JP5800618B2 - Slime peeling method - Google Patents
Slime peeling method Download PDFInfo
- Publication number
- JP5800618B2 JP5800618B2 JP2011161416A JP2011161416A JP5800618B2 JP 5800618 B2 JP5800618 B2 JP 5800618B2 JP 2011161416 A JP2011161416 A JP 2011161416A JP 2011161416 A JP2011161416 A JP 2011161416A JP 5800618 B2 JP5800618 B2 JP 5800618B2
- Authority
- JP
- Japan
- Prior art keywords
- stage
- water
- slime
- acid
- treated
- 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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- 229910052801 chlorine Inorganic materials 0.000 claims description 82
- 206010040844 Skin exfoliation Diseases 0.000 claims description 64
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 49
- QWPPOHNGKGFGJK-UHFFFAOYSA-N hypochlorous acid Chemical compound ClO QWPPOHNGKGFGJK-UHFFFAOYSA-N 0.000 claims description 46
- JSYGRUBHOCKMGQ-UHFFFAOYSA-N dichloramine Chemical compound ClNCl JSYGRUBHOCKMGQ-UHFFFAOYSA-N 0.000 claims description 34
- QDHHCQZDFGDHMP-UHFFFAOYSA-N Chloramine Chemical compound ClN QDHHCQZDFGDHMP-UHFFFAOYSA-N 0.000 claims description 25
- 229910021529 ammonia Inorganic materials 0.000 claims description 24
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- JHVLLYQQQYIWKX-UHFFFAOYSA-N benzyl 2-bromoacetate Chemical compound BrCC(=O)OCC1=CC=CC=C1 JHVLLYQQQYIWKX-UHFFFAOYSA-N 0.000 description 1
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- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical class [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 description 1
- CEJLBZWIKQJOAT-UHFFFAOYSA-N dichloroisocyanuric acid Chemical compound ClN1C(=O)NC(=O)N(Cl)C1=O CEJLBZWIKQJOAT-UHFFFAOYSA-N 0.000 description 1
- 229940090960 diethylenetriamine pentamethylene phosphonic acid Drugs 0.000 description 1
- ZPWVASYFFYYZEW-UHFFFAOYSA-L dipotassium hydrogen phosphate Chemical compound [K+].[K+].OP([O-])([O-])=O ZPWVASYFFYYZEW-UHFFFAOYSA-L 0.000 description 1
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- 229910000396 dipotassium phosphate Inorganic materials 0.000 description 1
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- 239000012990 dithiocarbamate Substances 0.000 description 1
- DUYCTCQXNHFCSJ-UHFFFAOYSA-N dtpmp Chemical compound OP(=O)(O)CN(CP(O)(O)=O)CCN(CP(O)(=O)O)CCN(CP(O)(O)=O)CP(O)(O)=O DUYCTCQXNHFCSJ-UHFFFAOYSA-N 0.000 description 1
- NFDRPXJGHKJRLJ-UHFFFAOYSA-N edtmp Chemical compound OP(O)(=O)CN(CP(O)(O)=O)CCN(CP(O)(O)=O)CP(O)(O)=O NFDRPXJGHKJRLJ-UHFFFAOYSA-N 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
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- 150000002148 esters Chemical class 0.000 description 1
- 125000005670 ethenylalkyl group Chemical group 0.000 description 1
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- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 1
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- SAPIQCCFEBULSH-UHFFFAOYSA-M lithium;sulfamate Chemical compound [Li+].NS([O-])(=O)=O SAPIQCCFEBULSH-UHFFFAOYSA-M 0.000 description 1
- YZVJHCGMTYDKFR-UHFFFAOYSA-L magnesium;disulfamate Chemical compound [Mg+2].NS([O-])(=O)=O.NS([O-])(=O)=O YZVJHCGMTYDKFR-UHFFFAOYSA-L 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 229910000734 martensite Inorganic materials 0.000 description 1
- XJRBAMWJDBPFIM-UHFFFAOYSA-N methyl vinyl ether Chemical compound COC=C XJRBAMWJDBPFIM-UHFFFAOYSA-N 0.000 description 1
- JWZXKXIUSSIAMR-UHFFFAOYSA-N methylene bis(thiocyanate) Chemical compound N#CSCSC#N JWZXKXIUSSIAMR-UHFFFAOYSA-N 0.000 description 1
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- MEFBJEMVZONFCJ-UHFFFAOYSA-N molybdate Chemical compound [O-][Mo]([O-])(=O)=O MEFBJEMVZONFCJ-UHFFFAOYSA-N 0.000 description 1
- 229910000402 monopotassium phosphate Inorganic materials 0.000 description 1
- 235000019796 monopotassium phosphate Nutrition 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- MGFYIUFZLHCRTH-UHFFFAOYSA-N nitrilotriacetic acid Chemical compound OC(=O)CN(CC(O)=O)CC(O)=O MGFYIUFZLHCRTH-UHFFFAOYSA-N 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- JPMIIZHYYWMHDT-UHFFFAOYSA-N octhilinone Chemical compound CCCCCCCCN1SC=CC1=O JPMIIZHYYWMHDT-UHFFFAOYSA-N 0.000 description 1
- 239000003002 pH adjusting agent Substances 0.000 description 1
- FJKROLUGYXJWQN-UHFFFAOYSA-N papa-hydroxy-benzoic acid Natural products OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 description 1
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical compound CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 description 1
- QPCDCPDFJACHGM-UHFFFAOYSA-K pentetate(3-) Chemical compound OC(=O)CN(CC([O-])=O)CCN(CC([O-])=O)CCN(CC(O)=O)CC([O-])=O QPCDCPDFJACHGM-UHFFFAOYSA-K 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- PJNZPQUBCPKICU-UHFFFAOYSA-N phosphoric acid;potassium Chemical compound [K].OP(O)(O)=O PJNZPQUBCPKICU-UHFFFAOYSA-N 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920001444 polymaleic acid Polymers 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 229920001282 polysaccharide Polymers 0.000 description 1
- 239000005017 polysaccharide Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 description 1
- BTAAXEFROUUDIL-UHFFFAOYSA-M potassium;sulfamate Chemical compound [K+].NS([O-])(=O)=O BTAAXEFROUUDIL-UHFFFAOYSA-M 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- YBBJKCMMCRQZMA-UHFFFAOYSA-N pyrithione Chemical compound ON1C=CC=CC1=S YBBJKCMMCRQZMA-UHFFFAOYSA-N 0.000 description 1
- 238000005057 refrigeration Methods 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 238000001223 reverse osmosis Methods 0.000 description 1
- 229960004889 salicylic acid Drugs 0.000 description 1
- 239000002455 scale inhibitor Substances 0.000 description 1
- 235000015170 shellfish Nutrition 0.000 description 1
- 238000003307 slaughter Methods 0.000 description 1
- 229960004025 sodium salicylate Drugs 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 210000003802 sputum Anatomy 0.000 description 1
- 208000024794 sputum Diseases 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 125000000542 sulfonic acid group Chemical group 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 230000009182 swimming Effects 0.000 description 1
- 229950009390 symclosene Drugs 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 239000008399 tap water Substances 0.000 description 1
- 235000020679 tap water Nutrition 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
- WJCNZQLZVWNLKY-UHFFFAOYSA-N thiabendazole Chemical compound S1C=NC(C=2NC3=CC=CC=C3N=2)=C1 WJCNZQLZVWNLKY-UHFFFAOYSA-N 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- YBNLWIZAWPBUKQ-UHFFFAOYSA-N trichloro(trichloromethylsulfonyl)methane Chemical compound ClC(Cl)(Cl)S(=O)(=O)C(Cl)(Cl)Cl YBNLWIZAWPBUKQ-UHFFFAOYSA-N 0.000 description 1
- 241001148471 unidentified anaerobic bacterium Species 0.000 description 1
- 239000011345 viscous material Substances 0.000 description 1
- 239000002349 well water Substances 0.000 description 1
- 235000020681 well water Nutrition 0.000 description 1
- 150000003751 zinc Chemical class 0.000 description 1
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- 229910052725 zinc Inorganic materials 0.000 description 1
Landscapes
- Treatment Of Water By Oxidation Or Reduction (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
Description
本発明は、冷却水系、紙パルプ製造プロセスの各種水系、鉄鋼製造プロセスの各種水系、集塵水系、排水系統、切削油などの金属加工処理水系などの各種水系において、スライムの剥離効果に優れ、しかも安全性が高いスライム剥離方法に関する。 The present invention is excellent in slime peeling effect in various water systems such as cooling water system, various water systems of paper pulp manufacturing process, various water systems of steel manufacturing process, dust collection water system, drainage system, metal processing water system such as cutting oil, Moreover, the present invention relates to a highly safe slime peeling method.
