JPH04200693A - Method for removing total organic halogen compound in chlorine-treated waste water of kraft pulp bleaching stage - Google Patents
Method for removing total organic halogen compound in chlorine-treated waste water of kraft pulp bleaching stageInfo
- Publication number
- JPH04200693A JPH04200693A JP32957190A JP32957190A JPH04200693A JP H04200693 A JPH04200693 A JP H04200693A JP 32957190 A JP32957190 A JP 32957190A JP 32957190 A JP32957190 A JP 32957190A JP H04200693 A JPH04200693 A JP H04200693A
- Authority
- JP
- Japan
- Prior art keywords
- waste water
- chlorine
- treated waste
- wastewater
- organic halogen
- 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.)
- Granted
Links
- 239000002351 wastewater Substances 0.000 title claims abstract description 49
- 239000002655 kraft paper Substances 0.000 title claims abstract description 19
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 title claims abstract description 13
- 239000000460 chlorine Substances 0.000 title claims abstract description 13
- 229910052801 chlorine Inorganic materials 0.000 title claims abstract description 13
- 150000002896 organic halogen compounds Chemical class 0.000 title claims description 26
- 238000000034 method Methods 0.000 title claims description 22
- 238000004076 pulp bleaching Methods 0.000 title abstract 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 26
- 229910052742 iron Inorganic materials 0.000 claims abstract description 18
- -1 iron ions Chemical class 0.000 claims abstract description 11
- 239000003513 alkali Substances 0.000 claims abstract description 8
- 238000004061 bleaching Methods 0.000 claims description 15
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 abstract description 6
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 abstract description 4
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 abstract description 4
- 239000000920 calcium hydroxide Substances 0.000 abstract description 4
- 235000011116 calcium hydroxide Nutrition 0.000 abstract description 4
- 229910001861 calcium hydroxide Inorganic materials 0.000 abstract description 4
- WQYVRQLZKVEZGA-UHFFFAOYSA-N hypochlorite Chemical compound Cl[O-] WQYVRQLZKVEZGA-UHFFFAOYSA-N 0.000 abstract description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 abstract description 3
- 229910000019 calcium carbonate Inorganic materials 0.000 abstract description 2
- 235000011121 sodium hydroxide Nutrition 0.000 abstract description 2
- 229910052736 halogen Inorganic materials 0.000 abstract 2
- 150000002367 halogens Chemical class 0.000 abstract 2
- 235000010216 calcium carbonate Nutrition 0.000 abstract 1
- 150000002500 ions Chemical class 0.000 abstract 1
- 229910000029 sodium carbonate Inorganic materials 0.000 abstract 1
- 235000017550 sodium carbonate Nutrition 0.000 abstract 1
- 238000007514 turning Methods 0.000 abstract 1
- OSVXSBDYLRYLIG-UHFFFAOYSA-N dioxidochlorine(.) Chemical compound O=Cl=O OSVXSBDYLRYLIG-UHFFFAOYSA-N 0.000 description 8
- 239000004155 Chlorine dioxide Substances 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 235000019398 chlorine dioxide Nutrition 0.000 description 4
- 239000000843 powder Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 238000005660 chlorination reaction Methods 0.000 description 2
- 239000003657 drainage water Substances 0.000 description 2
- 238000010828 elution Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000011122 softwood Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000006228 supernatant Substances 0.000 description 2
- 238000004065 wastewater treatment Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000007844 bleaching agent Substances 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 238000010411 cooking Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 150000004045 organic chlorine compounds Chemical class 0.000 description 1
- 239000000123 paper Substances 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 239000010802 sludge Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- 238000000108 ultra-filtration Methods 0.000 description 1
Landscapes
- Removal Of Specific Substances (AREA)
Abstract
Description
【発明の詳細な説明】
［産業上の利用分野］
本発明はクラフトバルブ漂白工程排水からの全有機ハロ
ゲン化合物の除去方法に関する。更に詳しくは、クラフ
トバルブの漂白に塩素、ハイポクロライド、二酸化塩素
などを用いる漂白工程を有するクラフトバルブ漂白工程
排水中の全有機塩素化合物の除去方法に関する。DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a method for removing all organic halogen compounds from Kraft valve bleaching process wastewater. More specifically, the present invention relates to a method for removing all organic chlorine compounds from wastewater from a Kraft valve bleaching process, which includes a bleaching process using chlorine, hypochloride, chlorine dioxide, etc. for bleaching Kraft valves.
