JPS5929081A - Treatment of waste water containing humic acid and fulvic acid - Google Patents

Abstract

PURPOSE:To reduce effectively COD, by irradiating waste water contg. humic acid and fulvic acid with ionizing radiation under nitrogen-saturated conditions, adding an iron salt and H2O2, and adjusting pH to flocculate an iron component as iron hydroxide floc. CONSTITUTION:Gaseous N2 is diffused from a diffusion pipe 3 from an N2 feed pipe 2 into the waste water flowing 11 into a waste water tank 1 to form an N2 saturated state by aeration of the waste water. This water is introduced into a reactor 5, and irradiated with ionizing radiation, such as gamma-rays emitted by radioactive isotopes, generated from an electron beam accelerator 4. The irradiated waste water is introduced into an oxidation vessel, H2O2 and an iron salt, such as ferrous sulfate, are added 8, 9, and soluble polymer oxides are decomposed by oxidation in the waste water. An alkali soln. is added 10 to said decomposed water to adjust pH to >=4, the water is stored in a settling tank 7, pollutants are allowed to flocculate as iron hydroxide floc, and discharged 12, and the supernatant is allowed to flow out as the treated waste water acceptable by the water quality standard.

Description

【発明の詳細な説明】 法に関し，特にＣＯＤを低Ｆせしめる新規な廃水処理方
法に関する。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method, and particularly to a novel wastewater treatment method that reduces COD to a low F.

フミン酸やフルボ酸は広く廃水中に含まれ，特に都市ご
み浸出液や下水汚泥の湿式酸化分離液中海は多酸に含ま
れそおり，色度やＣＯＤを高くする原因となっている。Humic acid and fulvic acid are widely contained in wastewater, and in particular, municipal waste leachate and sewage sludge wet oxidation separation liquid Nakaumi tend to be contained in polyacids, causing high chromaticity and COD.

これらのｔ吻質は自浄作用では分解出来ず，また廃水処
理に広く行われている生物処理によっても分解出来ない
ことから，環境汚染上重要な問題になってきている。そ
こで各種の廃水処理方法が開発されているが，いずれも
汚濁負荷量の高い廃水の処理のためには大規模な設備や
膨大なラニングコストがかかるばかりでなく。These truncates cannot be decomposed by self-purification, nor can they be decomposed by biological treatment, which is widely used in wastewater treatment, so they have become an important problem in terms of environmental pollution. Various wastewater treatment methods have been developed to address this issue, but all of them not only require large-scale equipment and enormous running costs to treat wastewater with a high pollution load.

十分な処理効果が得られていない。１クリえば代表的処
理方法である活性炭吸着法では，フミン酸やフルボ酸が
有機高分子ｆヒ合物であるために活性炭中の細孔への吸
着、拡散が著しく不良であり、捷た他の代表的処理方法
であるオゾン酸化法では酸化外１’＋’ｉにより一部Ｃ
ＯＤＭル　を低下させることが出来るが１選択性がある
ためその効果は低く、又酸化分解の過稈でに：成した低
分子化合物は生物易分解性物質に変化してＢＯＤを増大
させるなど両処理方法共欠売をｆＴ　してぃて実用−に
大きな間順になっている。これらの処理方法に比べ凝喝
沈澱処理方法は、フミン酸やフルボ酸の物理化学的特注
を利殖して分離する有′切な方法であるが、その有効訃
は「水のようにフミン酸やフルボ酸の含有量が低い重合
に限られ、ｆダ濁負ＩＷｊ量の高い廃水でＩ′１ＣＯＤ
を低下せしめる効果は急激に減じてし１う欠点があった
。Sufficient treatment effect is not obtained. In the activated carbon adsorption method, which is a typical treatment method, since humic acid and fulvic acid are organic polymer f-hybrid compounds, adsorption and diffusion into the pores in the activated carbon are extremely poor, resulting in breakage and other problems. In the ozone oxidation method, which is a typical treatment method for
Although it is possible to reduce ODM, the effect is low due to monoselectivity, and low-molecular-weight compounds formed by excessive oxidative decomposition change into easily biodegradable substances and increase BOD. The treatment method is commonly used for fT, and it is in the order of practical use. Compared to these treatment methods, the coagulation-precipitation treatment method is an effective method for harvesting and separating the physicochemical customization of humic acid and fulvic acid. Limited to polymerization with low acid content, I'1 COD in wastewater with high f da turbidity negative IWj content.
The disadvantage was that the effect of reducing the

本発明の目的は、上記〔疋来技術の欠点を除去し。The purpose of the present invention is to eliminate the above-mentioned drawbacks of the conventional technology.