冷却水系、紙パルプ製造工程や鉄鋼製造工程などの各種プロセス水系、切削油水系などの水系では、細菌類、真菌類、藻類などから構成されるスライムが系内に発生し、伝熱効率の低下、配管の閉塞、金属材質の腐食などの微生物障害を引き起こす。このような微生物障害を回避する方法として、付着したスライムを剥離洗浄するスライム剥離剤、あるいは殺菌や殺藻やスライムの付着を防止するためのスライムコントロール剤などが使用されている。スライムコントロール剤は主に水中の微生物の生育を抑制することにより微生物の付着を低減させるものであり、菌の酵素反応の阻害や細胞膜の変性などにより菌を死滅させたり、菌の増殖を抑制する。一方、スライム剥離剤は主に細胞外に生成される多糖類に由来する粘性物質の粘性を低下させることにより、細菌の集合体を分散させスライムを剥離する。このようにそれぞれの作用が異なるため、スライムコントロール剤として有効な薬剤であってもスライム剥離剤としては有効とはいえない。 In the cooling water system, various process water systems such as paper pulp manufacturing process and steel manufacturing process, and water systems such as cutting oil water system, slime composed of bacteria, fungi, algae, etc. is generated in the system, and the heat transfer efficiency decreases. Causes microbial damage such as blockage of pipes and corrosion of metal materials. As a method for avoiding such microbial damage, a slime remover that peels and cleans the attached slime, or a slime control agent for preventing sterilization, algicide, and slime adhesion is used. The slime control agent mainly reduces the adhesion of microorganisms by suppressing the growth of microorganisms in water, kills the bacteria by inhibiting the enzyme reaction of the bacteria, denatures the cell membrane, and suppresses the growth of the bacteria. . On the other hand, the slime remover disperses bacterial aggregates and peels slime by lowering the viscosity of a viscous substance derived mainly from polysaccharides generated extracellularly. Thus, since each effect | action differs, even if it is a chemical | medical agent effective as a slime control agent, it cannot be said that it is effective as a slime peeling agent.
従来、水系で発生する微生物由来のスライムを剥離するための洗浄剤として次亜ハロゲン酸生成化合物、過酸化水素やヒドラジンが知られている。次亜ハロゲン酸生成化合物はスライム剥離効果が認められる濃度で使用すると、熱交換器や配管などの金属材質に対する腐食が顕著である。過酸化水素は金属に対する腐食性は低いが、スライム剥離効果を発揮するためには高濃度の添加が必要であり、経済的でない。ヒドラジンは有毒であり発癌性の疑いがあるため、環境上の問題や安全性の面から使用されない傾向にある。 Conventionally, hypohalous acid generating compounds, hydrogen peroxide, and hydrazine are known as cleaning agents for removing microorganism-derived slime generated in an aqueous system. When a hypohalous acid generating compound is used at a concentration at which a slime peeling effect is observed, corrosion of a metal material such as a heat exchanger or piping is remarkable. Although hydrogen peroxide has low corrosiveness to metals, it needs to be added at a high concentration in order to exert a slime peeling effect, and is not economical. Since hydrazine is toxic and suspected of being carcinogenic, it tends not to be used because of environmental problems and safety.
特許文献１には、塩素系酸化剤と、スルファミン酸および／またはその塩を含有するスライム剥離剤が開示されている。この方法は、塩素系酸化剤とスルファミン酸が反応して生成するクロロスルファミン酸が効果を発現するものであるが、モノクロラミンや次亜塩素酸と比較すると酸化力が弱く、スライムの剥離効果も十分ではない。 Patent Document 1 discloses a slime remover containing a chlorine-based oxidizing agent and sulfamic acid and / or a salt thereof. In this method, chlorosulfamic acid produced by the reaction of a chlorinated oxidant and sulfamic acid is effective, but its oxidizing power is weaker than monochloramine and hypochlorous acid, and it also has a slime peeling effect. Not enough.
特許文献２には、次亜塩素酸ナトリウムと硫酸アンモニアとを残留塩素（Ｃｌ２）に対するアンモニウムイオンのモル比が１：１．２〜１．８で混合した混合液を用いることを特徴とする微生物の生育を抑制する方法が示されているが、一旦付着したスライムを剥離する方法は開示されていない。 Patent Document 2 is characterized by using a mixed solution in which sodium hypochlorite and ammonium sulfate are mixed at a molar ratio of ammonium ions to residual chlorine (Cl 2 ) of 1: 1.2 to 1.8. Although a method for suppressing the growth of microorganisms has been shown, there is no disclosure of a method for stripping the slime once adhered.
本発明の課題は上記の問題点を克服することであり、具体的にはスライムの剥離効果に優れ、かつ安全性が高いスライム剥離方法を提供することである。 An object of the present invention is to overcome the above-described problems, and specifically, to provide a slime peeling method that is excellent in slime peeling effect and high in safety.
本発明者らは、前記課題を達成するために鋭意研究を重ねた結果、被処理水中に、（Ａ）アンモニアおよび／またはアンモニウム塩と（Ｂ）スルファミン酸および／またはスルファミン酸塩と（Ｃ）次亜塩素酸の反応によって得られるモノクロラミン性結合塩素とジクロラミン性結合塩素を存在させて処理するスライム剥離方法であれば、比較的低い添加量で効果的にスライムを剥離でき、また、ヒドラジンを用いないので取り扱い上の安全性が高いことを既に見出している。 As a result of intensive studies to achieve the above-mentioned problems, the present inventors have found that (A) ammonia and / or ammonium salt, (B) sulfamic acid and / or sulfamate, and (C) in the water to be treated. If the slime stripping method treats monochloramine-bound chlorine and dichloramine-bound chlorine obtained by the reaction of hypochlorous acid, the slime can be stripped effectively with a relatively low addition amount, and hydrazine can be removed. Since it is not used, it has already been found that the safety in handling is high.
本発明者らは、このスライム剥離方法におけるモノクロラミン性結合塩素とジクロラミン性結合塩素の作用を更に検討したところ、モノクロラミン性結合塩素が主にスライム層の表層部を殺菌剥離し、ジクロラミン性結合塩素が主にスライム層の底層部に浸透して剥離分散していることを見出し、両方の特徴を最大限に生かすスライム剥離方法として本発明に到達した。 The present inventors further examined the action of monochloramine-bound chlorine and dichloramine-bound chlorine in this slime peeling method. Monochloramine-bound chlorine mainly disinfects the surface layer of the slime layer, and dichloramine-bound. It was found that chlorine mainly penetrated into the bottom layer of the slime layer and was peeled and dispersed, and the present invention was reached as a slime peeling method that makes the best use of both features.
すなわち請求項１に係る発明は、被処理水中に、（Ａ）アンモニアおよび／またはアンモニウム塩（ただし、スルファミン酸アンモニウムを除く）と（Ｃ）次亜塩素酸の反応によって得られるモノクロラミン性結合塩素を存在させる第一段階の後に、（Ｂ）スルファミン酸および／またはスルファミン酸塩（ただし、スルファミン酸アンモニウムを除く）と（Ｃ）次亜塩素酸の反応によって得られるジクロラミン性結合塩素を存在させる第二段階を行なう（ここで、該ジクロラミン性結合塩素は主にＮ−モノクロロスルファミン酸であって、該ジクロラミン性結合塩素の濃度はジエチル−ｐ−フェニレンジアミン（ＤＰＤ）比色法、ＤＰＤ−第一硫酸鉄滴定法などで測定される）、二段階で処理するスライム剥離方法であって、
前記の第一段階において、被処理水に対する（Ａ）アンモニアおよび／またはアンモニウム塩（ただし、スルファミン酸アンモニウムを除く）と（Ｃ）次亜塩素酸の添加比率が、（Ｃ）次亜塩素酸のＣｌ ２ 換算のモル濃度に対する（Ａ）アンモニアおよび／またはアンモニウム塩（ただし、スルファミン酸アンモニウムを除く）のモル濃度の比として０．６〜１．５であり、かつ、前記第一段階の処理期間中の被処理水中のモノクロラミン性結合塩素濃度をＣｌ ２ 換算で１５〜３００ｍｇ／Ｌの範囲に維持するように前記（Ａ）、（Ｃ）の各成分を被処理水に添加し、続いて、前記の第二段階において、被処理水に対する（Ｂ）スルファミン酸および／またはスルファミン酸塩（ただし、スルファミン酸アンモニウムを除く）と（Ｃ）次亜塩素酸の添加比率が、（Ｃ）次亜塩素酸のＣｌ ２ 換算のモル濃度に対する（Ｂ）スルファミン酸および／またはスルファミン酸塩（ただし、スルファミン酸アンモニウムを除く）のモル濃度の比として０．６〜１．５であり、かつ、前記第二段階の処理期間中の被処理水中のジクロラミン性結合塩素濃度をＣｌ ２ 換算で１５〜３００ｍｇ／Ｌの範囲に維持するように前記（Ｂ）、（Ｃ）の各成分を被処理水に添加することを特徴とするスライム剥離方法である。
That is, the invention according to claim 1 is a monochloramine-bonded chlorine obtained by the reaction of (A) ammonia and / or an ammonium salt (excluding ammonium sulfamate) and (C) hypochlorous acid in the water to be treated. After the first stage of presenting (B) sulfamic acid and / or sulfamate (excluding ammonium sulfamate) and (C) dichloramine-bound chlorine obtained by the reaction of hypochlorous acid is present. Perform two steps (wherein the dichloramine-bound chlorine is mainly N-monochlorosulfuric acid and the concentration of the dichloramine-bound chlorine is determined by diethyl-p-phenylenediamine (DPD) colorimetric method, DPD-1 Is a slime peeling method that is processed in two steps ,
In the first stage, the ratio of (A) ammonia and / or ammonium salt (excluding ammonium sulfamate) to (C) hypochlorous acid relative to the water to be treated is (C) hypochlorous acid The ratio of the molar concentration of (A) ammonia and / or ammonium salt (excluding ammonium sulfamate) to the molar concentration in terms of Cl 2 is 0.6 to 1.5, and the treatment period of the first stage The components (A) and (C) are added to the water to be treated so that the concentration of monochloramine bound chlorine in the water to be treated is within the range of 15 to 300 mg / L in terms of Cl 2 , In the second stage, (B) sulfamic acid and / or sulfamic acid salt (excluding ammonium sulfamate) and (C) hypochlorous acid to the water to be treated Addition ratio of periodate, 0 as the ratio of the molar concentration of (C) hypophosphite to the molar concentration of Cl 2 Conversion chlorate (B) sulfamic acid and / or sulfamic acid salts (except ammonium sulfamate). (B), so as to maintain a dichloramine-bound chlorine concentration in the water to be treated during the treatment period of the second stage in the range of 15 to 300 mg / L in terms of Cl 2, which is 6 to 1.5. A slime peeling method characterized in that each component of (C) is added to water to be treated .
