JP2668711B2 - Paper and pulp wastewater coagulation treatment method - Google Patents
Paper and pulp wastewater coagulation treatment methodInfo
- Publication number
- JP2668711B2 JP2668711B2 JP63191567A JP19156788A JP2668711B2 JP 2668711 B2 JP2668711 B2 JP 2668711B2 JP 63191567 A JP63191567 A JP 63191567A JP 19156788 A JP19156788 A JP 19156788A JP 2668711 B2 JP2668711 B2 JP 2668711B2
- Authority
- JP
- Japan
- Prior art keywords
- paper
- wastewater
- floc
- pulp wastewater
- added
- 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.)
- Expired - Fee Related
Links
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- Separation Of Suspended Particles By Flocculating Agents (AREA)
Description
【発明の詳細な説明】 〔産業上の利用分野〕 本発明は製紙工場等から排出される紙・パルプ成分を
懸濁物として含む廃水の凝集処理方法に関する。DETAILED DESCRIPTION OF THE INVENTION [Industrial field of use] The present invention relates to a method for coagulating waste water containing paper / pulp components discharged from a paper mill or the like as a suspension.
紙・パルプ廃水の凝集処理には、硫酸アルミニウム、
ポリ塩化アルミニウム等の無機凝集剤と、ポリアクリル
アミドまたはその加水分解物等のノニオン性あるいはア
ニオン性の高分子凝集剤とを併用して凝集処理をする方
法が一般に行なわれている。この場合通常、無機凝集剤
を添加すると廃水のpHが酸性になるため必要に応じてア
ルカリによつてpH調整が行なわれている。Aluminum sulfate,
A method of performing an aggregating treatment using an inorganic aggregating agent such as polyaluminum chloride and a nonionic or anionic polymer aggregating agent such as polyacrylamide or a hydrolyzate thereof in combination is generally used. In this case, the pH of the wastewater is usually acidified when an inorganic coagulant is added, so that the pH is adjusted with an alkali if necessary.
しかしながら、無機凝集剤とアニオン性高分子凝集剤
を併用する場合には無機凝集剤によつて低くなつた廃水
のpHを中性付近に調整しなければ良好な凝集処理を行う
ことができないことから、多量のアルカリを要し経済的
に好ましい方法とは言えない。However, when the inorganic coagulant and the anionic polymer coagulant are used together, good coagulation treatment cannot be performed unless the pH of the wastewater lowered by the inorganic coagulant is adjusted to near neutral. It requires a large amount of alkali and is not economically preferable.
また、無機凝集剤とノニオン性高分子凝集剤を併用す
る場合には低pH領域すなわち酸性側でもフロツクを形成
し凝集は行われるものの、そのフロツクの大きさ、強さ
などが充分でなく必ずしも満足な結果が得られていな
い。When an inorganic flocculant and a nonionic polymer flocculant are used together, floc is formed and flocculation is performed even in a low pH region, that is, on the acidic side, but the size and strength of the floc are not sufficient and are not always satisfactory. No results have been obtained.
かかる現状に鑑み本発明者等はpH調整が不要で凝集性
能の優れた処理方法について検討し、特定の無機系凝集
剤と特定の有機高分子凝集剤との併用による紙・パルプ
廃水の凝集処理方法を見い出し本発明を完成させた。In view of the present situation, the present inventors have examined a treatment method that does not require pH adjustment and has excellent flocculation performance, and consolidate paper / pulp wastewater by co-using a specific inorganic flocculant and a specific organic polymer flocculant. A method was found and the present invention was completed.
本発明の要旨は紙・パルプ廃水に対してアルミニウム
塩系の無機凝集剤を添加し、次いでアクリルアミドと下
記のモノマー（ａ） との重量組成比が98〜50:2〜50なる共重合体であり固有
粘度［η］が８以上であるカオチン性高分子凝集剤を添
加する紙・パルプ廃水の凝集処理方法にある。The gist of the present invention is to add an aluminum salt-based inorganic coagulant to paper / pulp wastewater, and then add acrylamide and the following monomer (a) Is a copolymer having a weight composition ratio of 98 to 50: 2 to 50 and a chaotic polymer flocculant having an intrinsic viscosity [η] of 8 or more.
