin and/or tannin Download PDF

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JP2011016048A
JP2011016048A JP2009161109A JP2009161109A JP2011016048A JP 2011016048 A JP2011016048 A JP 2011016048A JP 2009161109 A JP2009161109 A JP 2009161109A JP 2009161109 A JP2009161109 A JP 2009161109A JP 2011016048 A JP2011016048 A JP 2011016048A
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tannin
lignin
wastewater
flocculants
cultivation
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Toshihiro Okita
俊博 尾北
Hitoshi Nakao
均 中尾
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ACT Co Ltd
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Abstract

PROBLEM TO BE SOLVED: To provide a method of efficiently decoloring and purifying wastewater, which is a dark brown colored liquid containing organic components giving BOD and COD values, and lignin and/or tannin, without generating hazardous substances.SOLUTION: In the new decoloring and purifying method, iron chloride or iron sulfate and an alkali metal aluminate are added, and then, preferably, coagulation treatment using an organic polymer coagulant, an inorganic coagulant, or a composite coagulant comprising the organic polymer coagulant and the inorganic coagulant is carried out, and more preferably solid-liquid separation is additionally carried out.

Description

本発明は、緑茶などの製茶過程や椎茸などの栽培設備から排出されるような、高いCOD・BOD値を与える有機物成分を含み、且つリグニン及びタンニンを含有する黒褐色着色排水を、効率良くしかも有害物質を生じることなく、脱色浄化できる新規な処理方法に関する。   The present invention efficiently and harmfully removes black-brown colored wastewater containing organic components that give high COD / BOD values, such as discharged from tea making processes such as green tea and cultivation facilities such as shiitake mushrooms, and containing lignin and tannin. The present invention relates to a novel processing method capable of decolorizing and purifying without generating substances.

茶類の製造方法は一様ではないが、例えば、緑茶の場合、摘み取った茶葉を原料にして、葉打ち、粗揉む、中揉み、乾燥、等の一連の工程が採用されている。そして、この製造工程からは、高いCOD値及びBOD値を与える有機物成分を含み、かつ黒褐色に着色した製茶排水が排出される。この製茶排水は、従来特に処理されることなく、河川に放流されていたが、環境保全のため法律上でも規制される可能性がある。今後、茶類の生産量の増加につれ、排水に関する規制が厳しくなされることは必須で、何らかの浄化処理が必要である。 For example, in the case of green tea, a series of processes such as leaf punching, rough kneading, medium kneading, and drying are employed in the case of green tea. And from this manufacturing process, the tea-making waste water which contains the organic substance component which gives a high COD value and a BOD value, and was colored black brown is discharged | emitted. The tea wastewater has conventionally been discharged into rivers without any particular treatment, but may be regulated by law for environmental conservation. In the future, as tea production increases, it is essential that regulations regarding drainage be tightened, and some sort of purification treatment is necessary.

一方、健康への意識向上に伴って椎茸の需要も増しており、近年では人工栽培法として原木栽培又は菌床栽培によって多量に生産流通されている。原木栽培とは、天然の木を用い、木材腐朽菌のキノコを栽培する方法で、伐採し枯れた丸太に直接種菌を植え付ける方法である。丸太(原木)をそのまま使うことから原木栽培と呼ばれている。一方、菌床栽培は、木質基材と米糠などの栄養源を混ぜた人工培地でキノコを栽培する方法である。最近では、市場に流通している椎茸は原木栽培又は菌床栽培された物が殆どを占め、その内でも生産効率の点から菌床栽培が主流となりつつある。但し、いずれの栽培法においても、黒褐色に着色した排水が発生し、その処理が社会的問題となりつつある。   On the other hand, the demand for shiitake mushrooms has increased along with the improvement of health awareness. In recent years, a large amount of shiitake mushrooms are produced and distributed by artificial wood cultivation or fungus bed cultivation. Raw wood cultivation is a method of cultivating mushrooms of wood-rotting fungi using natural wood, and is a method of planting inoculum directly on logs that have been cut and withered. It is called log cultivation because it uses logs (logs) as they are. On the other hand, fungus bed cultivation is a method of cultivating mushrooms on an artificial medium in which a nutrient material such as a wood substrate and rice bran is mixed. Recently, most shiitake mushrooms on the market are cultivated with log or fungus bed, and among them, fungus bed cultivation is becoming mainstream from the viewpoint of production efficiency. However, in any cultivation method, waste water colored in blackish brown is generated, and its treatment is becoming a social problem.