［従来の技術］
クラフトバルブ化工程からの排水、特に漂白クラフトバ
ルブを製造している工場排水中には、塩素、ハイポクロ
ライド、二酸化塩素などを用いるため、その排水中には
有機ハロゲン化合物（有機塩素化合物）が含まれている
。このような塩素漂白設備を有する紙バルブ工場排水の
化学成分及びその排水の流れる河川、海域への影響につ
いては現在のところ十分には分かっていないが、今後有
機ハロゲン化合物の影響がはっきりしてきた場合には、
全く塩素系の漂白剤を使用しない漂白法、あるいは効率
的な外部処理による河川への有機ハロゲン化合物の流出
を最低限におさえる方法が必要となる。[Prior art] Wastewater from the kraft valve manufacturing process, especially the wastewater from factories manufacturing bleached kraft valves, uses chlorine, hypochloride, chlorine dioxide, etc., so the wastewater contains organic halogen compounds (organic Contains chlorine compounds). At present, the chemical composition of wastewater from a paper valve factory with chlorine bleaching equipment and its impact on the rivers and sea areas through which it flows are not fully understood, but if the impact of organic halogen compounds becomes clearer in the future. for,
A bleaching method that does not use any chlorine bleach or an efficient external treatment method that minimizes the flow of organic halogen compounds into rivers is needed.
全有機ハロゲン化合物の発生量を少なくするための対策
としてバルブ蒸解時間の延長、酸素漂白の導入、塩素に
比べ有機ハロゲン化合物の生成が少ない二酸化塩素の添
加率を増やす等が実施されている。Measures taken to reduce the amount of total organic halogen compounds generated include extending bulb cooking time, introducing oxygen bleaching, and increasing the addition rate of chlorine dioxide, which generates fewer organic halogen compounds than chlorine.
また、排水中の有機ハロゲン化合物の処理法として、限
外濾過膜の利用、活性汚泥などの生物処理が良い等の提
案があるが、いずれの方法も多額の設備投資が必要であ
り、また運転経費が嵩み、既存設備では簡単に適用でき
ないという問題点を有していた。In addition, as a treatment method for organic halogen compounds in wastewater, there are proposals such as the use of ultrafiltration membranes and biological treatment such as activated sludge, but all of these methods require a large amount of capital investment and are not suitable for operation. The problem was that it was expensive and could not be easily applied with existing equipment.
［発明が解決しようとする課題］
かかる現状に鑑み、本発明者らは安価で且つ容易なりラ
フトバルブ排水中の有機ハロゲン化合物を除去する方法
を鋭意検討した結果、クラフトバルブ漂白工程の塩素処
理水と鉄屑を接触させ、鉄イオンを溶解せしめた排水に
、アルカリを添加してｐＨを８．０以上とすることが極
めて効果的であることを見出し、本発明に到達した。[Problems to be Solved by the Invention] In view of the current situation, the present inventors have intensively investigated a method for removing organic halogen compounds from raft valve wastewater in a cheap and easy manner. The inventors have discovered that it is extremely effective to add an alkali to wastewater that has been brought into contact with iron scraps to dissolve iron ions to adjust the pH to 8.0 or higher, and have thus arrived at the present invention.