本発明において処理対象となる紙・パルプ廃水は製紙
工場等から排出される紙・パルプ成分を懸濁物として含
む廃水である。The paper / pulp wastewater to be treated in the present invention is a wastewater containing paper / pulp components discharged from a paper mill or the like as a suspension.
これらの廃水に対して先ず硫酸アルミニウム、ポリ塩
化アルミニウム等のアルミニウム塩系の無機凝集剤を添
加するが、通常負電荷を有している紙・パルプ廃水中の
懸濁粒子は無機凝集剤によつてその負電荷が中和され微
細な凝結フロツクを形成する。Aluminum salt-based inorganic coagulants such as aluminum sulfate and polyaluminum chloride are first added to these wastewaters, but suspended particles in paper / pulp wastewater, which usually have a negative charge, are not added by the inorganic coagulant. The negative charge is then neutralized to form a fine floc.
これらの無機凝集剤の添加量は廃水の性状に応じて適
宜選定されうるが通常廃水に対してアルミニウム換算と
して２〜100ppm程度添加すればよい。The addition amount of these inorganic coagulants may be appropriately selected according to the properties of the wastewater, but it is usually added to the wastewater in an amount of about 2 to 100 ppm in terms of aluminum.
無機凝集剤の添加によつて廃水のpH値は低下して酸性
となるが、本発明においては、通常特別のpH調整をする
ことなくカオチン性高分子凝集剤が添加される。但しpH
値が5.5より低い場合は凝集性が低下するため若干のア
ルカリ成分の添加によつてpH値を5.5〜7.0の範囲にすれ
ば更に良好な結果を得ることができる。The pH value of the wastewater is lowered and becomes acidic by the addition of the inorganic coagulant, but in the present invention, the chaotic polymer coagulant is usually added without special pH adjustment. However, pH
When the value is lower than 5.5, the cohesiveness decreases, so that a better result can be obtained by adjusting the pH value in the range of 5.5 to 7.0 by adding a little alkali component.
本発明において無機凝集剤の添加に続いて特定のカオ
チン性有機高分子凝集剤を添加するが、これによつて前
記の凝結フロツクが更に大きなフロツクに成長し、強度
が強くて沈降性の良好なフロツクとなる。In the present invention, a specific chaotic organic polymer flocculant is added subsequent to the addition of the inorganic flocculant, whereby the flocculation floc grows into a larger floc and has a strong strength and good sedimentation. Become a flock.
カオチン性高分子凝集剤としては前記の共重合体が用
いられるが、カオチン性のモノマー（ａ）としてはジメ
チルアミノエチルメタクリレート、ジエチルアミノエチ
ルメタクリレート、ジエチルアミノエチルアクリレー
ト、ジメチルアミノエチルアクリレート、ジメチルアミ
ノプロピルメタクリルアミド、ジメチルアミノプロピル
アクリルアミド、などの酸塩、第４級アンモニウム塩な
どを挙げることができる。The above-mentioned copolymer is used as the chaotic polymer flocculant, and as the chaotic monomer (a), dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate, diethylaminoethyl acrylate, dimethylaminoethyl acrylate, dimethylaminopropyl methacrylamide. , Dimethylaminopropylacrylamide, and the like, and quaternary ammonium salts.
このカオチン性高分子凝集剤において、アクリルアミ
ドをカオチン性のモノマー（ａ）との重量組成比が前記
範囲をはずれると凝集性能が低下するので好ましくな
い。即ち、カオチン性のモノマー（ａ）の含有量が50重
量部を超えた凝集剤を使用する場合は大きなフロツクが
形成されるもののフロツクのしまりが悪いためその沈降
性が不充分であると共に水流によつてフロツクが破壊さ
れ微小フロツクが処理水中に流出するという問題が生じ
る。又、モノマー（ａ）の含有量が２重量％より少ない
と懸濁物の負荷電が充分に中和されないため処理水のCO
D値が高く、清澄度が不充分なものとなる。尚、カオチ
ン性高分子凝集剤中の両モノマーの重量組成比は95〜7
0:5〜30の範囲であることがより好ましい。In this chaotic polymer flocculant, if the weight composition ratio of acrylamide to the chaotic monomer (a) is out of the above range, the flocculation performance is deteriorated, which is not preferable. That is, when a flocculant having a content of the chaotic monomer (a) exceeding 50 parts by weight is used, a large floc is formed, but the flocculence is poor due to poor flocculation, and the sedimentation is insufficient and the water flow is reduced. Therefore, there is a problem that the flocks are destroyed and minute flocs flow into the treated water. If the content of the monomer (a) is less than 2% by weight, the negative charge of the suspension will not be sufficiently neutralized and the CO
The D value is high and the clarity is insufficient. Incidentally, the weight composition ratio of both monomers in the chaotic polymer flocculant is 95 to 7
The range of 0: 5 to 30 is more preferable.