請求項２に係る発明は、スライム剥離処理期間が、前記第一段階は３０分以上であり、前記第二段階は２時間以上であり、該第一段階と該第二段階の合計処理時間は４８時間以内である請求項１記載のスライム剥離方法である。
In the invention according to claim 2, the slime peeling treatment period is 30 minutes or more in the first stage, the second stage is 2 hours or more, and the total treatment time of the first stage and the second stage is The slime peeling method according to claim 1, wherein the slime peeling method is within 48 hours .
本発明のスライム剥離方法を冷却水系、冷温水系、チラー水、紙パルプ製造プロセスの各種水系、鉄鋼製造プロセスの各種水系、集塵水系、排水系統、逆浸透装置、水泳プール、貯水槽、浴槽、切削油などの金属加工処理水系などの各種水系に適用することにより、各種微生物によって生成されたスライムを効果的に剥離することができる。また、使用する薬剤は取り扱い上の安全性が高いという効果もある。 The slime peeling method of the present invention is a cooling water system, cold / hot water system, chiller water, various water systems of paper pulp manufacturing process, various water systems of steel manufacturing process, dust collection water system, drainage system, reverse osmosis device, swimming pool, water tank, bathtub, By applying to various water systems such as a metal processing water system such as cutting oil, slime produced by various microorganisms can be effectively peeled off. In addition, there is an effect that the drug used is highly safe in handling.
本発明の（Ａ）アンモニアおよび／またはアンモニウム塩（「（Ａ）成分」と称する）は、アンモニア、アンモニア水、アンモニウム塩として市販されているものがそのまま使用できる。アンモニウム塩の種類は特に限定されないが、例えば硫酸アンモニウム、塩化アンモニウム、硝酸アンモニウム、炭酸アンモニウム、リン酸アンモニウムなどの水溶性塩類が使用される。
As the (A) ammonia and / or ammonium salt (referred to as “component (A)”) of the present invention, those commercially available as ammonia, aqueous ammonia and ammonium salts can be used as they are. Type of the ammonium salt is not particularly limited, such as ammonium sulfate, ammonium chloride, ammonium nitrate, ammonium carbonate, which water-soluble salts of ammonium phosphate beam is used.
本発明の（Ｂ）スルファミン酸および／またはスルファミン酸塩（「（Ｂ）成分」と称する）は市販されているのがそのまま使用できる。スルファミン酸塩の種類は特に限定されないが、例えばスルファミン酸ナトリウム、スルファミン酸カリウム、スルファミン酸リチウム、スルファミン酸カルシウム、スルファミン酸マグネシウム、スルファミン酸亜鉛などの水溶性塩類が使用される。
The (B) sulfamic acid and / or sulfamic acid salt of the present invention (referred to as “component (B)”) is commercially available and can be used as it is. The type of sulfamic acid salt is not particularly limited, for example, sodium sulfamate, potassium sulfamate, lithium sulfamate, calcium sulfamate, magnesium sulfamate, which water-soluble salts of sulphamic SanA lead is used.
本発明の（Ｃ）次亜塩素酸（「（Ｃ）成分」と称する）は水中で溶解して次亜塩素酸を生成する化合物が用いられるが、例えば次亜塩素酸ナトリウム、次亜塩素酸カリウム、次亜塩素酸カルシウムなどの次亜塩素酸塩、液化塩素、ブロモクロロジメチルヒダントイン、ジクロロジメチルヒダントインなどのハロゲン化ジメチルヒダントイン化合物類やトリクロロイソシアヌル酸、ジクロロイソシアヌル酸、クロロイソシアヌル酸やそれらの塩類などが挙げられるが、好ましくは次亜塩素酸塩と液化塩素である。前記次亜塩素酸塩の形態としては、水溶性および経済性などの観点からナトリウム塩やカリウム塩などのアルカリ金属塩が好適である。また、次亜塩素酸は塩化物イオンを含む水溶液を電気分解して得ることもできる。 (C) hypochlorous acid (referred to as “component (C)”) of the present invention is a compound that dissolves in water to produce hypochlorous acid. For example, sodium hypochlorite, hypochlorous acid Hypochlorites such as potassium and calcium hypochlorite, liquefied chlorine, halogenated dimethylhydantoin compounds such as bromochlorodimethylhydantoin, dichlorodimethylhydantoin, trichloroisocyanuric acid, dichloroisocyanuric acid, chloroisocyanuric acid and their salts Of these, hypochlorite and liquefied chlorine are preferred. The form of the hypochlorite is preferably an alkali metal salt such as sodium salt or potassium salt from the viewpoint of water solubility and economy. Hypochlorous acid can also be obtained by electrolyzing an aqueous solution containing chloride ions.
本発明において、これらの次亜塩素酸を生成する化合物は一種を単独で用いてもよく、二種以上を組み合わせて用いてもよい。次亜塩素酸を生成する化合物は、安価で取り扱いが容易であり、水に速やかに溶解して次亜塩素酸を速やかに生成する化合物が好ましく、この点で次亜塩素酸ナトリウムが最適である。次亜塩素酸ナトリウムは、有効塩素がＣｌ２換算で１２％以上の市販品が使用できる。 In the present invention, these compounds producing hypochlorous acid may be used singly or in combination of two or more. A compound that generates hypochlorous acid is inexpensive and easy to handle, and a compound that dissolves quickly in water and quickly generates hypochlorous acid is preferred, and sodium hypochlorite is optimal in this respect. . As sodium hypochlorite, a commercially available product having an effective chlorine content of 12% or more in terms of Cl 2 can be used.
本発明のスライム剥離方法の第一段階では、（Ａ）アンモニアおよび／またはアンモニウム塩と（Ｃ）次亜塩素酸が反応して主にモノクロラミン性結合塩素が生成（反応１）し、その他に遊離塩素やジクロラミン性結合塩素も少量生成する。次いで、第二段階では、（Ｂ）スルファミン酸および／またはスルファミン酸塩と（Ｃ）次亜塩素酸が反応して主にジクロラミン性結合塩素が生成（反応２）し、その他に遊離塩素やモノクロラミン性結合塩素も少量生成する。 In the first stage of the slime peeling method of the present invention, (A) ammonia and / or ammonium salt and (C) hypochlorous acid react to produce mainly monochloramine bonded chlorine (reaction 1). Small amounts of free chlorine and dichloramine-bound chlorine are also produced. Next, in the second stage, (B) sulfamic acid and / or sulfamate and (C) hypochlorous acid react to produce mainly dichloramine-bonded chlorine (reaction 2), in addition to free chlorine and monochloric acid. A small amount of laminar bound chlorine is also produced.
１モルのアンモニアと１モルの次亜塩素酸を反応させる反応１では、下記式のように１モルのモノクロラミン性結合塩素（ＮＨ２Ｃｌ）が生成する。
Ｃｌ２＋Ｈ２Ｏ＝ＨＣｌＯ＋ＨＣｌ
ＮＨ３＋ＨＣｌＯ＝ＮＨ２Ｃｌ＋Ｈ２Ｏ
In Reaction 1 in which 1 mol of ammonia and 1 mol of hypochlorous acid are reacted, 1 mol of monochloramine-bonded chlorine (NH 2 Cl) is generated as shown in the following formula.
Cl 2 + H 2 O = HClO + HCl
NH 3 + HClO═NH 2 Cl + H 2 O
また、１モルのスルファミン酸と１モルの次亜塩素酸を反応させる反応２では、ほぼ１モルのジクロラミン性結合塩素が生成するが、ここで生成するジクロラミン性結合塩素の形態はジクロラミンではなく、主にＮ−モノクロロスルファミン酸（ＨＯ３Ｓ−ＮＨＣｌ）であると推定される。
ＨＯ３Ｓ−ＮＨ２＋ＨＣｌＯ＝ＨＯ３Ｓ−ＮＨＣｌ＋Ｈ２Ｏ
このことはＮ−モノクロロスルファミン酸はジクロラミンと同程度の酸化力を有することを意味する。
Further, in Reaction 2 in which 1 mol of sulfamic acid and 1 mol of hypochlorous acid are reacted, approximately 1 mol of dichloroamine-bound chlorine is produced, but the form of dichloramine-bound chlorine produced here is not dichloramine, It is presumed to be mainly N-monochlororosulmic acid (HO 3 S—NHCl).
HO 3 S—NH 2 + HClO═HO 3 S—NHCl + H 2 O
This means that N-monochlororosulmic acid has an oxidizing power comparable to that of dichloramine.
すなわち、本発明のスライム剥離方法では、第一段階で上記の反応１を進行させることにより、モノクロラミン性結合塩素が生成し、続く第二段階で反応２を進行させることにより、ジクロラミン性結合塩素が生成することにより、２種の異なった作用を有する結合塩素の相乗効果によって優れたスライム剥離効果を発現すると考えられる。 That is, in the slime peeling method of the present invention, the monochloramine-bound chlorine is generated by proceeding the above reaction 1 in the first stage, and the dichloramine-bound chlorine is caused by proceeding the reaction 2 in the subsequent second stage. It is considered that an excellent slime peeling effect is expressed by the synergistic effect of combined chlorine having two different actions.