従って、本発明の目的は安価で且つ容易な、クラフトバ
ルブ排水中の全有機ハロゲン化合物を除去する方法を提
供することにある。Therefore, an object of the present invention is to provide an inexpensive and easy method for removing all organic halogen compounds from kraft valve wastewater.
［課題を解決するための手段１
本発明はクラフトバルブ漂白工程の塩素処理排水と鉄屑
を接触させ、鉄イオンを溶解せしめた排水にアルカリを
添加してｐＨを８．０以上とすることを特徴とするクラ
フトバルブ漂白工程の塩素処理排水中の全有機ハロゲン
化合物の除去方法に関する６
本発明で対象とする排水にはクラフトバルブ漂白工程の
塩素処理排水の他にハイポクロライド処理排水、二酸化
塩素処理排水を含めても良い。鉄屑としてはダライ粉と
いった旋盤屑などが利用可能である。[Means for Solving the Problems 1] The present invention involves bringing chlorinated wastewater from the Kraft valve bleaching process into contact with iron scraps, and adding alkali to the wastewater in which iron ions have been dissolved to adjust the pH to 8.0 or higher. 6 Concerning the method for removing all organic halogen compounds from chlorinated wastewater of the Kraft valve bleaching process, which is characterized by 6. In addition to the chlorinated wastewater of the Kraft valve bleaching process, the wastewater targeted by the present invention includes hypochloride-treated wastewater and chlorine dioxide-treated wastewater. Drainage may also be included. As the iron scraps, lathe scraps such as dull powder can be used.
塩素処理排水と、鉄屑を接触させた時のｐＨは２．０以
下が望ましく、排水のｐＨが２．０以上の時には適時、
硫酸、塩酸等でｐＨ調整する必要がある。It is desirable that the pH when chlorinated wastewater and iron scraps come into contact is 2.0 or less, and if the pH of the wastewater is 2.0 or more,
It is necessary to adjust the pH using sulfuric acid, hydrochloric acid, etc.
接触時間は、塩素排水のｐ Ｈ等とも関係するが排水中
への鉄イオンの溶出が１００〜２００ｐｐｍであること
が好ましい６アルカリ源としては、クラフトバルブ漂白
工程のアルカリ処理排水も利用可能であり、また消石灰
、炭酸カルシウム、炭酸ソーダ、苛性ソーダ等が使用可
能である。The contact time is related to the pH of the chlorine wastewater, but it is preferable that the elution of iron ions into the wastewater be 100 to 200 ppm.6 As an alkali source, alkali-treated wastewater from the Kraft Valve bleaching process can also be used. , slaked lime, calcium carbonate, soda carbonate, caustic soda, etc. can also be used.
処理設備としては、タラリファイヤー、シックナーとい
′った通常の排水処理用の設備が利用可能である。従来
のＣＯＤ （化学的酸素要求量）、色度、ＳＳ（懸濁物
質）等の除去を目的とした、凝集沈殿処理のｐ Ｈ域５
．０〜７．５では全有機ハロゲン化合物の除去は皆無で
はないが除去率は非常に悪い。しかし本発明の処理ｐ
Ｈを８．０以上、望ましくは１０以上とすることにより
極めて効果的に全有機ハロゲン化合物が除去されること
が判明した。As the treatment equipment, ordinary wastewater treatment equipment such as a tallifier and a thickener can be used. pH range 5 of conventional coagulation-sedimentation treatment aimed at removing COD (chemical oxygen demand), chromaticity, SS (suspended solids), etc.
．． At 0 to 7.5, all organic halogen compounds are not completely removed, but the removal rate is very poor. However, the treatment p of the present invention
It has been found that all organic halogen compounds can be removed extremely effectively by setting H to 8.0 or more, preferably 10 or more.
以下、実施例に基づき本発明を更に詳しく説明する。Hereinafter, the present invention will be explained in more detail based on Examples.