また、フロツク大きさ、しまり等を考慮すると、カオ
チン性高分子凝集剤は固有粘度〔η〕（1N−NaNO3、30
℃）が８（dl/g）以上のものであることが好ましく10
（dl/g）以上のものであることがより好ましい。In consideration of the floc size, tightness, etc., the chaotic polymer flocculant has an intrinsic viscosity [η] (1N-NaNO 3 , 30
C) is preferably 8 (dl / g) or more.
(Dl / g) or more is more preferable.
以下に実施例を用いて本発明をさらに具体的に説明す
る。Hereinafter, the present invention will be described more specifically with reference to examples.
なお、各種の測定は以下の方法に準拠して行つた。
又、実施例においてはアクリルアミドと第１表のカオチ
ン性のモノマー（ａ）からなるカオチン性高分子凝集剤
を使用した。Various measurements were performed according to the following methods.
Further, in the examples, a chaotic polymer flocculant comprising acrylamide and the chaotic monomer (a) shown in Table 1 was used.
（１） カオチン度 コニカルビーカーに脱イオン水90mlをとり、試料ポリ
マーの500ppm溶液10mlを加え、塩酸水溶液でpHを4.0と
し、約１分間撹拌する。(1) Degree of Kaothin Take 90 ml of deionized water in a conical beaker, add 10 ml of a 500 ppm solution of the sample polymer, adjust the pH to 4.0 with an aqueous hydrochloric acid solution, and stir for about 1 minute.
次に、トルイジンブル−指示薬を２〜３滴加え、N/40
0ポリビニル硫酸カリウム（PVSK）試薬で滴定される。Next, add 2-3 drops of toluidine-indicator and add N / 40
0 Titrated with polyvinyl potassium sulfate (PVSK) reagent.
滴定速度は2ml/分とし、検水が青から赤紫色に変色し
10秒以上保持する時点を終点とする。The titration speed was 2 ml / min, and the sample changed color from blue to magenta.
The end point is the time of holding for 10 seconds or more.
カオチン度は下記の計算式により求められる。 The degree of chaotin is determined by the following formula.
（２） アニオン度 コニカルビーカーに脱イオン水90mlをとり、N/10の苛
性ソーダ水溶液0.5mlを加え、撹拌下N/20メチルグリコ
ールキトサン試薬5mlを滴下し、１分間以上撹はんす
る。 (2) Degree of anion Take 90 ml of deionized water in a conical beaker, add 0.5 ml of an N / 10 aqueous solution of caustic soda, add 5 ml of N / 20 methyl glycol chitosan reagent dropwise with stirring, and stir for 1 minute or more.
次に、試料ポリマーの500ppm溶液10mlをゆつくり滴下
し、滴下後さらに５分間以上撹拌した後、トルイジンブ
ル−指示薬を２〜３滴加え、N/400ポリビニル硫酸カリ
ウム（PVSK）試薬で滴定する。Next, 10 ml of a 500 ppm solution of the sample polymer is slowly added dropwise, and after the addition, the mixture is stirred for 5 minutes or more. Then, 2 to 3 drops of toluidine-indicator are added, and titrated with N / 400 polyvinyl potassium sulfate (PVSK) reagent.
滴定速度は2ml/分とし、検水が青から赤紫色に変色し
10秒以上保持する時点を終点とする。The titration speed was 2 ml / min, and the sample changed color from blue to magenta.