本発明のスライム剥離方法の第一段階において、（Ａ）アンモニアおよび／またはアンモニウム塩と（Ｃ）次亜塩素酸を被処理水に添加する方法、及び第二段階において、（Ｂ）スルファミン酸および／またはスルファミン酸塩と（Ｃ）次亜塩素酸を被処理水に添加する方法に特に制限はなく、（Ａ）アンモニアおよび／またはアンモニウム塩と（Ｃ）次亜塩素酸、あるいは、（Ｂ）スルファミン酸および／またはスルファミン酸塩と（Ｃ）次亜塩素酸を、被処理水にそれぞれ別個に添加しても良いが、次亜塩素酸がアンモニアやスルファミン酸と反応する前に光や熱などにより分解したり、被処理水中の有機物や還元性物質と反応してしまい目的とする反応生成物が効率よく得られなくなるのを防止するために、好ましくは希釈水の入った容器に次亜塩素酸を生成する化合物を加えて撹拌し、次いでアンモニアおよび／またはアンモニウム塩、あるいは、スルファミン酸および／またはスルファミン酸塩を加えて撹拌して調製した混合溶液を被処理水に添加する。このとき、この混合溶液中における次亜塩素酸の濃度はＣｌ２換算で０．００５〜３％の範囲になるように配合することが好ましく、次亜塩素酸濃度がこの範囲を超えると目的の反応生成物を効率よく生成することができず、十分な剥離効果が得られない。 In the first stage of the slime peeling method of the present invention, (A) a method of adding ammonia and / or ammonium salt and (C) hypochlorous acid to the water to be treated, and in the second stage, (B) sulfamic acid and There is no particular limitation on the method of adding sulfamate and / or (C) hypochlorous acid to the water to be treated. (A) Ammonia and / or ammonium salt and (C) hypochlorous acid, or (B) Sulfamic acid and / or sulfamic acid salt and (C) hypochlorous acid may be added separately to the water to be treated, but light, heat, etc. before hypochlorous acid reacts with ammonia or sulfamic acid. In order to prevent the target reaction product from being efficiently obtained due to decomposition or reaction with organic substances or reducing substances in the water to be treated, Add the compound that produces hypochlorous acid to the vessel and stir, then add ammonia and / or ammonium salt, or sulfamic acid and / or sulfamate, and add the mixed solution prepared by stirring to the water to be treated To do. At this time, the hypochlorous acid in the mixed solution concentration is preferably formulated to be in a range of 0.005 to 3% in Cl 2 terms, hypochlorous acid concentration purpose of exceeding this range A reaction product cannot be produced efficiently, and a sufficient peeling effect cannot be obtained.
また、上記の混合溶液で用いられる希釈水は、有機物、還元性物質、及び無機イオンの含有量が少ない清水が好ましく、工業用水、水道水、井水、軟化水、脱イオン水などが使用できる。 The dilution water used in the above mixed solution is preferably fresh water having a small content of organic substances, reducing substances, and inorganic ions, and industrial water, tap water, well water, softened water, deionized water, and the like can be used. .
また、本発明のスライム剥離方法の第一段階において、前記の添加順序を逆にして（Ｃ）次亜塩素酸を生成する化合物を（Ａ）アンモニアおよび／またはアンモニウム塩の後で加えると、局所的に高濃度となった次亜塩素酸が（Ａ）アンモニアと反応してモノクロラミン性結合塩素以外に不安定なジクロラミンが生成し、モノクロラミン性結合塩素の収率が２０％ほど低下するため好ましくない。 In addition, in the first stage of the slime peeling method of the present invention, when the addition order is reversed and (C) a compound that generates hypochlorous acid is added after (A) ammonia and / or ammonium salt, The hypochlorous acid having a high concentration reacts with (A) ammonia to produce unstable dichloramine other than monochloramine-bound chlorine, and the yield of monochloramine-bound chlorine decreases by about 20%. It is not preferable.
本発明のスライム剥離方法の第一段階における、（Ｃ）次亜塩素酸のＣｌ２換算のモル濃度に対する（Ａ）アンモニアおよび／またはアンモニウム塩のモル濃度の比、及び第二段階における、（Ｃ）次亜塩素酸のＣｌ２換算のモル濃度に対する（Ｂ）スルファミン酸および／またはスルファミン酸塩のモル濃度の比は、共に通常０．６〜１．５の範囲であり、好ましくは０．８〜１．２である。上記の、希釈水の入った容器に次亜塩素酸を生成する化合物を加えて撹拌し、次いでアンモニアおよび／またはアンモニウム塩、あるいは、スルファミン酸および／またはスルファミン酸塩を加えて撹拌して調製する混合溶液においても、このモル濃度比の範囲で調製する。 In the first stage of the slime peeling method of the present invention, (C) the ratio of the molar concentration of ammonia and / or ammonium salt to the molar concentration of hypochlorous acid in terms of Cl 2 , and (C The ratio of the molar concentration of (B) sulfamic acid and / or sulfamate to the molar concentration of hypochlorous acid in terms of Cl 2 is usually in the range of 0.6 to 1.5, preferably 0.8. ~ 1.2. Add the compound that generates hypochlorous acid to the container containing dilution water and stir, then add ammonia and / or ammonium salt, or sulfamic acid and / or sulfamate, and stir to prepare. The mixed solution is also prepared within this molar concentration ratio range.
上記のモル濃度比が０．６未満では、本発明のスライム剥離方法の第一段階、第二段階のいずれにおいても、未反応の次亜塩素酸が被処理水系に供給され、被処理水系における腐食性が増す。一方、この比が１．５を超えると、第一段階においては、未反応のアンモニアが被処理水系に供給され、被処理水系に存在する銅合金などの金属の腐食が発生し易くなり、また、第二段階においては、被処理水系に供給された未反応のスルファミン酸がスライム剥離に関与せず、スルファミン酸が高価なため、非経済的となる。 If the molar concentration ratio is less than 0.6, unreacted hypochlorous acid is supplied to the treated water system in both the first stage and the second stage of the slime peeling method of the present invention. Increases corrosivity. On the other hand, if this ratio exceeds 1.5, unreacted ammonia is supplied to the treated water system in the first stage, and corrosion of metals such as copper alloys existing in the treated water system is likely to occur, In the second stage, unreacted sulfamic acid supplied to the water system to be treated does not participate in slime peeling, and sulfamic acid is expensive, which is uneconomical.
本発明のスライム剥離方法の第一段階では、例えば、前記のように、次亜塩素酸を生成する化合物を水で希釈し、そこに、アンモニアおよび／またはアンモニウム塩を加えて撹拌して調製した混合溶液を被処理水系に添加すればよいが、調製後の混合溶液を５分間以内に被処理水系に速やかに添加することが重要である。これは、アンモニアと次亜塩素酸との反応により生成するモノクロラミン性結合塩素の貯蔵安定性が劣るためである。 In the first stage of the slime peeling method of the present invention, for example, as described above, a compound that generates hypochlorous acid is diluted with water, and ammonia and / or ammonium salt is added thereto and stirred. The mixed solution may be added to the treated water system, but it is important to quickly add the prepared mixed solution to the treated water system within 5 minutes. This is because the storage stability of monochloramine-bonded chlorine produced by the reaction between ammonia and hypochlorous acid is inferior.
一方、本発明のスライム剥離方法の第二段階で用いる、スルファミン酸と次亜塩素酸との反応により生成するＮ−モノクロロスルファミン酸はアルカリ性であれば貯蔵安定性が良いので、例えば、スルファミン酸と次亜塩素酸塩とアルカリ金属水酸化物の混合水溶液を保存しておくことが可能である。 On the other hand, since N-monochlorosulfuramic acid produced by the reaction of sulfamic acid and hypochlorous acid used in the second stage of the slime peeling method of the present invention is alkaline, it has good storage stability. For example, sulfamic acid and It is possible to store a mixed aqueous solution of hypochlorite and alkali metal hydroxide.
本発明のスライム剥離方法の第一段階では、被処理水中におけるモノクロラミン性結合塩素濃度がＣｌ２換算で通常１〜１０００ｍｇ／Ｌになるように添加されるが、好ましくは１５〜３００ｍｇ／Ｌ、より好ましくは１５〜２００ｍｇ／Ｌの範囲であり、第二段階では、被処理水中におけるジクロラミン性結合塩素濃度がＣｌ２換算で通常１〜１０００ｍｇ／Ｌになるように添加されるが、好ましくは１５〜３００ｍｇ／Ｌ、より好ましくは１５〜２００ｍｇ／Ｌの範囲である。 In the first stage of the slime peeling method of the present invention, the monochloramine bond chlorine concentration in the water to be treated is usually added so as to be 1 to 1000 mg / L in terms of Cl 2 , preferably 15 to 300 mg / L, More preferably, it is in the range of 15 to 200 mg / L, and in the second stage, it is added so that the dichloramine-bound chlorine concentration in the water to be treated is usually 1 to 1000 mg / L in terms of Cl 2 , but preferably 15 It is -300 mg / L, More preferably, it is the range of 15-200 mg / L.