実施例１
針葉樹クラフトバルブの塩素処理時の排水をダライ粉１
ｋｇを入れた５０１ポリバケツに入れ、鉄イオンの溶
出を行った６
塩素処理排水のｐＨが２．３であったため、少量の硫酸
を添加してｐ Ｈ１，９とし、５分間に１回撹拌棒で撹
拌し、２０分間保持した。この鉄イオンを溶出させた塩
素処理排水中の鉄イオンは、１２０ｐｐｍであった。ま
たこの塩素処理排水の全有機ハロゲン化合物は７４ｐｐ
ｍであり、ＣＯＤは３６０ｐｐｍであった。全有機ハロ
ゲン化合物は三菱化成社製、測定機ＴＯＸ−１０を用い
、またＣＯＤはＪＩＳ法（ＪＩＳ０１０２）によって行
った。Example 1 Drainage water from chlorination of softwood craft valves was treated with powder 1
6. Since the pH of the chlorinated wastewater was 2.3, a small amount of sulfuric acid was added to bring the pH to 1.9, and the pH was adjusted to 1.9 using a stirring bar once every 5 minutes. and held for 20 minutes. The iron ion content in the chlorinated wastewater from which the iron ions were eluted was 120 ppm. In addition, the total organic halogen compounds in this chlorinated wastewater were 74pp.
m, and the COD was 360 ppm. Total organic halogen compounds were measured using a measuring device TOX-10 manufactured by Mitsubishi Kasei Corporation, and COD was measured according to the JIS method (JIS0102).
この鉄イオン溶出排水を用いて下記のテストを行った。The following tests were conducted using this iron ion elution wastewater.
テストはジャーテスターを使用し、排水５００ｍ１を採
取し、これに消石灰を添加して所定のｐ Ｈとし、１０
分間撹拌後、静澄化した上澄水の全有機ハロゲン化合物
およびＣＯＤを測定した。結果を第１表に示す。For the test, use a jar tester to collect 500 ml of wastewater, add slaked lime to the specified pH, and adjust the pH to 10.
After stirring for a minute, the total organic halogen compounds and COD of the clarified supernatant water were measured. The results are shown in Table 1.
ｐ ＋（５，２〜７．６といった領域の、テストＮｏ、
１〜３では全有機ハロゲン化合物の除去率は非常に悪
いが、本発明のｐＨ８，０以上の領域、テストＮｏ、
４へ・７ては全有機ハロゲン化合物は極めて効果的に除
去が可能である。従来の排水処理のｐＨ領域５．０〜７
．５の領域でも本発明のｐ Ｈ８，，０以上の領域でも
ＣＯＤの除去率は全有機ハロゲン化合物の除去率に比べ
、それ程高くないことが分かる。p + (test No. in the region such as 5, 2 to 7.6,
1 to 3, the removal rate of all organic halogen compounds is very poor, but in the pH 8.0 or higher region of the present invention, test No.
4 and 7, all organic halogen compounds can be removed extremely effectively. Conventional wastewater treatment pH range 5.0-7
．． It can be seen that the removal rate of COD is not so high compared to the removal rate of all organic halogen compounds both in the range of pH 5 and in the range of pH 8.0 or higher according to the present invention.
実施例２
針葉樹クラフトバルブの塩素処理時の排水をダライ粉１
ｋｇを入れた５０１ポリバケツに入れ、実施例１と同
′様に鉄イオンの溶出を行った。保持時間を３０分とし
、この時塩素処理排水中に溶出している鉄イオンは１７
０ｐｐｍであった。Example 2 Drainage water during chlorination of softwood craft valve was treated with powder 1
kg was placed in a 501 polyethylene bucket, and iron ions were eluted in the same manner as in Example 1. The holding time was 30 minutes, and at this time the iron ions eluted into the chlorinated wastewater were 17
It was 0 ppm.