フミノ酸、フルボ酸による汚濁自荷量の高い廃水の重合
でもＣＯＤを効果的に低下させることができる廃水処理
方法を提供することにある。It is an object of the present invention to provide a wastewater treatment method that can effectively reduce COD even in the polymerization of wastewater with a high pollutant content due to humino acids and fulvic acids.

本発明者らは、汚濁負荷量の高い廃水に窒素飽和下で電
離性放射線を照射することにより、溶存有機物が高分子
化されることを見出し２　さらにこの生成した高分子物
質を効果的に除去する方法について研死を重ねた結唄、
この高分子物質を過酸ｆヒ水素と４塩とを用いて処理し
１次いでｐｆ■調節することにより、高効率で凝集分離
を行なうことができることを見出し９本発明に到達し７
た。The present inventors discovered that dissolved organic matter was polymerized by irradiating wastewater with a high pollution load with ionizing radiation under nitrogen saturation.2 Furthermore, the generated polymeric substances were effectively removed. Yuuta, who has spent a lot of time researching how to
It was discovered that coagulation and separation could be carried out with high efficiency by treating this polymeric substance with peracid f arsenic and tetrasalt and then adjusting pf. 9 Achieving the present invention 7
Ta.

すなわち１本発明はフミン酸、フルボ酸含有廃水を降水
処理するに際し、窒素飽和条件下で電離成分を水酸化秩
ブロックとして凝集分離させることを特徴とするもので
ある。Namely, the present invention is characterized in that, when wastewater containing humic acid and fulvic acid is subjected to precipitation treatment, ionized components are coagulated and separated as hydroxide blocks under nitrogen-saturated conditions.

以Ｆ１図…１を用いて本発明の詳細な説明する。Hereinafter, the present invention will be explained in detail using FIG.

１４１図は、フミン酸、フルボ酸を含有する下水汚泥湿
式酸化分離液を廃水として用い、これを窒素飽和条Ｐ′
ｌ：（曲線イ）と酸素飽和条件（曲線口）との各条件下
で５０Ｃｏ　　をｂ（射した場合の線量に対する廃液の
ＣＩＪ　ＤＭ７Ｌ　　の変ｒヒを示したものである。第
１図から酸素１唱和条件下では放射線による水、酸素の
分解が辱こってラジカルが生成し、　　ＣＯＩ）Ｍｎが
崖・シに減少するのに７１１２．窒素飽和条件下ではＣ
０Ｄｙｎ、　ｉはほぼ−・宝であることが分る。そこで
第１（ツ１の？Ｓ素砲和条注Ｆで１０．９　Ｍ　ｒｏｄ
照射した場合の啼液の汚濁物賓の分子量分イｆｉの変化
を、カラムトシてセファデックスＧ　２５（１７ｍｍ１
１．Ｘ　３７０＝ｎｍ　Ｈ）を１史甲したケルクロマト
グラフィで求めた浩采（曲線ハ）を未照射の場合のそれ
（曲細二）と削出して第２図に示す。第２図の曲線ハと
曲線変移しているのが４められ、これより４素中和下で
電離性放射線を照射することにより、廃液中の溶存有機
′吻質が高分子化されることが明らかである。」、記現
象は放射線照射によって溶存有機物のベンセン環の開裂
や結合の切断が起こり、鄭素飽和条件下であれば酸化に
よる低分子化が題行するのにｉＪＬ、窒素飽和条件下に
おいては重合により高分子ｆヒが起こるためである。Figure 141 shows that a sewage sludge wet oxidation separation liquid containing humic acid and fulvic acid is used as wastewater, and this is subjected to a nitrogen-saturated condition P'.
Figure 1 shows the change in CIJ DM7L of the waste liquid with respect to the dose when 50Co is irradiated with b (curve A) and oxygen saturation conditions (curve inlet). Under one chorus condition, the decomposition of water and oxygen by radiation is humiliated and radicals are generated, and COI)Mn decreases to a cliff/shi.7112. Under nitrogen saturated conditions, C
It can be seen that 0Dyn, i is almost a treasure. Therefore, the first (tsu1?S gun Wajo note F is 10.9 M rod
The change in the molecular weight of the contaminated liquid when irradiated was measured using Sephadex G 25 (17 mm 1
1. The curve (curve C) determined by Kernel chromatography using X370=nm H) is shown in FIG. It can be seen that the curve 4 shifts from the curve C in Figure 2, which indicates that the dissolved organic proboscis in the waste liquid is polymerized by irradiation with ionizing radiation under tetranuclear neutralization. is clear. '', the phenomenon described is that radiation irradiation causes the cleavage of benzene rings and bonds in dissolved organic matter, and under nitrogen-saturated conditions, the molecules are reduced by oxidation, but under nitrogen-saturated conditions, polymerization occurs. This is because polymer f-hi occurs.