本発明のスライム剥離方法において、第一段階処理期間中の被処理水中のモノクロラミン性結合塩素濃度をＣｌ２換算で例えば１５〜３００ｍｇ／Ｌの範囲に維持するためには、第一段階処理期間中に被処理水中のモノクロラミン性結合塩素濃度を測定し、その結果に基づいて、適宜、（Ａ）と（Ｃ）の各成分、又は上記記載の（Ａ）成分と（Ｃ）成分の混合溶液を被処理水系に添加すればよいが、該混合溶液を被処理水系に添加することが簡便で好ましい。 In the slime peeling method of the present invention, in order to maintain the monochloramine bound chlorine concentration in the water to be treated during the first stage treatment period in the range of, for example, 15 to 300 mg / L in terms of Cl 2 , the first stage treatment period The monochloramine bound chlorine concentration in the water to be treated is measured, and based on the results, the components (A) and (C), or the mixture of the components (A) and (C) described above are appropriately used. The solution may be added to the treated water system, but it is simple and preferable to add the mixed solution to the treated water system.
また、第二段階処理期間中の被処理水中のジクロラミン性結合塩素濃度をＣｌ２換算で例えば１５〜３００ｍｇ／Ｌの範囲に維持するためには、第二段階処理期間中に被処理水中のジクロラミン性結合塩素濃度を測定し、その結果に基づいて、適宜、（Ｂ）と（Ｃ）の各成分、又は上記記載の（Ｂ）成分と（Ｃ）成分の混合溶液を被処理水系に添加すればよいが、該混合溶液を被処理水系に添加することが簡便で好ましい。 Further, in order to maintain the range of dichloramine of combined chlorine concentration and Cl 2 in terms of for example 15~300mg / L in the water to be treated in the second stage treatment period, dichloramine in the for-treatment water in the second stage treatment period Measure the concentration of sex-bonded chlorine, and based on the results, add the components (B) and (C) or the mixed solution of the components (B) and (C) described above to the treated water system. However, it is convenient and preferable to add the mixed solution to the water system to be treated.
第一段階処理期間中の被処理水中のモノクロラミン性結合塩素濃度、又は第二段階処理期間中の被処理水中のジクロラミン性結合塩素濃度がＣｌ２換算で１５ｍｇ／Ｌを下回ると、スライム剥離効果が低下し、それ以上のスライム剥離が進行しなくなる可能性があり、また、第一段階処理期間中の被処理水中のモノクロラミン性結合塩素濃度、又は第二段階処理期間中の被処理水中のジクロラミン性結合塩素濃度がＣｌ２換算で３００ｍｇ／Ｌを上回る場合は、スライム剥離効果は十分発揮されるが、適用する薬剤量の増加に見合うスライム剥離効果の上昇が認められず、費用に見合う効果が期待できない可能性がある。 When the monochloramine-bound chlorine concentration in the treated water during the first stage treatment period or the dichloramine-bound chlorine concentration in the treated water during the second stage treatment period is less than 15 mg / L in terms of Cl 2 , the slime peeling effect In the treated water during the first stage treatment period, or in the treated water during the second stage treatment period. When the dichloramine-bound chlorine concentration exceeds 300 mg / L in terms of Cl 2 , the slime peeling effect is sufficiently exerted, but no increase in the slime peeling effect commensurate with the increase in the amount of drug applied is observed, and the effect worth the cost May not be expected.
剥離処理期間中の被処理水中のモノクロラミン性結合塩素濃度やジクロラミン性結合塩素濃度の測定は、ＪＩＳ Ｋ０１０１「工業用水試験方法」などに記載されているジエチル−ｐ―フェニレンジアミン（ＤＰＤ）比色法、ＤＰＤ−第一硫酸鉄滴定法などで測定できるが、濃度測定法の具体例を以下に示す。 The measurement of monochloramine-bound chlorine concentration and dichloramine-bound chlorine concentration in treated water during the stripping treatment period is a colorimetric diethyl-p-phenylenediamine (DPD) described in JIS K0101 “Industrial water test method”. A specific example of the concentration measurement method is shown below.
（残留塩素測定方法）
Ｎ，Ｎ−ジエチル−ｐ−フェニレンジアミン硫酸塩の１．０ｇとエチレンジアミン四酢酸二ナトリウム・二水和物の１．０ｇとリン酸一水素カリウムの３８．２ｇとリン酸二水素カリウムの５９．８ｇを乳鉢で混合してＤＰＤ希釈粉末とする。
（１）２００ｍＬトールビーカーに０．５ｇのＤＰＤ希釈粉末を加える。
（２）１００mＬの試験水を加え、攪拌してＤＰＤ希釈粉末を溶解させる。
（３）速やかに２．８２ｍＭ硫酸第一鉄溶液で滴定する。赤色が無色になった点を終点とする。このときの滴定量をＡ（ｍＬ）する。
（４）更に０．５％ヨウ化カリウム溶液０．１ｍＬを加えて、速やかに２．８２ｍＭ硫酸第一鉄溶液で滴定し、赤色が無色になった点を終点とする。このときの滴定量をＢ（ｍＬ）する。
（５）更にヨウ化カリウム１ｇを加えて溶かし、約２分間静置して赤に発色させる。速やかに２．８２ｍＭ硫酸第一鉄溶液で滴定し、赤色が無色になった点を終点とする。このときの滴定量をＣ（ｍＬ）する。
（６）次式により各成分の濃度が示される。
遊離残留塩素（ｍｇＣｌ２／Ｌ）＝Ａ
モノクロラミン性結合塩素（ｍｇＣｌ２／Ｌ）＝Ｂ
ジクロラミン性結合塩素（ｍｇＣｌ２／Ｌ）＝Ｃ
(Residual chlorine measurement method)
1.0 g of N, N-diethyl-p-phenylenediamine sulfate, 1.0 g of disodium ethylenediaminetetraacetate dihydrate, 38.2 g of potassium monohydrogen phosphate and 59. of potassium dihydrogen phosphate. 8 g is mixed with a mortar to make a DPD diluted powder.
(1) Add 0.5 g of DPD diluted powder to a 200 mL tall beaker.
(2) Add 100 mL of test water and stir to dissolve the DPD diluted powder.
(3) Rapidly titrate with 2.82 mM ferrous sulfate solution. The point where the red color becomes colorless is the end point. The titer at this time is A (mL).
(4) Further, 0.1 mL of a 0.5% potassium iodide solution is added, and the solution is immediately titrated with a 2.82 mM ferrous sulfate solution, and the point at which the red color becomes colorless is regarded as the end point. The titer at this time is B (mL).
(5) Add 1 g of potassium iodide and dissolve it, and let it stand for about 2 minutes to develop red color. Immediately titrate with 2.82 mM ferrous sulfate solution, and the point at which the red color became colorless is the end point. The titer at this time is C (mL).
(6) The concentration of each component is shown by the following equation.
Free residual chlorine (mgCl 2 / L) = A
Monochloramine bound chlorine (mgCl 2 / L) = B
Dichloramine bonded chlorine (mgCl 2 / L) = C
本発明のスライム剥離方法を、例えば、冷却水系に適用する場合は、該水系のブローを閉止した上で、循環水中に、適宜、（Ａ）と（Ｃ）の各成分、又は上記記載の（Ａ）成分と（Ｃ）成分の混合溶液を被処理水系に所定量添加してスライム剥離処理を開始する。このとき、可能な限り該水系の熱負荷を下げ、できれば、熱負荷なしとすることが望ましいが、熱負荷が掛かった状態であっても本スライム剥離方法は適用できる。ただし、熱負荷が掛かった状態では、次第に水系の濃縮度が上昇するため、濃縮度の管理範囲を越える場合は、適宜、間欠ブローを実施し、それに伴って第一段階では低下する（Ａ）、（Ｃ）の各成分を、第二段階では低下する（Ｂ）、（Ｃ）の各成分を、循環水中のモノクロラミン性結合塩素濃度やジクロラミン性結合塩素濃度の測定結果に基づいて、適宜、追加添加する。この場合、上記記載の混合溶液を追加添加することが簡便で好ましい。 When the slime peeling method of the present invention is applied to, for example, a cooling water system, each of the components (A) and (C) or the above-mentioned ( A predetermined amount of the mixed solution of the component A) and the component (C) is added to the treated water system, and the slime peeling treatment is started. At this time, it is desirable to reduce the heat load of the water system as much as possible, and if possible, it is desirable that there is no heat load. However, in a state where a thermal load is applied, the concentration of the aqueous system gradually increases. Therefore, if the control range of the concentration is exceeded, intermittent blow is appropriately performed, and accordingly, the first stage decreases (A). The components (C) are reduced in the second stage. The components (B) and (C) are appropriately reduced based on the measurement results of the monochloramine-bound chlorine concentration and the dichloramine-bound chlorine concentration in the circulating water. Add additional. In this case, it is convenient and preferable to add the above-mentioned mixed solution additionally.
本発明のスライム剥離方法における剥離処理期間は、対象となる水系や、そのスライム付着状況によって異なるが、第一段階が、通常は３０分以上、好ましくは１時間以上であり、第二段階が、通常は２時間以上、好ましくは６時間以上である。第一段階と第二段階の合計処理時間の上限は特に無いが、通常４８時間以内である。 The exfoliation treatment period in the slime exfoliation method of the present invention varies depending on the target aqueous system and the slime adhesion state, but the first stage is usually 30 minutes or more, preferably 1 hour or more, and the second stage is Usually, it is 2 hours or more, preferably 6 hours or more. There is no particular upper limit on the total processing time of the first stage and the second stage, but it is usually within 48 hours.
本発明のスライム剥離方法を適用する被処理水系のｐＨは特に制限はないが、通常ｐＨ５〜１１の範囲である。本発明のスライム剥離方法を適用する被処理水系の水温は特に制限はなく、通常は０〜８０℃の範囲であるが、十分なスライム剥離効果を得るためには５０℃以下であることが好ましく、４０℃以下であることがより好ましい。 Although there is no restriction | limiting in particular in the pH of the to-be-processed water system which applies the slime peeling method of this invention, Usually, it is the range of pH 5-11. The water temperature of the water to be treated to which the slime peeling method of the present invention is applied is not particularly limited and is usually in the range of 0 to 80 ° C., but is preferably 50 ° C. or less in order to obtain a sufficient slime peeling effect. More preferably, it is 40 ° C. or lower.
