JP5729399B2 - Slime control method in pulp and paper water system - Google Patents
Slime control method in pulp and paper water system Download PDFInfo
- Publication number
- JP5729399B2 JP5729399B2 JP2013015666A JP2013015666A JP5729399B2 JP 5729399 B2 JP5729399 B2 JP 5729399B2 JP 2013015666 A JP2013015666 A JP 2013015666A JP 2013015666 A JP2013015666 A JP 2013015666A JP 5729399 B2 JP5729399 B2 JP 5729399B2
- Authority
- JP
- Japan
- Prior art keywords
- water
- paper pulp
- salt
- sulfamic acid
- chlorine
- 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.)
- Active
Links
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims description 104
- 238000000034 method Methods 0.000 title claims description 27
- 229920001131 Pulp (paper) Polymers 0.000 claims description 55
- 239000000460 chlorine Substances 0.000 claims description 47
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 39
- 229910052801 chlorine Inorganic materials 0.000 claims description 39
- 239000007800 oxidant agent Substances 0.000 claims description 38
- 230000001590 oxidative effect Effects 0.000 claims description 37
- -1 sulfamic acid compound Chemical class 0.000 claims description 37
- 150000003839 salts Chemical class 0.000 claims description 36
- 239000000645 desinfectant Substances 0.000 claims description 18
- 239000000203 mixture Substances 0.000 claims description 11
- 230000001629 suppression Effects 0.000 claims description 9
- 239000008235 industrial water Substances 0.000 claims description 8
- 150000003863 ammonium salts Chemical class 0.000 claims description 3
- 239000005708 Sodium hypochlorite Substances 0.000 description 20
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 20
- 241000894006 Bacteria Species 0.000 description 10
- 239000003112 inhibitor Substances 0.000 description 10
- 238000004519 manufacturing process Methods 0.000 description 10
- 230000000844 anti-bacterial effect Effects 0.000 description 9
- 239000007864 aqueous solution Substances 0.000 description 7
- 238000005260 corrosion Methods 0.000 description 7
- 230000007797 corrosion Effects 0.000 description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 239000003899 bactericide agent Substances 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- LNOPIUAQISRISI-UHFFFAOYSA-N n'-hydroxy-2-propan-2-ylsulfonylethanimidamide Chemical compound CC(C)S(=O)(=O)CC(N)=NO LNOPIUAQISRISI-UHFFFAOYSA-N 0.000 description 6
- 230000000855 fungicidal effect Effects 0.000 description 5
- 239000000417 fungicide Substances 0.000 description 5
- 238000002360 preparation method Methods 0.000 description 5
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 239000013626 chemical specie Substances 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 238000004537 pulping Methods 0.000 description 3
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 2
- 229920002472 Starch Polymers 0.000 description 2
- SWLVFNYSXGMGBS-UHFFFAOYSA-N ammonium bromide Chemical compound [NH4+].[Br-] SWLVFNYSXGMGBS-UHFFFAOYSA-N 0.000 description 2
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 2
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 2
- 235000011130 ammonium sulphate Nutrition 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- OGQPUOLFKIMRMF-UHFFFAOYSA-N chlorosulfamic acid Chemical compound OS(=O)(=O)NCl OGQPUOLFKIMRMF-UHFFFAOYSA-N 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 230000033116 oxidation-reduction process Effects 0.000 description 2
- 239000010893 paper waste Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000008107 starch Substances 0.000 description 2
- 235000019698 starch Nutrition 0.000 description 2
- 230000001954 sterilising effect Effects 0.000 description 2
- 239000002023 wood Substances 0.000 description 2
- GEHMBYLTCISYNY-UHFFFAOYSA-N Ammonium sulfamate Chemical compound [NH4+].NS([O-])(=O)=O GEHMBYLTCISYNY-UHFFFAOYSA-N 0.000 description 1
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000000498 cooling water Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000005188 flotation Methods 0.000 description 1
- 239000008103 glucose Substances 0.000 description 1
- 239000003673 groundwater Substances 0.000 description 1