この排水にクラフトバルブ漂白時のアルカリ処理排水を
混合し、この混合排水を用いてジャーテスターによる全
有機ハロゲン化合物の除去性についてテストした。供試
排水の全有機ハロゲン化合物は、４１ｐｐｍであり、Ｃ
ＯＤは４０７ｐｐｍであった。This wastewater was mixed with wastewater treated with alkali during Kraft Valve bleaching, and the mixed wastewater was used to test the removability of all organic halogen compounds using a jar tester. The total organic halogen compounds in the sample wastewater were 41 ppm, and C
OD was 407 ppm.
テストはジャーテスターを使用し、混合排水５００ｍ１
を採取し、これに消石灰を添加して、所定のｐＨとし１
０分間撹拌後、静澄化した上澄水の全有機ハロゲン化合
物およびＣＯＤを測定した。結果を第２表に示す。The test was conducted using a jar tester, and 500ml of mixed wastewater was used.
was collected, slaked lime was added to it, and the pH was adjusted to 1.
After stirring for 0 minutes, the total organic halogen compounds and COD of the clarified supernatant water were measured. The results are shown in Table 2.
従来性われている凝集沈澱のｐ）（域５．０〜７．５（
テストＮｏ、 ８〜１１）では、全有機ハロゲン化合物
の除去率は低いが、本発明のｐＨａ−ｏ以上の領域（テ
ストＮｏ、 １２〜１５）では全有機ハロゲン化合物の
除去率が極めて高いことが判明した。p) (range 5.0 to 7.5 (
In Test Nos. 8 to 11), the removal rate of all organic halogen compounds is low, but in the pH range of the present invention above pH-o (Test Nos. 12 to 15), the removal rate of all organic halogen compounds is extremely high. found.
（以下余白）
第 １ 表
第 ２ 表
［発明の効果］
本発明によりクラフトバルブ漂白工程の塩素処理排水中
の全有機ハロゲン化合物を安価にまた極めて効率よく除
去できることが可能になった。(The following is a blank space) Table 1 Table 2 [Effects of the Invention] The present invention has made it possible to remove all organic halogen compounds in chlorinated wastewater from the Kraft valve bleaching process at low cost and extremely efficiently.
Claims (1)
させ、鉄イオンを溶解せしめた排水に、アルカリを添加
してｐＨを８．０以上とすることを特徴とするクラフト
バルブ漂白工程の塩素処理排水中の全有機ハロゲン化合
物の除去方法。Chlorine treatment in the Kraft valve bleaching process, characterized by adding alkali to the chlorinated wastewater from the Kraft valve bleaching process and the wastewater in which iron ions are dissolved by contacting with iron scraps to adjust the pH to 8.0 or higher. Method for removing all organic halogen compounds from wastewater.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2329571A JP2558179B2 (en) | 1990-11-30 | 1990-11-30 | Method for removing all organic halogen compounds in chlorinated wastewater from kraft pulp bleaching process |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2329571A JP2558179B2 (en) | 1990-11-30 | 1990-11-30 | Method for removing all organic halogen compounds in chlorinated wastewater from kraft pulp bleaching process |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH04200693A true JPH04200693A (en) | 1992-07-21 |
| JP2558179B2 JP2558179B2 (en) | 1996-11-27 |
Family
ID=18222839
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2329571A Expired - Fee Related JP2558179B2 (en) | 1990-11-30 | 1990-11-30 | Method for removing all organic halogen compounds in chlorinated wastewater from kraft pulp bleaching process |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2558179B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105399158A (en) * | 2015-12-12 | 2016-03-16 | 常州大学 | Treating method for acidic silicon carbide waste water |
-
1990
- 1990-11-30 JP JP2329571A patent/JP2558179B2/en not_active Expired - Fee Related
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105399158A (en) * | 2015-12-12 | 2016-03-16 | 常州大学 | Treating method for acidic silicon carbide waste water |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2558179B2 (en) | 1996-11-27 |
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|---|---|---|---|
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