原木栽培において黒褐色に着色した排水が発生する機構としては、下記のプロセスが原因と考えられる。即ち、原木に椎茸菌を接種した後、自然環境中で250日〜300日間、椎茸菌を培養する。その後、椎茸を発生させる目的で、6〜12時間程度水に漬けて刺激を与え、その刺激により椎茸を発生させる。この水に浸漬する際に黒褐色の排水が発生する。
一方、菌床栽培においては、まず広葉樹のチップとオガクズや米糠などの栄養剤を混合した菌床(チップ等を固めたブロック状のもの)を製造する。その後、菌床を一旦加熱殺菌して雑菌を死滅させてから、当該菌床に椎茸菌を接種して培養し、椎茸を発生させる。原木栽培との大きな違いは、菌床の製造から栽培までの作業を温湿度調整(温度:20〜30℃、相対湿度約70%RH)されたハウス内で行う点にある。菌床栽培においては、菌床を製造した後、一旦殺菌目的で加熱する際、その熱が菌床内に十分伝わるように予めチップなどに水を十分含ませた状態にしておくため、チップなどには頻繁に散水する。その際に黒褐色の排水が排出される。また、ハウス内の湿度管理を行うためや、原木栽培と同様に椎茸菌の発生を促すための刺激として散水する際に、黒褐色の排水が排出される。
The following process is thought to be the cause of the generation of black-brown colored wastewater in raw wood cultivation. That is, after inoculating shiitake mushrooms on the log, shiitake mushrooms are cultured in a natural environment for 250 to 300 days. Then, for the purpose of generating shiitake mushrooms, it is immersed in water for about 6 to 12 hours to give a stimulus, and shiitake is generated by the stimulus. When immersed in this water, blackish brown wastewater is generated.
On the other hand, in fungus bed cultivation, first, fungus beds (block-shaped ones in which chips and the like are solidified) are prepared by mixing hardwood chips and nutrients such as sawdust and rice bran. Thereafter, the fungus bed is once sterilized by heating to kill miscellaneous bacteria, and then the fungus bed is inoculated and cultured with shiitake mushrooms to generate shiitake mushrooms. The major difference from log cultivation is that the operation from the production of the fungus bed to the cultivation is carried out in a house where the temperature and humidity are adjusted (temperature: 20 to 30 ° C., relative humidity about 70% RH). In fungus bed cultivation, after heating the fungus bed, once it is heated for sterilization purposes, the tip etc. should be in a state in which water is sufficiently contained in the tip so that the heat is sufficiently transmitted to the fungus bed. There is frequent watering. At that time, black-brown waste water is discharged. In addition, black-brown wastewater is discharged when water is used for humidity control in the house or when watering as a stimulus for promoting the generation of shiitake mushrooms as in the case of log cultivation.

かかる椎茸栽培排水や製茶排水を浄化する場合、簡易に実施する方法として、有機又は無機の凝集剤等を添加し、COD値及びBOD値の原因成分とともに着色成分を凝集物として除去する方法がある。しかし、凝集剤のみによる除去方法の場合は、必ずしも充分な浄化処理が達成されず、特に着色物質の除去が困難であった。椎茸栽培排水や製茶排水の黒褐色成分がどのようなものであるかについては、正確には分かってはいない。しかし、例えば、前者においては、栽培に使用されるチップ・オガクズや栄養剤のフスマ・米糠から散水によって抽出されるリグニン及びタンニン、後者においては茶類に含有されるタンニンやカフェインなどが、水中の重金属類と反応し、有色の錯体化合物となる結果と推定されるが、これを簡易に効率的に除去する手段はあまり知られていない。 When purifying such shiitake cultivation wastewater or tea wastewater, there is a method of simply implementing organic or inorganic flocculants and removing colored components as agglomerates together with components causing COD and BOD values. . However, in the case of the removal method using only the flocculant, sufficient purification treatment is not necessarily achieved, and it is particularly difficult to remove the colored substance. It is not known exactly what the dark brown components of shiitake cultivation wastewater or tea wastewater are. However, for example, in the former case, lignin and tannin extracted by sprinkling water from chips, sawdust and nutrient bran, rice bran used for cultivation, and in the latter case, tannin and caffeine contained in tea It is presumed that this results in the formation of a colored complex compound by reacting with heavy metals, but there are few known means for easily and efficiently removing this.