本発明のスライム剥離方法では、各種の好気性バクテリア、嫌気性バクテリア、黴、酵母、大腸菌などの微生物や貝類、原生動物、藻類などの系内に付着している微生物や水棲生物を剥離除去できるだけでなく、殺菌・殺藻・殺黴・殺貝作用などにより微生物や水棲生物を殺滅することもできる。また、レジオネラ属菌の剥離や殺菌に対しても有効である。 The slime stripping method of the present invention can strip and remove various aerobic bacteria, anaerobic bacteria, sputum, yeast, Escherichia coli and other microorganisms and shellfish, protozoa, algae and other microorganisms and aquatic organisms. In addition, microorganisms and aquatic organisms can be killed by sterilization, algae killing, slaughtering, and shelling action. It is also effective for exfoliation and sterilization of Legionella spp.
本発明のスライム剥離方法は、炭素鋼、鋳鉄、オーステナイト系やフェライト系やマルテンサイト系の各種のステンレス鋼、純銅、及び、りん脱酸銅、アルミニウム黄銅、アドミラルティ黄銅、キュプロニッケルなどの各種の銅合金、更に各種のアルミニウム合金などの金属材質に対して適用可能である。 The slime peeling method of the present invention includes various types of carbon steel, cast iron, austenitic and ferritic and martensitic stainless steels, pure copper, phosphorous deoxidized copper, aluminum brass, admiralty brass, cupronickel, etc. The present invention can be applied to metal materials such as copper alloys and various aluminum alloys.
本発明のスライム剥離方法では、本発明の効果を減じない範囲で、腐食抑制剤、他のスライムコントロール剤やスライム剥離剤、スケール抑制剤、分散剤、キレート剤、ｐＨ調整剤、界面活性剤、消泡剤などを同時に用いてもよい。 In the slime peeling method of the present invention, as long as the effect of the present invention is not reduced, the corrosion inhibitor, other slime control agent and slime remover, scale inhibitor, dispersant, chelating agent, pH adjuster, surfactant, You may use an antifoamer etc. simultaneously.
本発明のスライム剥離方法は、被処理水系の金属材質に対する腐食性が小さいが、腐食防止剤と併用することにより腐食をさらに低減することができる。例えば、被処理水系に銅系材質がある場合、腐食抑制剤としてベンゾトリアゾールおよびその誘導体の添加が好ましい。ベンゾトリアゾールおよびその誘導体は、１，２，３−ベンゾトリアゾールや置換−１，２，３−ベンゾトリアゾール（置換基としてアルキル基、カルボキシル基、塩素、臭素、水酸基、ニトロ基、スルホン酸基、ホスホン酸基から選択される１種以上）などであり、これらの２種以上組み合わせて使用してもよい。また、被処理水系に鉄系材質がある場合、腐食抑制剤として有機ホスホン酸、ホスフィノポリカルボン酸、ホスホノカルボン酸、リン酸、重合リン酸塩、亜鉛塩、モリブデン酸塩、ポリマレイン酸、ポリイタコン酸などを併用するのが好ましい。 The slime peeling method of the present invention is less corrosive to the metal material of the water system to be treated, but the corrosion can be further reduced by using it together with a corrosion inhibitor. For example, when there is a copper-based material in the water to be treated, it is preferable to add benzotriazole and its derivatives as a corrosion inhibitor. Benzotriazole and its derivatives include 1,2,3-benzotriazole and substituted-1,2,3-benzotriazole (alkyl groups, carboxyl groups, chlorine, bromine, hydroxyl groups, nitro groups, sulfonic acid groups, phosphonic groups as substituents) One or more selected from acid groups), and a combination of two or more of these may be used. In addition, when there is an iron-based material in the water system to be treated, organic phosphonic acid, phosphinopolycarboxylic acid, phosphonocarboxylic acid, phosphoric acid, polymerized phosphate, zinc salt, molybdate, polymaleic acid as corrosion inhibitors, It is preferable to use polyitaconic acid together.
本発明のスライム剥離方法では、スライムコントロール剤として公知の化合物を併用してもよい。このようなスライムコントロール剤の例として、２−メチルイソチアゾリン−３−オン、２−メチル−４−クロロイソチアゾリン−３−オン、２−メチル−５−クロロイソチアゾリン−３−オン、２−メチル−４，５−ジクロロイソチアゾリン−３−オン、１，２−ベンズイソチアゾリン−３−オン、２−ｎ−オクチル−４−イソチアゾリン−３−オン、４，５−ジクロロ−２−ｎ−オクチル−３（２Ｈ）イソチアゾリン等のイソチアゾリン化合物；２，２−ジブロモ−２−ニトロエタノール、２−ブロモ−２−ニトロプロパン−１，３−ジオール、２，２−ジブロモ−３−ニトリロプロピオンアミド等の有機ブロム化合物；メチレンビスチオシアネート、ビス−（１，４−ジブロムアセトキシ）−２−ブテン、ベンジルブロムアセテート、ソジウムブロマイド、α−ブロモシンナムアルデヒド、２−ピリジンチオール−１−オキシドナトリウム、ビス（２−ピリジンチオール−１−オキシド）亜鉛、２−（４−チアゾリル）ベンツイミダゾール、ヘキサヒドロ−１，３，５−トリス−（２−ヒドロキシエチル）−Ｓ−トリアジン、ビス（トリクロルメチル）スルホン、ジチオカーバメート、３，５−ジメチルテトラヒドロ−１，３，５，２Ｈ−チアジアジン−２−チオン、ブロム酢酸エチルチオフェニルエステル、α−クロルベンゾアルドキシムアセテート、２，４，５，６−テトラクロロイソフタロニトリル、１，２−ジブロモ−２，４−ジシアノブタン、３−ヨード−２−プロペニルブチルカルバメート、サリチル酸、サリチル酸ナトリウム、パラオキシ安息香酸エステル、及びｐ−クロル−ｍ−キシレノールなどが挙げられる。 In the slime peeling method of the present invention, a known compound may be used in combination as a slime control agent. Examples of such slime control agents include 2-methylisothiazolin-3-one, 2-methyl-4-chloroisothiazoline-3-one, 2-methyl-5-chloroisothiazoline-3-one, 2-methyl-4 , 5-dichloroisothiazolin-3-one, 1,2-benzisothiazolin-3-one, 2-n-octyl-4-isothiazolin-3-one, 4,5-dichloro-2-n-octyl-3 (2H ) Isothiazoline compounds such as isothiazoline; organic bromide compounds such as 2,2-dibromo-2-nitroethanol, 2-bromo-2-nitropropane-1,3-diol, 2,2-dibromo-3-nitrilopropionamide; Methylene bis thiocyanate, bis- (1,4-dibromoacetoxy) -2-butene, benzyl bromoacetate, Dium bromide, α-bromocinnamaldehyde, 2-pyridinethiol-1-oxide sodium, bis (2-pyridinethiol-1-oxide) zinc, 2- (4-thiazolyl) benzimidazole, hexahydro-1,3,5- Tris- (2-hydroxyethyl) -S-triazine, bis (trichloromethyl) sulfone, dithiocarbamate, 3,5-dimethyltetrahydro-1,3,5,2H-thiadiazin-2-thione, bromoacetic acid ethylthiophenyl ester , Α-chlorobenzoaldoxime acetate, 2,4,5,6-tetrachloroisophthalonitrile, 1,2-dibromo-2,4-dicyanobutane, 3-iodo-2-propenylbutylcarbamate, salicylic acid, sodium salicylate , Paraoxybenzoic acid esters, and Such as the p- chloro -m- xylenol.
本発明のスライム剥離方法では、スライム剥離剤として公知の化合物と併用してもよい。このようなスライム剥離剤の例として、アルキルベンゼンスルホン酸塩、ジアルキルスルホコハク酸塩などのアニオン性界面活性剤、ポリエチレングルコールとポリプロピレングリコールのブロックコポリマー、ポリアルキレングルコールアルキルフェニルエーテル、ポリアルキレングルコールアルキルエーテルなどのノニオン性界面活性剤、アルキレンポリグルコシド、高級不飽和脂肪族ジメチルアミド、酵素などが挙げられる。 In the slime peeling method of this invention, you may use together with a well-known compound as a slime peeling agent. Examples of such slime release agents include anionic surfactants such as alkylbenzene sulfonates and dialkylsulfosuccinates, block copolymers of polyethylene glycol and polypropylene glycol, polyalkylene glycol alkyl phenyl ether, polyalkylene glycol alkyl. Nonionic surfactants such as ethers, alkylene polyglucosides, higher unsaturated aliphatic dimethylamides, enzymes and the like can be mentioned.
本発明のスライム剥離方法では、スライムの粘性により抱き込まれた無機粒子が再分散されるため、これらの無機粒子の再沈着を防止するための分散剤やキレート剤の添加が好ましい、 In the slime peeling method of the present invention, since the inorganic particles embraced by the viscosity of the slime are redispersed, it is preferable to add a dispersant or a chelating agent to prevent re-deposition of these inorganic particles.