次に第」図に示した各線量の放射＠照射廃液を試料とし
て用い、従来法に従いこれに横１（ＦｐＣｌ−３）によ
る凝集沈殿を行って沈殿物を除去した処理廃液のＣＯＤ
Ｍル低丁状態を第３図に示す。第３図中の各曲線毎の試
料に照射されていた放射線量は。Next, using the radiation @ irradiation waste liquid of each dose shown in Figure 1 as a sample, the COD of the treated waste liquid was subjected to coagulation sedimentation with horizontal 1 (FpCl-3) to remove the precipitate according to the conventional method.
FIG. 3 shows the M-le low state. What is the radiation dose irradiated to the sample for each curve in Figure 3?

ホ：未照り、↑　−＼：　：”、、２　ｔＶＩ　ｒａｄ
、　　）　：　７．８１ＶＩｒａｄ、チ：　Ｊ、　Ｏ（
Ｊ　Ｍ　ｒａｄである。この結果から、試作［である廃
液が放射線未照射（曲線ホ）である場合に比べ、放射線
を照射した場合、その線量が増加するに従い、　、Ｆｇ
ＣＡ３による処理廃液のＣ０Ｉ）＋、ｕｔ　の低下度合
そのものは未だ１−分ではない。Ho: Unlit, ↑ -\: :”,, 2 tVI rad
, ): 7.81 VIrad, Chi: J, O(
JM rad. From this result, when the waste liquid in the prototype [was irradiated with radiation compared to when it was not irradiated (curve E), as the dose increased, , Fg
The degree of decrease in C0I)+, ut of the treated waste liquid by CA3 is still not 1 min.

次に第１図の場合とｌｒｊ日壬にし２て得た！ｉシ射線
隈１０、７　Ｍｒａｄの処理廃液と未照射廃液とに対し
。Next, in the case of Figure 1 and lrj Hijimi, we obtained 2! For treated waste liquid and unirradiated waste liquid of 10,7 Mrad.

鉄塩（Ｆｅ５Ｏ４）と過酸化水素による酸化・凝集処理
を行った場合のＣＯＤ＋Ａｎ　の低下因襲を第１表に示
す。Table 1 shows the decrease in COD+An when oxidation/coagulation treatment with iron salt (Fe5O4) and hydrogen peroxide is performed.

第　　　　１　　　　表 ＝：’４ｐ　ＦｃＳＯ４ばＦｅｍＷ、　Ｈ２Ｏ，２は有
効酸素（Ｈ２０２中ｏ）逆算第１表の結束から、同じ鉄
塩と過酸化水素に−よる酸ずヒ・イ疑１イモ処理による
場合でも、予め放射線を照射しておく場合は照射しない
場合に比べてＣＯＤｅｉｎは太幅に低−Ｆすることが分
る。また第３図の曲線チ（照射線量１０．９　Ｍ　ｒａ
ｄ　）と第１表の照射線量Ｊ、　０．　’７　Ｍｒａ、
ｄの場合を比較すると、照射線量はほぼ同等であるにも
拘らず、従来法にょる鉄塩のみによる凝集沈殿たけでは
ＣＯＤＭ＋Ｌ　は３９０〜／ｌまでしか低下しないのに
比べ、鉄塩と過酸ｒヒ水素とを使用して酸化・凝集沈殿
処理することにより９８ｍグ／ｌ−４でＣＯＤＭ　ｎ　
　を減少させることが出来。Table 1 =: '4p FcSO4 is FemW, H2O,2 is available oxygen (O in H202) Back calculation From the combination in Table 1, by acid treatment with the same iron salt and hydrogen peroxide. It can be seen that even in the case where radiation is irradiated in advance, CODein becomes wider and lower in -F than when not irradiated. In addition, the curve Q in Figure 3 (irradiation dose 10.9 M ra
d) and the irradiation dose J in Table 1, 0. '7 Mra,
Comparing case d, even though the irradiation dose is almost the same, CODM+L only decreases to 390~/l with the conventional method of coagulation and precipitation using only iron salts, whereas with iron salts and peracid CODM n at 98 mg/l-4 by oxidation and coagulation-precipitation treatment using r arsenic.
can be reduced.