- QWPPOHNGKGFGJK-UHFFFAOYSA-N hypochlorous acid Chemical compound ClO QWPPOHNGKGFGJK-UHFFFAOYSA-N 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 238000009287 sand filtration Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 238000004659 sterilization and disinfection Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000008399 tap water Substances 0.000 description 1
- 235000020679 tap water Nutrition 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/76—Treatment of water, waste water, or sewage by oxidation with halogens or compounds of halogens
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N59/00—Biocides, pest repellants or attractants, or plant growth regulators containing elements or inorganic compounds
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H21/00—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties
- D21H21/02—Agents for preventing deposition on the paper mill equipment, e.g. pitch or slime control
- D21H21/04—Slime-control agents
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H21/00—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties
- D21H21/14—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties characterised by function or properties in or on the paper
- D21H21/36—Biocidal agents, e.g. fungicidal, bactericidal, insecticidal agents
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/26—Nature of the water, waste water, sewage or sludge to be treated from the processing of plants or parts thereof
- C02F2103/28—Nature of the water, waste water, sewage or sludge to be treated from the processing of plants or parts thereof from the paper or cellulose industry
Landscapes
- Life Sciences & Earth Sciences (AREA)
- Pest Control & Pesticides (AREA)
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Wood Science & Technology (AREA)
- Zoology (AREA)
- Health & Medical Sciences (AREA)
- Inorganic Chemistry (AREA)
- Dentistry (AREA)
- General Health & Medical Sciences (AREA)
- Agronomy & Crop Science (AREA)
- Plant Pathology (AREA)
- Environmental Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Organic Chemistry (AREA)
- Paper (AREA)
- Treatment Of Water By Oxidation Or Reduction (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
Description
本発明は、紙パルプ水系におけるスライムを抑制する方法に関する。 The present invention relates to a method for suppressing slime in a paper pulp water system.
製紙パルプ製造工程の水には、木質の成分やデンプンなどのＣＯＤ成分が豊富に含まれ、工業用水などに比べて菌数が多い。そのためスライムが生育しやすく、紙パルプの品質や生産性を悪化させる。 The water in the pulp and paper manufacturing process contains abundant wood components and COD components such as starch, and has a larger number of bacteria than industrial water. Therefore, slime is easy to grow, and deteriorates the quality and productivity of paper pulp.
近年、紙パルプ水系ではスライムを抑制するために、高い殺菌力を有する無機系の酸化性殺菌剤が使用されている。しかし、これらの無機系酸化性殺菌剤は、酸化力が高く、紙パルプ水系の設備を腐食するリスクが高い。無機系酸化性殺菌剤の添加量を少なくすれば、紙パルプ水系の設備を腐食するリスクを小さくすることができるが、菌数の高い紙パルプ水系ではスライムを十分に抑制できなくなる。 In recent years, an inorganic oxidizing disinfectant having a high bactericidal power has been used in order to suppress slime in paper pulp water systems. However, these inorganic oxidizing disinfectants have high oxidizing power and have a high risk of corroding paper pulp water-based equipment. If the addition amount of the inorganic oxidizing disinfectant is reduced, the risk of corroding the paper pulp water system equipment can be reduced, but the slime cannot be sufficiently suppressed in the paper pulp water system having a high number of bacteria.
近年、塩素系酸化剤とスルファミン酸またはその塩との混合物が、殺菌力はほとんど有してはないが、スライムの生育を抑制する剤として、使用しうることがわかった（特許文献１）。塩素系酸化剤とスルファミン酸またはその塩との混合物は、菌数が少ない水系において、スライムを抑制、またはスライムを剥離し得るとともに、無機系酸化性殺菌と比べて、酸化力が低いため、紙パルプ水系の設備を腐食するリスクが低い。しかし、塩素系酸化剤とスルファミン酸またはその塩との混合物を単独で添加をしても、菌数が多い紙パルプ水系において、十分なスライム抑制効果を有しない。 In recent years, it has been found that a mixture of a chlorine-based oxidizing agent and sulfamic acid or a salt thereof can be used as an agent that suppresses the growth of slime, although it has little bactericidal power (Patent Document 1). A mixture of a chlorinated oxidant and sulfamic acid or a salt thereof can suppress slime or peel slime in an aqueous system with a small number of bacteria, and has a lower oxidizing power than inorganic oxidative sterilization. Low risk of corroding pulp water equipment. However, even if a mixture of a chlorine-based oxidizing agent and sulfamic acid or a salt thereof is added alone, it does not have a sufficient slime-inhibiting effect in a paper pulp water system having a large number of bacteria.