このような分散剤の例として、モノエチレン性不飽和スルホン酸とモノエチレン性不飽和カルボン酸の共重合体、あるいはモノエチレン性不飽和スルホン酸とモノエチレン性不飽和カルボン酸と他の共重合可能なモノエチレン性不飽和単量体との共重合体などが挙げられる。ここで、モノエチレン性不飽和カルボン酸として、アクリル酸、メタクリル酸、マレイン酸、無水マレイン酸、フマル酸、イタコン酸、無水イタコン酸などの１種以上が用いられる。他の共重合可能なモノエチレン性不飽和単量体としては、（メタ）アクリル酸アルキルエステル、（メタ）アクリル酸ヒドロキシルアルキルエステルなどの（メタ）アクリル酸エステル；（メタ）アクリルアミド、Ｎ−アルキル置換（メタ）アクリルアミドなどの（メタ）アクリルアミド；エチレン、プロピレン、イソプロピレン、ブチレン、イソブチレン、ヘキセン、２−エチルヘキセン、ペンテン、イソペンテン、オクテン、イソオクテンなどの炭素数２〜８のオレフィン；ビニルメチルエーテル、ビニルエチルエーテルなどのビニルアルキルエーテル；マレイン酸アルキルエステルなどがあげられ、その１種または２種以上が用いられる。分散剤の好ましい例は、２−アクリルアミド−２−メチルプロパンスルホン酸と（メタ）アクリル酸の共重合体、３−アリロキシ−２−ヒドロキシ−１−プロパンスルホン酸と（メタ）アクリル酸の共重合体、共役ジエンスルホン化物と（メタ）アクリル酸の共重合体などである。分散剤の分子量は、平均分子量として１，０００〜１００，０００が好ましいが、より好ましくは４，０００〜２０，０００である。 Examples of such dispersants include copolymers of monoethylenically unsaturated sulfonic acid and monoethylenically unsaturated carboxylic acid, or other copolymers of monoethylenically unsaturated sulfonic acid and monoethylenically unsaturated carboxylic acid And a copolymer with a possible monoethylenically unsaturated monomer. Here, as the monoethylenically unsaturated carboxylic acid, one or more of acrylic acid, methacrylic acid, maleic acid, maleic anhydride, fumaric acid, itaconic acid, itaconic anhydride and the like are used. Other copolymerizable monoethylenically unsaturated monomers include (meth) acrylic acid esters such as (meth) acrylic acid alkyl esters and (meth) acrylic acid hydroxyl alkyl esters; (meth) acrylamides and N-alkyls. (Meth) acrylamides such as substituted (meth) acrylamides; ethylene, propylene, isopropylene, butylene, isobutylene, hexene, 2-ethylhexene, pentene, isopentene, octene, isooctene and other olefins having 2 to 8 carbon atoms; vinyl methyl ether And vinyl alkyl ethers such as vinyl ethyl ether; maleic acid alkyl esters and the like, and one or more of them are used. Preferred examples of the dispersant include a copolymer of 2-acrylamido-2-methylpropanesulfonic acid and (meth) acrylic acid, and a copolymer of 3-allyloxy-2-hydroxy-1-propanesulfonic acid and (meth) acrylic acid. And a copolymer of conjugated diene sulfonate and (meth) acrylic acid. The molecular weight of the dispersant is preferably 1,000 to 100,000 as the average molecular weight, more preferably 4,000 to 20,000.
また、前記のキレート剤の好ましい例として、エチレンジアミン四酢酸塩、ヒドロキシエチルエチレンジアミン三酢酸塩、ニトリロ三酢酸塩、ジエチレントリアミン五酢酸塩、トリエチレンテトラミン六酢酸塩、１，３−プロパンジアミン四酢酸塩、１，３−ジアミノ−２−ヒドロキシプロパン四酢酸塩、ヒドロキシエチルイミノ二酢酸塩、ジヒドロキシエチルグリシン、グルコン酸塩、ヘプトグルコン酸塩、Ｎ，Ｎ−ジカルボキシメチルグルタミン酸塩、２−ヒドロキシエチリデン−２，２−ジホスホン酸、ニトリロトリメチレンホスホン酸、エチレンジアミンテトラメチレンホスホン酸、ジエチレントリアミンペンタメチレンホスホン酸、２−ホスホノブタン−１，２，４−トリカルボン酸などが挙げられる。 Preferred examples of the chelating agent include ethylenediaminetetraacetate, hydroxyethylethylenediaminetriacetate, nitrilotriacetate, diethylenetriaminepentaacetate, triethylenetetraminehexaacetate, 1,3-propanediaminetetraacetate, 1,3-diamino-2-hydroxypropanetetraacetate, hydroxyethyliminodiacetate, dihydroxyethylglycine, gluconate, heptogluconate, N, N-dicarboxymethylglutamate, 2-hydroxyethylidene-2, Examples include 2-diphosphonic acid, nitrilotrimethylenephosphonic acid, ethylenediaminetetramethylenephosphonic acid, diethylenetriaminepentamethylenephosphonic acid, and 2-phosphonobutane-1,2,4-tricarboxylic acid.
以下に本発明を具体的に説明するが、本発明はこれらの実施例に限定されるものではない。 The present invention will be specifically described below, but the present invention is not limited to these examples.
（実施例１）
８０冷凍トン、保有水量３ｍ３の実機冷却塔における実施例である。冷却塔入口・出口の循環水の温度はそれぞれ３７℃と３２℃であった。実機冷却塔に付着していたスライムの一定量（１．２ｇ）を２００メッシュのナイロン製ネットに入れたものを３個用意して冷却塔の水槽に設置した。ブローダウンを停止後、６０Ｌポリ容器に水４５Ｌと１２％（Ｃｌ２換算）次亜塩素酸ナトリウムの２．５Ｋｇを加えた溶液に２５％アンモニアの０．２８Ｋｇを速やかに溶解混合してモノクロラミン性結合塩素溶液を調製し、直ちに水槽に添加した。この時の、（Ｃ）次亜塩素酸のＣｌ２換算のモル濃度に対する（Ａ）アンモニアのモル濃度の比は、０．９７であった。モノクロラミン性結合塩素溶液を添加して１．２時間後にジクロラミン性結合塩素溶液を添加した。ここでジクロラミン性結合塩素溶液は、２０Ｌポリ容器に水１０Ｌと１２％（Ｃｌ２換算）次亜塩素酸ナトリウムの０．７５Ｋｇを加えた溶液にスルファミン酸ナトリウムの０．１５Ｋｇを速やかに溶解混合して調製した。この時の、（Ｃ）次亜塩素酸のＣｌ２換算のモル濃度に対する（Ｂ）スルファミン酸ナトリウムのモル濃度の比は、１．２であった。モノクロラミン性結合塩素とジクロラミン性結合塩素の測定結果を表１に示す。
(Example 1)
This is an example in an actual cooling tower having 80 refrigeration tons and a retained water amount of 3 m 3 . The temperatures of circulating water at the cooling tower inlet and outlet were 37 ° C. and 32 ° C., respectively. Three pieces of a certain amount (1.2 g) of slime adhering to the actual cooling tower were put in a 200-mesh nylon net and installed in the water tank of the cooling tower. After stopping the blowdown, a monochloramine is obtained by quickly dissolving and mixing 0.28 kg of 25% ammonia in a solution obtained by adding 45 kg of water and 2.5 kg of 12% (Cl 2 equivalent) sodium hypochlorite to a 60 l plastic container. A sex-bound chlorine solution was prepared and immediately added to the water bath. At this time, the ratio of the molar concentration of (A) ammonia to the molar concentration of (C) hypochlorous acid in terms of Cl 2 was 0.97. After 1.2 hours from the addition of the monochloramine-bound chlorine solution, the dichloramine-bound chlorine solution was added. Here, the dichloramine bonded chlorine solution is obtained by quickly dissolving and mixing 0.15 kg of sodium sulfamate in a solution obtained by adding 10 L of water and 0.75 kg of 12% (Cl 2 equivalent) sodium hypochlorite to a 20 L plastic container. Prepared. At this time, the ratio of the molar concentration of sodium sulfamate (B) to the molar concentration of (C) hypochlorous acid in terms of Cl 2 was 1.2. Table 1 shows the measurement results of monochloramine-bound chlorine and dichloramine-bound chlorine.
モノクロラミン性結合塩素溶液を添加して第一段階の剥離処理を開始した後、経過時間１．２時間の第一段階終了時に１個のナイロン製ネットを取り出しスライムの重量を測定したところ、スライム減少率は７０％であった。ジクロラミン性結合塩素溶液を添加して第二段階の剥離処理を開始した後、経過時間６時間と２４時間（第二段階終了時であって剥離処理終了時）にナイロン製ネットを取り出しスライムの重量を測定したところ、スライム減少率はそれぞれ８５％と９５％であった。 After adding the monochloramine-bonded chlorine solution and starting the first stage of peeling treatment, when one stage of the first stage with an elapsed time of 1.2 hours was completed, one nylon net was taken out and the weight of the slime was measured. The reduction rate was 70%. After adding the dichloramine-bound chlorine solution and starting the second-stage release treatment, the nylon net is taken out at the elapsed time of 6 hours and 24 hours (at the end of the second stage and at the end of the release treatment). The slime reduction rate was 85% and 95%, respectively.
ここで、スライム重量の減少は、ナイロン製ネット内のスライム塊が２００メッシュを通過するほどに細かく崩され分散し、微細化したスライムがネット内から抜け出たことを示しており、特に粘着性の低下や分散によるスライム剥離の指標であり、減少率が大きいほど、スライム剥離効果が高いと判断できる。尚、スライム減少率は剥離処理開始前のスライム重量（１．２ｇ）に対する、処理後の減少したスライム重量の割合である。 Here, the reduction of the slime weight indicates that the slime mass in the nylon net is finely broken and dispersed so as to pass through 200 mesh, and the refined slime has escaped from the net. It is an index of slime peeling due to reduction or dispersion, and it can be judged that the slime peeling effect is higher as the decrease rate is larger. The slime reduction rate is the ratio of the reduced slime weight after the treatment to the slime weight (1.2 g) before the start of the peeling treatment.