製茶排水の処理方法としては、COD含有量が100ppm以上で黒褐色に着色した製茶排水を、好ましくは凝集剤を添加し、沈降成分を沈降処理せしめた後に、表面が白金族金属である電極とする電解装置に供給して通電処理し、CODを50ppm以下である無色透明に脱色、浄化せしめる方法が提案されている。(特許文献1)しかし、該処理方法では、大がかりな電解装置と電源装置が必要であるので、自然環境内で行うには大きな制約を有する。
一方、染色汚泥を含む染色排水に対して、粉末活性炭を投入攪拌した後、ミョウバン、中和剤及びアクリル系高分子から成る凝集剤を投入攪拌し、さらに塩化鉄水溶液を投入して攪拌した後、静置して染色汚泥を凝集沈殿させる方法も提案されている。(特許文献2)しかしながら、当該方法では処理工程がやや煩雑であり、しかも椎茸栽培排水や製茶排水を浄化する目的に用いることができるかどうか、不明である。
特開2003−126859公報 特開2008−110280公報よって、椎茸栽培排水や製茶排水の場合には、処理場所が、田畑、森林、山野などの自然環境が保持されている地域にあり、少しの二次汚染も許されない地域である。かくして、これらの椎茸栽培排水や製茶排水中のCOD値及びBOD値を与える有機物成分及び着色成分を除去して、脱色浄化することは喫緊の課題になっている。
As a method for treating tea effluent, tea effluent colored with a dark brown color with a COD content of 100 ppm or more is preferably added to a coagulant to cause precipitation components to settle, and then the surface is a platinum group metal electrode. There has been proposed a method in which an electrolysis apparatus is supplied and energized to decolorize and purify COD in a colorless and transparent state of 50 ppm or less. (Patent Document 1) However, since this processing method requires a large-scale electrolysis apparatus and power supply apparatus, it has a great restriction to perform in a natural environment.
On the other hand, after charging and stirring powdered activated carbon for dyeing wastewater containing dyeing sludge, adding and stirring agglomerates composed of alum, neutralizing agent and acrylic polymer, and further adding iron chloride aqueous solution and stirring Also, a method of allowing the dyed sludge to settle and settle is proposed. (Patent Document 2) However, in this method, the treatment process is somewhat complicated, and it is unclear whether it can be used for the purpose of purifying shiitake cultivation wastewater or tea wastewater.
JP 2003-126859 A According to Japanese Patent Laid-Open No. 2008-110280, in the case of shiitake cultivation wastewater or tea wastewater, the treatment place is in a region where the natural environment is maintained such as fields, forests, and mountainous areas, and no secondary contamination is allowed. It is. Thus, it is an urgent issue to remove and purify organic components and coloring components that give COD and BOD values in shiitake cultivation wastewater and tea wastewater.

よって、本発明の目的は、例えば椎茸栽培及び製茶プロセスからの排水であって、BOD及びCOD値をもたらす有機物成分およびリグニン及び/又はタンニンを含み黒褐色の着色液体である排水を、有害な物質を生じることなく効率的に脱色浄化処理する新規な方法を提供することにある。 Therefore, an object of the present invention is to discharge wastewater from, for example, shiitake cultivation and tea-making processes, which is an organic component that produces BOD and COD values and lignin and / or tannin and is a black-brown colored liquid. It is an object of the present invention to provide a novel method for efficiently performing a decolorizing and purifying process without occurring.