The end point is the time of holding for 10 seconds or more.
なお、上記操作において、試料を添加しない場合をブ
ランク試験とする。In the above operation, the case where no sample is added is defined as a blank test.
アニオン度は下記の計算式により求められる。 The degree of anion is determined by the following formula.
（３） 凝集沈降試験（ジヤーテスト） 無機凝集剤を添加し、所定のpHに調整した製紙工場廃
水各々500mlをビーカーにとり、ジヤーテスターにか
け、高分子凝集剤を所定量添加混合し、フロツクの大き
さ、沈降速度、処理水のCODを測定する。 (3) Coagulation sedimentation test (Jar test) Add 500 ml each of paper mill wastewater adjusted to a predetermined pH by adding an inorganic coagulant to a beaker, place it in a jar tester, add and mix a predetermined amount of a polymer coagulant, Measure sedimentation velocity and COD of treated water.
実施例１〜４及び参考例１〜４ Ａ製紙工場の製紙廃水（COD215ppm）にポリ塩化アル
ミニウム（200ppm）を加えたところpHは5.7となつた。
この液500mlづつビーカーに分取してジヤーテスターに
かけ第１表に示した高分子凝集剤〜を各0.5ppm/廃
水の割合で添加して撹拌混合し、フロツク径、フロツク
の沈降速度、処理水のCODを測定した。Examples 1 to 4 and Reference Examples 1 to 4 A When polyaluminum chloride (200 ppm) was added to the papermaking wastewater (COD 215 ppm) of the paper mill, the pH was 5.7.
A 500 ml portion of this solution was taken into a beaker, placed in a beaker, and the polymer flocculant shown in Table 1 was added at a ratio of 0.5 ppm / waste water at a ratio of 0.5 ppm / waste water, followed by stirring and mixing. The floc diameter, floc sedimentation speed, and treated water COD was measured.
その結果を第２表に示すがいずれの場合もフロツク径
が大きくて沈降時間は短かく、フロツク強度、しまり等
も良好であつた。The results are shown in Table 2. In all cases, the flock diameter was large, the sedimentation time was short, and the flock strength and tightness were good.
尚、ポリ塩化アルミニウム添加後、アルカリによつて
pH値を6.8に調整してその他の条件は実施例１〜４と同
様にして凝集テストを実施したところこの場合も良好な
結果が得られた（参考例１〜４）。After adding polyaluminum chloride,
A pH value was adjusted to 6.8, and other conditions were the same as in Examples 1 to 4, and an aggregation test was carried out. Good results were obtained also in this case (Reference Examples 1 to 4).
比較例１〜４ 第１表の高分子凝集剤〜を用いて実施例１と同様
の条件で凝集性能を評価し、第２表の結果を得た。いず
れの場合もフロツク径が小さくて沈降時間は長く、COD
値も高かつた。Comparative Examples 1 to 4 Polymer flocculants of Table 1 were used to evaluate the flocculation performance under the same conditions as in Example 1, and the results of Table 2 were obtained. In each case, the floc diameter is small, the sedimentation time is long, and the COD
Value was high, too.
実施例５〜８ Ｂ製紙工場の製紙廃水（COD160ppm）に対して硫酸ア
ルミニウム250ppmを添加したところpH値は6.3になつ
た。この液500mlずつをビーカーに分取してジヤーテス
ターにかけ、第１表の高分子凝集剤〜を各々0.8ppm
/廃水の割合で添加して撹拌混合し、フロツク径、フロ
ツクの沈降速度、処理水COD等を測定し第２表の結果を
得た。Examples 5 to 8 When 250 ppm of aluminum sulfate was added to the papermaking wastewater (COD 160 ppm) of the B paper mill, the pH value became 6.3. 500 ml each of this solution was placed in a beaker and placed on a jar tester to give 0.8 ppm of each polymer coagulant in Table 1.
/ Add the wastewater at a ratio and stir-mix, measure the floc diameter, flocculation rate, treated water COD, etc., and obtain the results shown in Table 2.
いずれの場合もフロツク径が大きくて沈降時間が短
く、フロツクの強度、しまりも良好であつた。In each case, the floc diameter was large, the sedimentation time was short, and the floc strength and tightness were good.