（比較例１）
実施例１において、ジクロラミン性結合塩素を添加せず、全剥離処理時間の２４時間をモノクロラミン性結合塩素だけで処理した。その他の条件は実施例１と同じであった。
(Comparative Example 1)
In Example 1, no dichloramine-bonded chlorine was added, and the entire stripping treatment time was treated with monochloramine-bonded chlorine alone for 24 hours. Other conditions were the same as in Example 1.
モノクロラミン性結合塩素溶液を添加して経過時間１．２時間、６時間、及び２４時間（剥離処理終了時）に各１個のナイロン製ネットを取り出しスライムの重量を測定したところ、スライム減少率はそれぞれ６８％、７０％、及び７３％であった。 Monochloramine bound chlorine solution was added and each nylon net was taken out at 1.2 hours, 6 hours, and 24 hours (at the end of the peeling process) and the slime weight was measured. Were 68%, 70%, and 73%, respectively.
（比較例２）
実施例１において、モノクロラミン性結合塩素を添加せず、全剥離処理時間の２４時間をジクロラミン性結合塩素だけで処理した。その他の条件は実施例１と同じであった。
(Comparative Example 2)
In Example 1, no monochloramine-bound chlorine was added, and 24 hours of the total stripping treatment time was treated with dichloroamine-bound chlorine alone. Other conditions were the same as in Example 1.
ジクロラミン性結合塩素溶液を添加して経過時間１．２時間、６時間、及び２４時間（剥離処理終了時）に各１個のナイロン製ネットを取り出しスライムの重量を測定したところ、スライム減少率はそれぞれ４６％、５２％、及び５８％であった。 When a dichloramine-bound chlorine solution was added and each nylon net was taken out at an elapsed time of 1.2 hours, 6 hours, and 24 hours (at the end of the peeling process) and the weight of the slime was measured, the slime reduction rate was They were 46%, 52%, and 58%, respectively.
（比較例３）
実施例１の第一段階において、モノクロラミン性結合塩素の替わりにジクロラミン性結合塩素を添加し、第二段階において、ジクロラミン性結合塩素の替わりにモノクロラミン性結合塩素を添加した。その他の条件は実施例１と同じであった。
(Comparative Example 3)
In the first stage of Example 1, dichloramine bonded chlorine was added instead of monochloramine bonded chlorine, and in the second stage, monochloramine bonded chlorine was added instead of dichloramine bonded chlorine. Other conditions were the same as in Example 1.
ジクロラミン性結合塩素溶液を添加して第一段階の剥離処理を開始した後、経過時間１．２時間の第一段階終了時に１個のナイロン製ネットを取り出しスライムの重量を測定したところ、スライム減少率は４５％であった。モノクロラミン性結合塩素溶液を添加して第二段階の剥離処理を開始した後、経過時間６時間と２４時間（第二段階終了時であって剥離処理終了時）にナイロン製ネットを取り出しスライムの重量を測定したところ、スライム減少率はそれぞれ５７％と６８％であった。 After adding the dichloramine-bonded chlorine solution and starting the first-stage peeling treatment, when one stage of the first stage of 1.2 hours elapsed, one nylon net was taken out and the slime weight was measured. The rate was 45%. After adding the monochloramine-bonded chlorine solution and starting the second stage peeling process, the nylon net is taken out at 6 hours and 24 hours (at the end of the second stage and at the end of the peeling process) to remove the slime When the weight was measured, the slime reduction rates were 57% and 68%, respectively.
実施例１と比較例１〜３の結果から、モノクロラミン性結合塩素単独、ジクロラミン性結合塩素単独、及び、ジクロラミン性結合塩素処理後にモノクロラミン性結合塩素処理を行う方法では、十分なスライム剥離効果が得られず、本発明の、被処理水中に、（Ａ）アンモニアおよび／またはアンモニウム塩と（Ｃ）次亜塩素酸の反応によって得られるモノクロラミン性結合塩素を存在させる第一段階の後に、（Ｂ）スルファミン酸および／またはスルファミン酸塩と（Ｃ）次亜塩素酸の反応によって得られるジクロラミン性結合塩素を存在させる第二段階を行う順序のスライム剥離方法のみが、優れたスライム剥離効果を示すことが明らかになった。また、ヒドラジンを用いない本発明のスライム剥離方法は安全性が高い。 From the results of Example 1 and Comparative Examples 1 to 3, the monochloramine-bonded chlorine alone, the dichloramine-bonded chlorine alone, and the method of performing the monochloramine-bonded chlorine treatment after the dichloramine-bonded chlorine treatment have a sufficient slime peeling effect. After the first stage of the present invention in which the monochloramine bound chlorine obtained by the reaction of (A) ammonia and / or ammonium salt and (C) hypochlorous acid is present in the water to be treated, Only the slime peeling method in the order of performing the second stage in which dichloramine bond chlorine obtained by the reaction of (B) sulfamic acid and / or sulfamate and (C) hypochlorous acid is present has an excellent slime peeling effect. It became clear to show. Moreover, the slime peeling method of the present invention that does not use hydrazine is highly safe.
冷却水系、紙パルプ製造プロセスの各種水系、鉄鋼製造プロセスの各種水系、集塵水系、排水系統、切削油などの金属加工処理水系などの各種水系おいて、安全性が高く、かつ、効率的に、系内に付着しているスライムを剥離することができる。
Safe and efficient in various water systems such as cooling water systems, various water systems in the pulp and paper manufacturing process, various water systems in the steel manufacturing process, dust collection water systems, drainage systems, and metal processing water systems such as cutting oil. The slime adhering in the system can be peeled off.
Claims (2)
前記の第一段階において、被処理水に対する（Ａ）アンモニアおよび／またはアンモニウム塩（ただし、スルファミン酸アンモニウムを除く）と（Ｃ）次亜塩素酸の添加比率が、（Ｃ）次亜塩素酸のＣｌ ２ 換算のモル濃度に対する（Ａ）アンモニアおよび／またはアンモニウム塩（ただし、スルファミン酸アンモニウムを除く）のモル濃度の比として０．６〜１．５であり、かつ、前記第一段階の処理期間中の被処理水中のモノクロラミン性結合塩素濃度をＣｌ ２ 換算で１５〜３００ｍｇ／Ｌの範囲に維持するように前記（Ａ）、（Ｃ）の各成分を被処理水に添加し、続いて、前記の第二段階において、被処理水に対する（Ｂ）スルファミン酸および／またはスルファミン酸塩（ただし、スルファミン酸アンモニウムを除く）と（Ｃ）次亜塩素酸の添加比率が、（Ｃ）次亜塩素酸のＣｌ ２ 換算のモル濃度に対する（Ｂ）スルファミン酸および／またはスルファミン酸塩（ただし、スルファミン酸アンモニウムを除く）のモル濃度の比として０．６〜１．５であり、かつ、前記第二段階の処理期間中の被処理水中のジクロラミン性結合塩素濃度をＣｌ ２ 換算で１５〜３００ｍｇ／Ｌの範囲に維持するように前記（Ｂ）、（Ｃ）の各成分を被処理水に添加することを特徴とするスライム剥離方法。 After the first stage in which (A) ammonia and / or ammonium salt (excluding ammonium sulfamate) and (C) monochloramine bound chlorine obtained by reaction of hypochlorous acid are present in the water to be treated, (B) A second step is carried out in which dichloramine-bound chlorine obtained by the reaction of sulfamic acid and / or sulfamate (excluding ammonium sulfamate) and (C) hypochlorous acid is present (wherein The dichloramine-bound chlorine is mainly N-monochlororosulmic acid, and the concentration of the dichloramine-bound chlorine is measured by a diethyl-p-phenylenediamine (DPD) colorimetric method, a DPD-iron ferrous sulfate titration method, or the like. ) A slime exfoliation method that is processed in two steps ,
In the first stage, the ratio of (A) ammonia and / or ammonium salt (excluding ammonium sulfamate) to (C) hypochlorous acid relative to the water to be treated is (C) hypochlorous acid The ratio of the molar concentration of (A) ammonia and / or ammonium salt (excluding ammonium sulfamate) to the molar concentration in terms of Cl 2 is 0.6 to 1.5, and the treatment period of the first stage The components (A) and (C) are added to the water to be treated so that the concentration of monochloramine bound chlorine in the water to be treated is within the range of 15 to 300 mg / L in terms of Cl 2 , In the second stage, (B) sulfamic acid and / or sulfamic acid salt (excluding ammonium sulfamate) and (C) hypochlorous acid to the water to be treated Addition ratio of periodate, 0 as the ratio of the molar concentration of (C) hypophosphite to the molar concentration of Cl 2 Conversion chlorate (B) sulfamic acid and / or sulfamic acid salts (except ammonium sulfamate). (B), so as to maintain a dichloramine-bound chlorine concentration in the water to be treated during the treatment period of the second stage in the range of 15 to 300 mg / L in terms of Cl 2, which is 6 to 1.5. The slime peeling method characterized by adding each component of (C) to to-be-processed water.
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| JP7111308B2 (en) * | 2018-05-07 | 2022-08-02 | 智洋 石田 | High-concentration stabilization method and treatment method for bleaching agents for clothing and building interior and exterior materials |
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