本発明で対象とする椎茸栽培排水及び製茶排水などは、リグニン及び/又はタンニン及びその他の有機物を含む黒褐色の着色液体である。これに対して、上記の目的を達成すべく本発明者は鋭意研究を重ねた結果、塩化鉄又は硫酸鉄とアルミン酸アルカリ金属塩とを添加し、好ましくは、次に有機高分子凝集剤、無機凝集剤又は該有機高分子と該無機凝集剤とから成る複合凝集剤を用いる凝集処理を行い、より好ましくは、更に固液分離を行うことにより、前記目的を充分に満足する下記の新規な脱色浄化処理方法を開発するに至った。
(1)リグニン及び/又はタンニンを含む黒褐色排水を、塩化鉄又は硫酸鉄とアルミン酸アルカリ金属塩とを、順次もしくは互いに同時に添加して脱色浄化せしめることを特徴とする排水の脱色浄化処理方法。尚、該塩化鉄又は硫酸鉄、及びアルミン酸アルカリ金属塩を順次添加する場合は、順序はいずれが先でも良い。(以下同様である。)
(2)塩化鉄又は硫酸鉄とアルミン酸アルカリ金属塩とを添加後、さらに1種又は2種以上の、有機高分子凝集剤もしくは無機凝集剤又は該有機高分子凝集剤と該無機凝集剤との複合凝集剤による処理を行うことを特徴とする、リグニン及び/又はタンニンを含有する排水の脱色浄化処理方法。
(3)塩化鉄が塩化第二鉄であり、硫酸鉄が硫酸第二鉄であり、このいずれかとアルミン酸ナトリウムとを添加することを特徴とする、(1)又は(2)記載のリグニン及び/又はタンニンを含有する排水の脱色浄化処理方法。
(4)さらに固液分離を行うことを特徴とする、(1)乃至(3)記載のリグニン及び/又はタンニンを含有する排水の脱色浄化処理方法。
(5)リグニン及び/又はタンニンを含有する排水が、椎茸の栽培工程から排出されるものである、(1)乃至(4)記載の脱色浄化処理方法。
本発明者の研究によると、上記した特定の薬剤処理により、リグニン及び/又はタンニンを含み黒褐色の着色液体である、例えば椎茸栽培排水及び製茶排水は、後述する実施例に見られるように、そこに含まれるBOD及びCOD値が低下し、また黒褐色の発色現象を与える有機物成分が、極めて効率的にかつ充分に除去され得ることが見出された。そして、塩化鉄又は硫酸鉄とアルミン酸アルカリ金属塩とを順次添加する薬剤処理の後に、好ましくは、1種又は2種以上の、有機高分子凝集剤又は無機凝集剤又は該有機高分子凝集剤と該無機凝集剤との複合凝集剤による処理を行うことにより、より効率的に短時間で脱色浄化の目的が達成され、更に必要に応じて、最後に固液分離操作を行うことが一層好ましいことが判明した。
Shiitake cultivation drainage and tea drainage targeted by the present invention are black-brown colored liquids containing lignin and / or tannin and other organic substances. On the other hand, in order to achieve the above object, the present inventor has conducted extensive research, and as a result, added iron chloride or iron sulfate and an alkali metal aluminate, preferably, an organic polymer flocculant, An aggregating treatment using an inorganic flocculant or a composite flocculant composed of the organic polymer and the inorganic flocculant is performed, and more preferably, a solid-liquid separation is further performed to satisfy the above-mentioned object. The decolorization purification treatment method has been developed.
(1) A method for decolorizing and purifying wastewater, characterized in that black brown wastewater containing lignin and / or tannin is decolorized and purified by adding iron chloride or iron sulfate and alkali metal aluminate sequentially or simultaneously to each other. In addition, when adding this iron chloride or iron sulfate, and an alkali metal aluminate sequentially, any may be sufficient first. (The same applies hereinafter.)
(2) After adding iron chloride or iron sulfate and alkali metal aluminate, one or more organic polymer flocculants or inorganic flocculants or organic polymer flocculants and inorganic flocculants A method for decolorizing and purifying waste water containing lignin and / or tannin, characterized in that the treatment with a composite flocculant is performed.
(3) The lignin according to (1) or (2), wherein the iron chloride is ferric chloride, the iron sulfate is ferric sulfate, and any of these and sodium aluminate are added. A method for decolorizing and purifying wastewater containing tannin.
(4) The method for decolorizing and purifying wastewater containing lignin and / or tannin according to any one of (1) to (3), further comprising solid-liquid separation.
(5) The decolorization purification treatment method according to any one of (1) to (4), wherein the waste water containing lignin and / or tannin is discharged from a shiitake cultivation process.
According to the inventor's research, by the above-mentioned specific chemical treatment, for example, shiitake cultivation wastewater and tea wastewater, which are black-brown colored liquids containing lignin and / or tannin, are present in the examples described later. It has been found that organic components that reduce the BOD and COD values contained in the glass and give a dark brown coloring phenomenon can be removed very efficiently and sufficiently. And after the chemical treatment of sequentially adding iron chloride or iron sulfate and an alkali metal aluminate, preferably one or more organic polymer flocculants or inorganic flocculants or the organic polymer flocculants By performing the treatment with the composite flocculant with the inorganic flocculant, the purpose of decolorization purification is achieved more efficiently in a short time, and if necessary, it is more preferable to perform a solid-liquid separation operation at the end. It has been found.

本発明によれば、BOD及びCOD値をもたらす有機物成分とリグニン及び/又はタンニンを含み黒褐色の着色液体である、例えば椎茸栽培もしくは製茶工程からの排水を、有害な物質を生じることなく、効率的に脱色浄化処理することが可能である。   According to the present invention, an organic component that provides BOD and COD values and a black-brown colored liquid containing lignin and / or tannin, for example, drainage from shiitake cultivation or tea making process can be efficiently performed without producing harmful substances. It is possible to decolorize and purify.