そこで、本発明は、製紙パルプ製造工程において、スライムを抑制できる一方で、紙パルプ水系の設備の腐食を抑制することができるスライム抑制方法を提供することを目的とする。 Then, this invention aims at providing the slime suppression method which can suppress corrosion of the equipment of a paper pulp water system, while suppressing a slime in a paper pulp manufacturing process.
本発明者は、紙パルプ水系に給水される水に、塩素系酸化剤とスルファミン酸化合物またはその塩とを添加することで、紙パルプ水系への無機系酸化性殺菌剤の量を少なくして、スライムを抑制することができることを見出した。 The present inventor reduced the amount of the inorganic oxidizing disinfectant to the paper pulp water system by adding a chlorine-based oxidant and a sulfamic acid compound or a salt thereof to the water supplied to the paper pulp water system. And found that slime can be suppressed.
具体的には、本発明は以下の方法を提供する。 Specifically, the present invention provides the following methods.
（１）無機系酸化性殺菌剤が添加される紙パルプ水系に給水される水に、スルファミン酸化合物もしくはその塩、または塩素系酸化剤とスルファミン酸化合物もしくはその塩と、を添加する紙パルプ水系におけるスライム抑制方法。 (1) A paper pulp water system in which a sulfamic acid compound or a salt thereof, or a chlorine-based oxidizing agent and a sulfamic acid compound or a salt thereof is added to water supplied to a paper pulp water system to which an inorganic oxidizing fungicide is added. Slime control method.
（２）前記紙パルプ水系に給水される水に、塩素系酸化剤とスルファミン酸化合物またはその塩との混合物を添加する、（１）に記載のスライム抑制方法。 (2) The slime suppression method according to (1), wherein a mixture of a chlorine-based oxidizing agent and a sulfamic acid compound or a salt thereof is added to water supplied to the paper pulp water system.
（３）前記無機系酸化性殺菌剤が、塩素系酸化剤とアンモニウム塩との混合物、または塩素系酸化剤とアミノ化合物との混合物を含む、（１）または（２）に記載のスライム抑制方法。 (3) The slime suppression method according to (1) or (2), wherein the inorganic oxidizing bactericidal agent includes a mixture of a chlorine-based oxidizing agent and an ammonium salt, or a mixture of a chlorine-based oxidizing agent and an amino compound. .
（４）前記給水される水が工業用水または再利用水である、（１）〜（３）いずれかに記載のスライム抑制方法。 (4) The slime suppression method according to any one of (1) to (3), wherein the water supplied is industrial water or reused water.
本発明によれば、紙パルプ水系に給水される水および製紙パルプ製造工程の水の双方におけるスライムを抑制できる一方で、紙パルプ水系の設備の腐食を抑制することができる。 ADVANTAGE OF THE INVENTION According to this invention, while being able to suppress the slime in both the water supplied to a paper pulp water system and the water of a paper pulp manufacturing process, corrosion of a paper pulp water system equipment can be suppressed.
以下、本発明の実施形態について説明するが、これにより本発明が制限されるものではない。 Hereinafter, although embodiment of this invention is described, this invention is not restrict | limited by this.
本発明は、製紙パルプ製造工程の無機系酸化性殺菌剤が添加される紙パルプ水系に給水される水に、スルファミン酸化合物もしくはその塩、または塩素系酸化剤とスルファミン酸化合物もしくはその塩と、を添加するスライム抑制方法である。 The present invention provides water supplied to a paper pulp aqueous system to which an inorganic oxidizing fungicide in a paper pulp manufacturing process is added, sulfamic acid compound or a salt thereof, or a chlorine-based oxidizing agent and a sulfamic acid compound or a salt thereof, Is a method for suppressing slime.
製紙パルプ製造工程は、公知のものであってよく、例えば、木材パルプ、古紙パルプなどのパルプ化工程、調成工程、抄紙工程などを含む。パルプ化工程は、木材、古紙などをパルプ化する工程であり、調成工程は、各パルプを混合した紙料を調製する工程であり、抄紙工程は、水で薄めた原料から紙を抄く工程である。 The papermaking pulp manufacturing process may be a known one, and includes, for example, a pulping process such as wood pulp and waste paper pulp, a preparation process, and a papermaking process. The pulping process is a process for pulping wood, waste paper, etc., the preparation process is a process for preparing a stock mixed with each pulp, and the papermaking process is for making paper from raw materials diluted with water. It is a process.