その効果に大差があることが分る。It turns out that there is a big difference in the effects.

次に本発明で使用する諸要素を説明する。Next, various elements used in the present invention will be explained.

電離性放射線としては、アルファ線１重陽子線。Ionizing radiation includes alpha rays and single deuteron rays.

ベータ線、電子線、中性子線、ガンマ線のいずれを用い
ても良いが、効果や照射効率を考慮し９通常は放射性同
位元素からのノｊンマ線、又は電子線加速器からの電、
子線を照射するのがＯＴ寸しい。Any of beta rays, electron rays, neutron rays, and gamma rays may be used, but in consideration of effectiveness and irradiation efficiency, normal rays from radioactive isotopes or electrons from electron beam accelerators are usually used.
Irradiating the sub-rays is too OT.

窒素は純粋である必要はなく、市販品程度で充麿゛であ
る。Nitrogen does not need to be pure; commercially available nitrogen is sufficient.

本発明において、鉄塩としては硫酸第１鉄や塩化第１′
法などのＦｅ　（ＩＩ）　　イオンを有する化合′吻。In the present invention, iron salts include ferrous sulfate and ferrous chloride.
Compounds with Fe(II) ions such as

硫酸第２鉄や塩化第２鉄などのＦ’、！　（ＩＩＩ）　
　イオンを有する化合物が用いられ、７時に硫酸第１秩
が高い酸化触媒能の点で望°ましく、低廉な価格の点で
も有利である。また硝酸第１鉄や硝酸第２秩などの硝酸
塩も十分な酸化触媒作用を有していて使用することがで
きるが、帛栄善化などの点で使用上留意する必架がある
。これらの鉄塩は同形物のまま。F' such as ferric sulfate and ferric chloride,! (III)
A compound having ions is used, and sulfuric acid is preferred in terms of its high oxidation catalytic ability and is also advantageous in terms of its low price. In addition, nitrates such as ferrous nitrate and ferric nitrate have sufficient oxidation catalytic activity and can be used, but there are certain considerations that must be taken when using them in terms of improved performance. These iron salts remain isomorphic.

または水ｔ７４液として廃水へ４υ口することができる
。Alternatively, it can be discharged into waste water as a water t74 liquid.

鉄塩の添Ｕｎ量は多缶になる程Ｃ０Ｉ）や色兜を低下さ
せることができるが、一方ではスラノ／：ｌも１曽尺す
るため＋　’ｌ’ｌ　１嘱′Ｆ’ｅ２＋　とじて］、　
Ｏ〜１．５００１ｑ／１の範囲で添ノＪＩ＋される。又
堝酸化水素の添加量は通當は廃水中のＣＯＤＮ４ｎ　Ｋ
　ＴＪ　Ｌ過酸化水素中の有効酸素ＩＩｉ！！算で０１
〜２倍の範囲で添加される。これら快を席と過酸化水素
との添加量は一般には上記範囲内で被酸ｒヒ゛吻背の挿
項、濃度１反り時間などによって適宜・ぺ定される。As the number of cans increases, the amount of iron salt added can lower C0I) and colored helmets, but on the other hand, since Surano/:l also increases by 1 scale, + 'l'l 1嘱'F'e2+ ],
It is added JI+ in the range of O to 1.5001q/1. The amount of hydrogen oxide added is generally CODN4nK in wastewater.
TJ L Effective oxygen in hydrogen peroxide IIi! ! Calculation: 01
It is added in a range of ~2 times. The amount of hydrogen peroxide to be added is generally determined as appropriate within the above-mentioned range based on the interpolation of the oxidized r, the proboscis, the concentration per warping time, etc.