[浄化処理対象とする排水]
本発明により浄化処理されるリグニン及び/又はタンニンを含む典型的な排水としては、原木栽培法もしくは菌床栽培法である椎茸栽培工程及び製茶工程からの排水、などが挙げられる。前者の発生メカニズムについては前述した。後者の製茶排水としては、緑茶、紅茶、ウーロン茶など各種の製茶過程から排出される排水が対象とされる。かかる製茶排水中には、通常、BODが100〜2000ppm、CODが100〜1000ppm含まれるとともに、通常、褐色〜黒色の黒褐色に着色している。尚、該排水中にはBOD成分も含まれるが、本発明においてはCOD成分を指標とするので、以降BOD成分については言及しない。
[Wastewater to be treated]
Typical drainage containing lignin and / or tannin to be purified according to the present invention includes drainage from shiitake cultivation process and tea production process, which are log cultivation methods or fungus bed cultivation methods. The former generation mechanism has been described above. As the latter tea making waste water, waste water discharged from various tea making processes such as green tea, black tea and oolong tea is targeted. Such tea wastewater usually contains 100 to 2000 ppm of BOD and 100 to 1000 ppm of COD, and is usually colored brown to black. In addition, although BOD component is also contained in this waste_water | drain, since it uses COD component as a parameter | index in this invention, BOD component is not mentioned hereafter.

[排水処理プロセス]
本発明において、これらリグニン及び/又はタンニンを含み黒褐色の排水は、第1図に例示されるフローシートに従い、常温にて浄化処理が行われる。
即ち、リグニン及び/又はタンニンを含み黒褐色である排水を、被処理原水として処理槽に供給して、それに塩化鉄又は硫酸鉄を原水の色度の濃さに応じて100〜500ppm(有効成分として、以下同様)添加して、攪拌混合する。(以上、一次処理)次いで、アルミン酸アルカリ金属塩を100〜1,000ppm添加して攪拌混合し、pHを6.0〜8.0の範囲に調整することにより(以上、二次処理)、汚濁物質が凝集して沈殿物となるので、次いで濾過等の固液分離操作を施すことにより汚濁物質を分離除去できる。好ましくは、有機高分子凝集剤単独もしくは無機凝集剤又は該有機高分子凝集剤と該無機凝集剤との複合凝集剤を10〜500ppm添加する(三次処理)ことにより、水中での塊(フロック)が大きく且つ締まった形になり、結果的に固液分離が一層容易になる他、一層のCOD成分の除去が期待できる。尚、本発明で用いられる三次処理は、目的に応じた凝集剤を選定すればよく、市販されている凝集剤を適宜選択し使用すればよい、又、固液分離方法としては、デカンテーションの他、濾布濾過、砂濾過、フィルタープレスによる濾過、遠心分離法、サイクロン法、圧搾法など、通常用いられる如何なる方法を用いてもよく、現場での排水量とその汚染度に応じて操作性の良い方法を選択して用いればよい。尚、前記一次処理と二次処理は、略同時に行っても、或いは互いに添加順序を入れ替えても効果に変わりがないので特に断定するものではないが、pH調整のし易さ等の作業性等の点から、一次処理において塩化鉄又は硫酸鉄、二次処理においてアルミン酸アルカリ金属塩を用いる順序による順次添加が好ましい。
[Wastewater treatment process]
In the present invention, the black-brown wastewater containing lignin and / or tannin is purified at room temperature according to the flow sheet illustrated in FIG.
That is, wastewater that contains lignin and / or tannin and is dark brown is supplied to the treatment tank as raw water to be treated, and iron chloride or iron sulfate is added to it in an amount of 100 to 500 ppm (as an active ingredient) depending on the chromaticity of the raw water. , The same applies hereinafter) and stirring and mixing. (End, primary treatment) Next, 100-1,000 ppm of alkali metal aluminate is added and mixed by stirring. By adjusting the pH to the range of 6.0-8.0 (above, secondary treatment), pollutants are aggregated. Therefore, the contaminants can be separated and removed by performing a solid-liquid separation operation such as filtration. Preferably, an organic polymer flocculant alone or an inorganic flocculant, or a composite flocculant of the organic polymer flocculant and the inorganic flocculant is added in an amount of 10 to 500 ppm (tertiary treatment), whereby a mass in water (floc) As a result, the solid-liquid separation becomes easier, and further removal of COD components can be expected. In the tertiary treatment used in the present invention, a flocculant according to the purpose may be selected, and a commercially available flocculant may be appropriately selected and used. Also, as a solid-liquid separation method, decantation may be used. In addition, any commonly used method such as filter cloth filtration, sand filtration, filtration by a filter press, centrifugal separation method, cyclone method, pressing method, etc. may be used. A good method may be selected and used. It should be noted that the primary treatment and the secondary treatment are not particularly determined because the effect does not change even if they are performed almost simultaneously or the order of addition is interchanged, but workability such as ease of pH adjustment, etc. From this point, it is preferable to add them sequentially in the order of using iron chloride or iron sulfate in the primary treatment and alkali metal aluminate in the secondary treatment.