紙パルプ水系に給水される水は、製紙パルプ製造工程で使用される水を意味し、特に制限されないが、例えば、上水道水、冷却水、河川水、地下水などを含む工業用水や、製紙パルプ製造工程の排水を固液分離や生物処理を行って得られる再利用水の１以上であってよい。 Water supplied to the paper pulp water system means water used in the paper pulp manufacturing process, and is not particularly limited. For example, industrial water including tap water, cooling water, river water, ground water, and paper pulp manufacturing The waste water of the process may be one or more of reused water obtained by performing solid-liquid separation or biological treatment.
第１の実施形態において、製紙パルプ製造工程の無機系酸化性殺菌剤が添加されスライム抑制が行なわれる紙パルプ水系に給水される水に、塩素系酸化剤とスルファミン酸化合物またはその塩とを添加する。 In the first embodiment, a chlorine-based oxidizing agent and a sulfamic acid compound or a salt thereof are added to water supplied to a paper pulp aqueous system to which slime suppression is performed by adding an inorganic oxidizing fungicide in a paper pulp manufacturing process. To do.
塩素系酸化剤は、特に制限されないが、コスト、取扱性、安全性、水に対する溶解度などの面から、次亜塩素酸またはその塩（例えば、次亜塩素酸ソーダ）の１以上であってよく、次亜塩素酸ソーダが特に好ましい。次亜塩素酸ソーダとしては、一般に流通している１２％次亜塩素酸ソーダを用いることができる。次亜塩素酸ソーダは、酸化力が非常に高く、紙パルプ水系の設備を腐食しやすいが、スルファミン酸化合物またはその塩と併用されることで、紙パルプ水系の設備の腐食を抑制できる。なお、工業用水や再利用水は、一般的に次亜塩素酸ソーダによる簡易な処理が行われており、本発明においては水系に残留する次亜塩素酸ソーダを塩素系酸化剤として利用してもよい。 The chlorine-based oxidizing agent is not particularly limited, but may be one or more of hypochlorous acid or a salt thereof (for example, sodium hypochlorite) in terms of cost, handleability, safety, solubility in water, and the like. Sodium hypochlorite is particularly preferred. As sodium hypochlorite, 12% sodium hypochlorite which is generally available can be used. Sodium hypochlorite has a very high oxidizing power and easily corrodes paper pulp water-based equipment, but when used in combination with a sulfamic acid compound or a salt thereof, corrosion of paper pulp water-based equipment can be suppressed. In addition, industrial water and reused water are generally subjected to simple treatment with sodium hypochlorite, and in the present invention, sodium hypochlorite remaining in the water system is used as a chlorine-based oxidizing agent. Also good.
スルファミン酸化合物は、特に制限されないが、スルファミン酸、クロロスルファミン酸などであり、その塩は、スルファミン酸アンモニウムなどである。スルファミン酸化合物またはその塩は、これらの１以上であってよい。ヒドラジンのように有毒ではなく、安全性が高いため、スルファミン酸が特に好ましい。 The sulfamic acid compound is not particularly limited, and examples thereof include sulfamic acid and chlorosulfamic acid, and salts thereof include ammonium sulfamic acid and the like. The sulfamic acid compound or salt thereof may be one or more of these. Sulfamic acid is particularly preferred because it is not toxic like hydrazine and is highly safe.
塩素系酸化剤とスルファミン酸化合物またはその塩の添加方法は、特に制限されないが、混合物として添加してもよく、またはそれぞれを同じ場所もしくは異なる場所にそれらが添加後に混ざりあう態様で添加してもよい。塩素系酸化剤とスルファミン酸化合物が混ざり合うことで、塩素系酸化剤の酸化力が抑制された安定な化学種が形成されていることが推測される。そのため、塩素系酸化剤とスルファミン酸化合物またはその塩は、安定な化学種が大量に形成されうる混合物として使用するのが好ましい。 The method for adding the chlorine-based oxidizing agent and the sulfamic acid compound or a salt thereof is not particularly limited, but may be added as a mixture, or may be added in the form where they are mixed in the same place or different places after addition. Good. It is presumed that a stable chemical species in which the oxidizing power of the chlorine-based oxidizing agent is suppressed is formed by mixing the chlorine-based oxidizing agent and the sulfamic acid compound. Therefore, it is preferable to use the chlorinated oxidant and the sulfamic acid compound or a salt thereof as a mixture in which a large amount of stable chemical species can be formed.