反応時間は廃水中の被酸化物質の種類、儂妾。The reaction time depends on the type of oxidized substance in the wastewater.

反応温度、横置看、過酸化水素帛などにより異なるが、
　１１ｆｌ　、嘱′、常温で、″１分〜２４時間であり
、この間に反１芯は完結する。It varies depending on the reaction temperature, horizontal orientation, hydrogen peroxide cloth, etc.
It takes 1 minute to 24 hours at 11 fl liters, 100 ml, and room temperature, and one core is completed during this time.

酸化処理を終了した酸化処理廃水の〃Ｈを調節するため
に使用するアルカリ剤としては、アルカリ性を呈するも
のであれば良く９例えば苛叶ノータ、苛性カリ、消石灰
、生石灰などいずれもよい。The alkaline agent used to adjust the 〃H of the oxidized wastewater after oxidation treatment may be any alkaline agent, such as caustic powder, caustic potash, slaked lime, quicklime, etc.

次に本発明を実施するのに好適な装置系統の概略を第４
図に示す。第４図において、廃水タンク■には廃水が送
水管１１から流５人し、一方、窒素供給管２からは窒素
カスが散気管；３を通して廃水中に散気され、廃水を曝
気して窒素飽和状態にする。窒素飽和状態となった廃液
は反応器１５内に導入され、上方の電子線加速器４から
発生する電離性放射線が照射される。次に放射線を照射
された廃液は、酸化槽６に受は入れられ、これに過酸・
化水素注入管８と鉄塩投入管９とからそれぞれ薬剤が添
加され、廃液中の高分子化された溶存有機′吻を酸化分
解する。該酸化槽６の排液流路にはアル２ノリ液注入管
］０が役けられ、酸化分解後の廃液にアルカリ液がｐＨ
４以上の沈１ｉ−’ｆｆｉに適切なｐＦＩになるように
逐次注入される。ｐＨ調節後の廃水は沈殿槽７に貯留さ
れ、ここで汚濁物質を水酸化鉄ブロックとして沈殿させ
て排泥管１２から排出し。Next, the outline of the equipment system suitable for carrying out the present invention will be explained in the fourth section.
As shown in the figure. In Figure 4, wastewater flows into the wastewater tank ■ from the water supply pipe 11, while nitrogen sludge is diffused into the wastewater from the nitrogen supply pipe 2 through the aeration pipe 3, which aerates the wastewater and nitrogenizes it. Bring to saturation. The nitrogen-saturated waste liquid is introduced into the reactor 15 and irradiated with ionizing radiation generated from the electron beam accelerator 4 above. Next, the irradiated waste liquid is received in the oxidation tank 6, which is filled with peracid and
Chemicals are added from the hydrogen chloride injection pipe 8 and the iron salt injection pipe 9, respectively, to oxidize and decompose the polymerized dissolved organic compounds in the waste liquid. An alkaline liquid injection pipe] 0 is used in the drainage flow path of the oxidation tank 6, and the alkaline liquid adjusts the pH of the waste liquid after oxidation and decomposition.
Four or more precipitates 1i-'ffi are injected sequentially to the appropriate pFI. The pH-adjusted wastewater is stored in a sedimentation tank 7, where the pollutants are precipitated as iron hydroxide blocks and discharged from the sludge pipe 12.

上澄液は廃水処理されたξ置市水質の廃水として流出さ
せる。The supernatant liquid will be discharged as treated wastewater.

本発明によれば、自ａ）作用では分解できないフミン酸
やフルボ酸を旨い汚濁負荷量で含有する廃水を極めて簡
雫な操作で効率よく処理して良好な処理水とし−Ｃｌ１
ｔＪ流することができる。また処理コストも極めて安価
である。According to the present invention, a) wastewater containing humic acid and fulvic acid, which cannot be decomposed by natural action, in a high pollutant load is efficiently treated with extremely simple operations to produce good treated water - Cl1
tJ can flow. Furthermore, the processing cost is extremely low.

しＪ下１本発明を実施例により具体的に説明する。The present invention will be explained in more detail with reference to Examples.