[必須とする薬剤]
塩化鉄は、塩化第一鉄、塩化第二鉄もしくは該塩化第二鉄とケイ酸ナトリウム及び硫酸との混合物であるポリシリカ鉄から成る群から選択して用いることが可能であるが、これらの内では塩化第二鉄が最も好ましい。硫酸鉄は、硫酸第一鉄、硫酸第二鉄もしくは通称「ポリ硫酸第二鉄」として工業的に供給されており、これらのいずれを用いてもよいが、コスト・入手性等の点から、これらの内では硫酸第二鉄が好ましい。以上の鉄化合物の内では、塩化第二鉄が最も好ましい。尚、本発明では粉体、水溶液を問わず、いずれの形態のものでも使用可能である。
アルミン酸アルカリ金属塩としては、アルミン酸リチウム、アルミン酸ナトリウムもしくはアルミン酸カリウムが使用可能であるが、これらの内では、コスト・入手性等の点からアルミン酸ナトリウムが最も好ましい。尚、本発明では粉体、水溶液を問わず、いずれの形態のアルミン酸アルカリ金属塩でも使用可能である。
[Required drugs]
Iron chloride can be selected from the group consisting of ferrous chloride, ferric chloride or polysilica iron, which is a mixture of ferric chloride and sodium silicate and sulfuric acid. Then, ferric chloride is most preferable. Iron sulfate is industrially supplied as ferrous sulfate, ferric sulfate or commonly called “polyferric sulfate”, and any of these may be used, but from the viewpoint of cost, availability, etc. Of these, ferric sulfate is preferred. Of the above iron compounds, ferric chloride is most preferred. In the present invention, any form of powder and aqueous solution can be used.
As the alkali metal aluminate, lithium aluminate, sodium aluminate or potassium aluminate can be used, and among these, sodium aluminate is most preferable from the viewpoint of cost, availability and the like. In the present invention, any form of alkali metal aluminate can be used regardless of powder or aqueous solution.

[凝集剤]
本発明においては、塩化鉄又は硫酸鉄とアルミン酸アルカリ金属塩とによる薬剤処理の後に、好ましくは、1種又は2種以上の、有機高分子凝集剤もしくは、無機凝集剤又は該有機高分子凝集剤と該無機凝集剤との複合凝集剤による処理を行った上で、汚濁物質を除去することが適当である。
該有機高分子凝集剤としては、アルギン酸ナトリウム、キトサン、ポリグルタミン酸もしくはその誘導体、カルボキシメチルセルロースナトリウム塩、ポリアクリル酸ナトリウム、ポリアクリルアミド、ポリアクリルアミドの部分加水分解塩、ポリアクリルアミドと四級化モノマーとの共重合体、マレイン酸系共重合体、ポリチオ尿素、ポリエチレンイミン、ポリビニルピリジン、ゼラチン、苛性化デンプン、ヒドロキシエチルセルロース、カルボキシメチルセルロース、多糖類、リグニンスルホン酸ナトリウム、(メタ)アクリル酸とアクリルアミドとの共重合体等、から成る群から選択される非イオン性高分子、アニオン性高分子、もしくはカチオン性高分子の1種以上である。
該無機凝集剤としては、硫酸バンド、ポリ塩化アルミニウム、酸化アルミニウム、水酸化アルミニウム、水酸化カルシウム、塩化カルシウム、炭酸カルシウム、硫酸カルシウム、酸化マグネシウム、水酸化マグネシウム、炭酸マグネシウム、硫酸マグネシウム、塩化マグネシウム、珪酸ナトリウム、亜硫酸ナトリウム、アルミニウムミョウバン類から成る群から選択される1種以上である。
無機凝集剤同士又は無機凝集剤と他の無機化合物との複合凝集剤、又は有機高分子凝集剤と無機凝集剤との複合凝集剤は、前記凝集剤を適宜組み合わせた製品として市販されているので、目的に応じ適宜選択して使用すればよい。
[Flocculant]
In the present invention, after the chemical treatment with iron chloride or iron sulfate and an alkali metal aluminate, preferably one or more organic polymer flocculants, inorganic flocculants, or organic polymer flocculants are used. It is appropriate to remove the pollutant after the treatment with the composite flocculant of the agent and the inorganic flocculant.
Examples of the organic polymer flocculant include sodium alginate, chitosan, polyglutamic acid or its derivative, carboxymethylcellulose sodium salt, sodium polyacrylate, polyacrylamide, polyacrylamide partial hydrolysis salt, polyacrylamide and quaternized monomer. Copolymer, maleic acid copolymer, polythiourea, polyethyleneimine, polyvinylpyridine, gelatin, causticized starch, hydroxyethylcellulose, carboxymethylcellulose, polysaccharide, sodium lignin sulfonate, copolymer of (meth) acrylic acid and acrylamide One or more of a nonionic polymer, an anionic polymer, or a cationic polymer selected from the group consisting of polymers and the like.
Examples of the inorganic flocculant include sulfate band, polyaluminum chloride, aluminum oxide, aluminum hydroxide, calcium hydroxide, calcium chloride, calcium carbonate, calcium sulfate, magnesium oxide, magnesium hydroxide, magnesium carbonate, magnesium sulfate, magnesium chloride, One or more selected from the group consisting of sodium silicate, sodium sulfite, and aluminum alum.
Since composite flocculants of inorganic flocculants or inorganic flocculants and other inorganic compounds, or organic flocculants and inorganic flocculants are commercially available as products in which the flocculants are appropriately combined. These may be selected and used as appropriate according to the purpose.