比較例５〜８ 第１表の高分子凝集剤〜を用いて実施例５と同様
の条件で凝集性能を評価し第２表の結果を得た。いずれ
の場合もフロツク径が小さくて沈降時間は長かつた。Comparative Examples 5 to 8 Polymer aggregation agents shown in Table 1 were used to evaluate the aggregation performance under the same conditions as in Example 5, and the results shown in Table 2 were obtained. In each case, the floc diameter was small and the sedimentation time was long.
〔発明の効果〕 本発明の方法によれば充分な大きさと強度を有した沈
降性の優れたフロツクを形成させることができ、アルカ
リ添加によるpH調整をすることなく紙・パルプ廃水の凝
集処理を行なうことができる。 [Effects of the Invention] According to the method of the present invention, it is possible to form a floc having sufficient size and strength and excellent sedimentation property, and to perform coagulation treatment of paper / pulp wastewater without pH adjustment by addition of alkali. Can be done.
───────────────────────────────────────────────────── フロントページの続き (56)参考文献 特開 昭52−42649（ＪＰ，Ａ) 特開 昭56−101992（ＪＰ，Ａ) 特公 昭53−41911（ＪＰ，Ｂ２) ────────────────────────────────────────────────── ─── Continuation of the front page (56) Reference JP-A-52-42649 (JP, A) JP-A-56-101992 (JP, A) JP-B-53-41911 (JP, B2)
Claims (1)
の無機凝集剤を添加し、次いでアクリルアミドと下記の
モノマー（ａ）との重量組成比が98〜50:2〜50なる共重
合体であり固有粘度［η］が８以上であるカチオン性高
分子凝集剤を添加する紙・パルプ廃水の凝集処理方法。 1. A copolymer in which an aluminum salt-based inorganic coagulant is added to paper / pulp wastewater, and then a weight composition ratio of acrylamide and the following monomer (a) is 98-50: 2-50. Yes A method of coagulating paper / pulp wastewater, which comprises adding a cationic polymer coagulant having an intrinsic viscosity [η] of 8 or more.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63191567A JP2668711B2 (en) | 1988-07-29 | 1988-07-29 | Paper and pulp wastewater coagulation treatment method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63191567A JP2668711B2 (en) | 1988-07-29 | 1988-07-29 | Paper and pulp wastewater coagulation treatment method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0240287A JPH0240287A (en) | 1990-02-09 |
| JP2668711B2 true JP2668711B2 (en) | 1997-10-27 |
Family
ID=16276818
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP63191567A Expired - Fee Related JP2668711B2 (en) | 1988-07-29 | 1988-07-29 | Paper and pulp wastewater coagulation treatment method |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2668711B2 (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100318327B1 (en) * | 1995-12-16 | 2002-04-22 | 구광시 | Manufacturing method of emulsion type polymer coagulant |
| KR100278507B1 (en) * | 1998-08-24 | 2001-03-02 | 한성욱 | Water-soluble polymer dispersion for wastewater treatment containing inorganic coagulant and method for producing same |
| JP5659487B2 (en) * | 2009-12-24 | 2015-01-28 | 三菱レイヨン株式会社 | Wastewater coagulation method |
| JP5621260B2 (en) * | 2010-01-07 | 2014-11-12 | 三菱レイヨン株式会社 | Wastewater coagulation method |
| CN105439266A (en) * | 2015-11-24 | 2016-03-30 | 宜兴市丰烨化学有限公司 | Acrylamide and dimethylamine containing flocculant and preparation method thereof |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5242649A (en) * | 1975-09-30 | 1977-04-02 | Nittan Co Ltd | Method for processing pulp waste liquid |
| JPS5341911A (en) * | 1976-09-29 | 1978-04-15 | Hitachi Ltd | Out-trunk connection system for automatic exchanger image pickupsystem |
| JPS56101992A (en) * | 1980-01-11 | 1981-08-14 | Kurita Industrial Co Ltd | Recovery of valuable substance from white liquor |
-
1988
- 1988-07-29 JP JP63191567A patent/JP2668711B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0240287A (en) | 1990-02-09 |
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