実）Ａ、１列　　　４ ［水汚泥の湿式酸化分離液を原廃水として、先ずこれを
生物処理により凝集沈殿せしめて沈殿物を分離し、た後
、窒素で曝気で窒素飽和状態と（７゜次いて″Ｃｖ　　
を線源として電離開放射線を０．５　Ｍｒｑｄ　７時間
の線計率”７’　５．０　Ｍ　ｒａｄ　Ｉｆ！射した。Actual) A, row 1 4 [Using the wet oxidation separated liquid of water sludge as raw wastewater, it was first coagulated and precipitated by biological treatment to separate the precipitate, and then aerated with nitrogen to bring it to a nitrogen saturated state (7° Then ``Cv
Ionizing open radiation was emitted at a line rate of 7' 5.0 Mrad If! for 7 hours using a radiation source of 0.5 Mrqd.

次にＡ酸ｆヒ水素を有効酸素換算で１．５０　ｍｑ　／
　ｔと、硫４′第１．Ｔ＋をＦｌ！２＋　とじてｓａｏ
ｍ１７ｔとをそれぞれ添）ノｆ＋　して約１０分間酸化
した後、苛訃ノータによりｐＨを４．５〜５の範囲に調
整し、水酸ｆヒ第２鉄ブロックを沈殿分離した。各段階
及び婦略の放流水のＣＯｌ）＋Ａ１１　　を第２表に示
す。Next, add A acid f arsenic to 1.50 mq/in terms of effective oxygen.
t and sulfur 4' 1st. Fl T+! 2+ close sao
After oxidizing for about 10 minutes, the pH was adjusted to a range of 4.5 to 5 using a caustic heater, and the ferric hydroxide block was separated by precipitation. Table 2 shows the CO1+A11 of the effluent water at each stage and stage.

実Ｍｉｉ　ｌ＋１　　２ 都市ごみの熱分解撥水を原廃水として実施例１と同様に
廃水処理した。１目し、放射線ｌは２．０　＋ＶＩｒｎ
ｄ　、過酸化水素の冷加量は有効酸素換算で２０’ｎｇ
／　ｔ　、　ｆｉｇ第１秩ノ添加量ばＦｅ”として１０
０ｍｑ７ｔであった。結果を第２表に示す。Wastewater was treated in the same manner as in Example 1 using the pyrolyzed water repellent of Mii l+1 2 municipal waste as raw wastewater. 1 eye, radiation l is 2.0 +VIrn
d. The amount of hydrogen peroxide cooled is 20'ng in terms of effective oxygen.
/t, fig 1st addition amount is 10 as “Fe”
It was 0mq7t. The results are shown in Table 2.

実施例　３ 都市ごみ浸出液を凝集沈殿処理水を原廃水と（て実施例
１と同様に廃水処理した。但し、放射ｉ惜は３．０　Ｍ
　ｒａｄ　、過酸化水素の添加量は有効酸［換算で１０
０ｍｇ／ｌ、（＋Ｒ酸第１秩の添υ１１量はＦｅ２とし
て３００ｍ？／ｌであった。結果を第２表にンす。Example 3 Wastewater was treated in the same manner as in Example 1 by coagulating and precipitating the municipal waste leachate and treating the treated water with raw wastewater. However, the radiation concentration was 3.0 M.
rad, the amount of hydrogen peroxide added is equivalent to effective acid [10
The amount of added υ11 of the +R acid Daichichichichi was 300 m?/l as Fe2. The results are shown in Table 2.

第　　　２　　　表 〔ＣＯＤＭｎ：ｍｇ／ｌ ＊　原廃水を４倍希釈したもの 第２表から分るように、放射線処理の段階で（ＣＯＩ）
Ｍｎ（ｄ冶んど変化せず却って微増しているこれに過酸
化水素と鉄塩とによる酸化とさらにｐｆｌ調整による水
酸化鉄ブロックの化１股除去とを組み介わすることによ
り、ＣＯＤＭｎ　を顕著に低下させることができる。Table 2 [CODMn: mg/l *4-fold dilution of raw wastewater As can be seen from Table 2, at the stage of radiation treatment (COI)
By combining oxidation with hydrogen peroxide and iron salt and removal of the iron hydroxide block by adjusting pfl, CODMn (which does not change over time but increases slightly) can be reduced. can be significantly reduced.