以下、実施例により本発明を更に詳細に説明するが、本発明はこれに限定されるものではない。
[処理液の物性測定方法と目標値]
1)pH
本発明で記載するpHは、ガラス電極法(JIS Z8802:1984)により測定された値を示す。本発明においては、全国統一排水基準を念頭にして、処理液の最終pHとして6.0〜8.0を目標として調整を行った。
2)リグニン及びタンニンの含有率定量方法
リグニンとタンニンの合計含有量の測定方法は、上水試験方法2001年版(2001年8月23
日、日本水道協会刊行)571〜572頁に収載されている、No.29タンニン・リグニン試験法「リンモリブデン酸による吸光光度法」に準拠した。本発明においては、リグニン及びタンニンの含有率は最終的に色度に反映されるので、目標値は特段定めなかった。
尚、本発明では、リグニン、タンニン夫々単独の含有率については、測定が煩雑なので測定を試みなかった。
3)色度
原理的にはJIS K0101:1998「工業用水試験法」第10.1項に収載の「白金・コバルト色度」試験法に準拠する方法である。即ち、「白金・コバルト色度」とは、水に溶存又はコロイド状で存在する物質による、淡黄色から黄褐色の程度を示すもので、水1L中に白金・コバルト標準液1mL(白金1mg及びコバルト0.5mg)を加えたときの色を「白金・コバルト色度1度」とし、色度が高いほど着色度合いが強い。詳しくは、米国大気・河川改善評議会(NCASI、National Council for Air and Stream Improvement, Inc.)の測定方法253に準拠し、波長465nmにて、HACH社製「多項目迅速水質分析計DR/2500型」を用いて測定した。
4)COD(Mn)
JIS K0101:2008「工場排水試験法」第17項に収載されている「100℃における過マンガン酸カリウムによる酸素消費量」に従った。
EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not limited to this.
[Measurement method and target value of treatment liquid]
1) pH
The pH described in the present invention indicates a value measured by the glass electrode method (JIS Z8802: 1984). In the present invention, the final pH of the treatment solution was adjusted to 6.0 to 8.0 with the national unified wastewater standard in mind.
2) Method for determining the content of lignin and tannin The method for measuring the total content of lignin and tannin is the water test method 2001 version (August 23, 2001).
According to the No. 29 tannin / lignin test method “absorption photometric method using phosphomolybdic acid”, published on pages 571 to 572 of Japan Water Works Association). In the present invention, the content of lignin and tannin is finally reflected in the chromaticity, and thus the target value is not particularly defined.
In the present invention, the lignin and tannin content alone was not measured because the measurement was complicated.
3) Chromaticity In principle, this is a method based on the “platinum / cobalt chromaticity” test method listed in JIS K0101: 1998 “Industrial water test method”, paragraph 10.1. That is, “platinum / cobalt chromaticity” means a degree of pale yellow to yellowish brown due to a substance dissolved or colloidally present in water, and 1 mL of platinum / cobalt standard solution (1 mg of platinum and 1 mg of platinum / cobalt) in 1 L of water. The color when cobalt 0.5mg) is added is "platinum / cobalt chromaticity 1 degree". The higher the chromaticity, the stronger the coloring degree. For details, in accordance with the measurement method 253 of the National Council for Air and Stream Improvement, Inc. (NCASI), at a wavelength of 465 nm, HACH's “Multi-item Rapid Water Quality Analyzer DR / 2500 Measured using “type”.
4) COD (Mn)
According to “Oxygen consumption by potassium permanganate at 100 ° C.” listed in Section 17 of JIS K0101: 2008 “Factory Wastewater Test Method”.