４、　ｔ’２１　ｔｒｉの簡単な説明 第１図シま廃水の窒素飽和条件と酸素飽和条件との各集
注ドにおける放射線照射によるＣ０Ｄｕｎ、低下を比較
するグラフ、第２図は窒素飽和条件下での放射線照射に
よる溶存有機物の分子風分布の変イ）を示す図、第３図
は・疑集沈殿の前処理としての恢射線照射の有無および
線量の効果を示すグラフ。4. Brief explanation of t'21 tri Figure 1 is a graph comparing the decrease in C0Dun due to radiation irradiation under nitrogen-saturated conditions and oxygen-saturated conditions for wastewater. Figure 2 is a graph comparing the decrease in C0Dun due to radiation irradiation under nitrogen-saturated conditions and oxygen-saturated conditions. Fig. 3 is a graph showing the effects of radiation exposure and dose as a pretreatment for collective precipitation.

第４図は本発明方法を実姉する装置系統の慨略図である
。FIG. 4 is a schematic diagram of a system of equipment implementing the method of the present invention.

］　廃水タンク　　　　２−窒素Ｕ（給管３　散気管　
　　　　　４　電子線加ｉ末器５　反応器　　　　　　
６−酸化槽 ７・沈殿槽　　　　　　８・過酸化水素注入管９　鉄塩
投入管　　　１０・アルカリ液注入管１１　・送水管　
　　　　１２・・排泥管。] Wastewater tank 2-Nitrogen U (supply pipe 3 aeration pipe
4 Electron beam adder 5 Reactor
6-Oxidation tank 7・Sedimentation tank 8・Hydrogen peroxide injection pipe 9 Iron salt injection pipe 10・Alkali solution injection pipe 11 ・Water pipe
12...Sludge drainage pipe.

第１図 ０　　　　　　１０　　　　　２０　２４線量（Ｍ　ｒ
ａｄ　） 第２図 ボ’Ｉ工＋Ｌンク゛リコーＩＬ相当令子量（−）イ’ｉ
　　　ｎ　で１量　（ｍ！） 第３図 第４図 ４２５Figure 1 0 10 20 24 dose (M r
ad ) Figure 2 Bo' I work + L link Ricoh IL equivalent weight (-) I'i
1 quantity in n (m!) Figure 3 Figure 4 425

Claims (1)

【特許請求の範囲】 （１）　　フミン酸、フルボ酸含有廃水を廃水処理する
ＩＣ際し１．窒素飽和条件下で電離性放射線を照射した
後、横置と過酸ｒヒ水素とを添加して酸化分解し１次い
でｐＨを４以上に調整して峡＋Ｊ’ｉ分を水酸化鉄ブロ
ックとして凝集分離させることを特徴とするフミン酸、
フルボ酸含有廃水の処理方法。 ＋２１　　ｃ！ｙ訂請求の範囲第１頃において、ｕ；嘆
は（随−第］　ｒ′Ｉ６であることを特徴とするフミン
酸。 フルボ酸含有廃水の処理方法。 （３）　　特許請求の・！α囲第１項４たけ第２項にお
いて、横置の添加者はｈｓ、２＋　とじてｌ　Ｏ〜１．
５００ｍｙ　／　、ｌ−であるフミン酸、フルボ酸含有
廃水の処理方法。 （・ｌ）　侍へ′１請求の範囲第１項において、過酸ｆ
ヒ水素の添加ｌは、廃水中のＣＩ〕ＤＭ＋Ｌ　　に刑し
過酸化水素中の有効酸素換算で０１〜２倍であるフミン
酸、フルボ含有廃水の処理方法。[Scope of Claims] (1) When using an IC for treating wastewater containing humic acid and fulvic acid, 1. After being irradiated with ionizing radiation under nitrogen-saturated conditions, it was placed horizontally and oxidized and decomposed by adding arsenic peroxide, then the pH was adjusted to 4 or more, and the +J'i fraction was used as an iron hydroxide block. Humic acid characterized by coagulation and separation,
A method for treating wastewater containing fulvic acid. +21 c! Humic acid characterized in that in the first part of the claim, u; In the first term 4 and the second term, the horizontal additive is hs, 2+ and l O~1.
A method for treating wastewater containing humic acid and fulvic acid at a concentration of 500 my/l. (・l) To the Samurai'1 In claim 1, peracid f
A method for treating wastewater containing humic acid and fulvic acid, in which the amount of arsenic added is 0.1 to 2 times the amount of effective oxygen in hydrogen peroxide when the amount of CI in the wastewater is DM+L.