Figure 2011016048
Figure 2011016048

Figure 2011016048
Figure 2011016048

Figure 2011016048
Figure 2011016048

本発明を実施する一つの実施態様である、リグニン・タンニン含有排水の処理工程を示す。The treatment process of the lignin and tannin containing waste water which is one embodiment which implements this invention is shown. 椎茸栽培排水の被処理原水の写真を示す。A photograph of raw water for shiitake cultivation wastewater is shown. 椎茸栽培排水「実施例1」の写真を示す。左図:薬剤添加後、右図:固液分離後。The photograph of shiitake cultivation drainage "Example 1" is shown. Left: After drug addition, right: After solid-liquid separation. 椎茸栽培排水「実施例3」の写真を示す。左図:薬剤添加後、右図:固液分離後。The photograph of shiitake cultivation drainage "Example 3" is shown. Left: After drug addition, right: After solid-liquid separation. 椎茸栽培排水「比較例3」の写真を示す。左図:薬剤添加後、右図:固液分離後。The photograph of shiitake cultivation drainage "comparative example 3" is shown. Left: After drug addition, right: After solid-liquid separation.

Claims (5)

塩化鉄又は硫酸鉄とアルミン酸アルカリ金属塩とを添加することを特徴とする、リグニン及び/又はタンニンを含有する排水の脱色浄化処理方法。   A method for decolorizing and purifying waste water containing lignin and / or tannin, comprising adding iron chloride or iron sulfate and an alkali metal aluminate. 塩化鉄又は硫酸鉄とアルミン酸アルカリ金属塩とを添加後、さらに1種又は2種以上の、有機高分子凝集剤又は無機凝集剤又は該有機高分子凝集剤と該無機凝集剤との複合凝集剤による処理を行うことを特徴とする、リグニン及び/又はタンニンを含有する排水の脱色浄化処理方法。   After adding iron chloride or iron sulfate and alkali metal aluminate, one or more organic polymer flocculants or inorganic flocculants, or composite flocculants of the organic polymer flocculants and the inorganic flocculants A method for decolorizing and purifying wastewater containing lignin and / or tannin, characterized by performing treatment with an agent. 塩化鉄が塩化第二鉄であり、硫酸鉄が硫酸第二鉄であり、このいずれかとアルミン酸ナトリウムとを添加することを特徴とする、請求項1又は2記載のリグニン及び/又はタンニンを含有する排水の脱色浄化処理方法。   The lignin and / or tannin according to claim 1 or 2, characterized in that the iron chloride is ferric chloride and the iron sulfate is ferric sulfate, and any of these and sodium aluminate is added. Wastewater decolorization purification method. さらに固液分離を行うことを特徴とする、請求項1乃至3記載のリグニン及び/又はタンニンを含有する排水の脱色浄化処理方法。   4. The method for decolorizing and purifying waste water containing lignin and / or tannin according to claim 1, further comprising solid-liquid separation. リグニン及び/又はタンニンを含有する排水が、椎茸の栽培工程から排出されるものである、請求項1乃至4記載の脱色浄化処理方法。
The decolorization purification processing method of Claim 1 thru | or 4 with which the waste_water | drain containing a lignin and / or a tannin is discharged | emitted from the cultivation process of a shiitake mushroom.
JP2009161109A 2009-07-07 2009-07-07 Method of decoloring and purifying wastewater containing lignin and/or tannin Pending JP2011016048A (en)

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2012235732A (en) * 2011-05-11 2012-12-06 Noriomi Watanabe Hydroponic method for zingiber mioga
CN104445545A (en) * 2014-10-31 2015-03-25 田琳琳 Fast sewage treatment agent
CN109455842A (en) * 2018-11-13 2019-03-12 广东溢达纺织有限公司 A kind of efficient decolorizing technique of the organic solvent containing dyestuff
JP2021041318A (en) * 2019-09-09 2021-03-18 国立大学法人 宮崎大学 Method for making wood drying waste liquid colorless

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2012235732A (en) * 2011-05-11 2012-12-06 Noriomi Watanabe Hydroponic method for zingiber mioga
CN104445545A (en) * 2014-10-31 2015-03-25 田琳琳 Fast sewage treatment agent
CN109455842A (en) * 2018-11-13 2019-03-12 广东溢达纺织有限公司 A kind of efficient decolorizing technique of the organic solvent containing dyestuff
JP2021041318A (en) * 2019-09-09 2021-03-18 国立大学法人 宮崎大学 Method for making wood drying waste liquid colorless
JP7264473B2 (en) 2019-09-09 2023-04-25 国立大学法人 宮崎大学 Method for decolorizing wood drying waste liquid

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