塩素系酸化剤とスルファミン酸化合物またはその塩の添加比率は、特に制限されないが、安定な化学種を効率的に生成させる観点から塩素系酸化剤の塩素濃度とスルファミン酸化合物またはその塩のモル比が、２：１〜１：５であるのが好ましく、２：１〜１：２であるのが特に好ましい。水系に残留する次亜塩素酸ソーダを利用する場合、塩素系酸化剤の添加比率は、スルファミン酸化合物またはその塩に対し小さくなる。 The addition ratio of the chlorinated oxidant and the sulfamic acid compound or salt thereof is not particularly limited, but from the viewpoint of efficiently generating stable chemical species, the chlorine concentration of the chlorinated oxidant and the molar ratio of the sulfamic acid compound or salt thereof. Is preferably 2: 1 to 1: 5, particularly preferably 2: 1 to 1: 2. When using sodium hypochlorite remaining in the aqueous system, the addition ratio of the chlorinated oxidant is smaller than that of the sulfamic acid compound or a salt thereof.
塩素系酸化剤とスルファミン酸化合物またはその塩の添加濃度は、特に制限されないが、紙パルプ水系に０．０１〜２ｍｇ／Ｌ ａｓ Ｃｌ２、好ましくは０．５〜１ｍｇ／Ｌ ａｓ Ｃｌ２で残留させることで、紙パルプ水系に添加する無機系酸化性殺菌剤の量が少なくても十分な殺菌力を得られ、スライムを抑制できる一方で、紙パルプ水系の設備の腐食を抑制できる。紙パルプ水系の残留塩素濃度を上記の範囲内にするため、紙パルプ水系に導入される直前の水系に０．１〜１０ｍｇ／Ｌ ａｓ Ｃｌ２で残留するように塩素系酸化剤とスルファミン酸化合物またはその塩を添加するのが好ましく、２〜５ｍｇ／Ｌ ａｓ Ｃｌ２となるように塩素系酸化剤とスルファミン酸化合物またはその塩を添加するのが特に好ましい。なお、塩素系酸化剤とスルファミン酸化合物またはその塩を上記の濃度で残留させたとき、紙パルプ水系の酸化還元電位（ＯＲＰ）が、塩素系酸化剤とスルファミン酸化合物またはその塩とを添加しないときに比べて１０ｍＶ以上、好ましくは１２〜６０ｍＶ上昇させることができ、スライムを抑制できる一方で、紙パルプ水系の設備の腐食を抑制できる。水系に残留する次亜塩素酸ソーダを利用する場合、塩素系酸化剤の添加濃度は小さくなる。 The addition concentration of the chlorine-based oxidizing agent and the sulfamic acid compound or a salt thereof is not particularly limited, but remains in the paper pulp water system at 0.01 to 2 mg / L as Cl 2 , preferably 0.5 to 1 mg / L as Cl 2 . As a result, sufficient sterilizing power can be obtained even if the amount of the inorganic oxidizing disinfectant added to the paper pulp water system is small, and slime can be suppressed, while corrosion of the paper pulp water system can be suppressed. In order to keep the residual chlorine concentration of the paper pulp water system within the above range, the chlorine-based oxidizing agent and the sulfamic acid compound remain in the water system immediately before being introduced into the paper pulp water system at 0.1 to 10 mg / L as Cl 2 . Alternatively, it is preferable to add a salt thereof, and it is particularly preferable to add a chlorine-based oxidizing agent and a sulfamic acid compound or a salt thereof so as to be 2 to 5 mg / L as Cl 2 . In addition, when a chlorine-based oxidant and a sulfamic acid compound or a salt thereof are left at the above concentrations, the redox potential (ORP) of the paper pulp water system does not add a chlorine-based oxidant and a sulfamic acid compound or a salt thereof. It can be raised by 10 mV or more, preferably 12 to 60 mV compared to the case, and slime can be suppressed, while corrosion of paper pulp water-based equipment can be suppressed. When using sodium hypochlorite remaining in the aqueous system, the concentration of the chlorinated oxidant is reduced.
上記組み合わせには、塩素系酸化剤の保存安定性を向上する観点で、水酸化ナトリウムや水酸化カリウムなどのアルカリも含まれていてもよい。また、さらに他の酸化剤を添加してもよい。 The above combination may contain an alkali such as sodium hydroxide or potassium hydroxide from the viewpoint of improving the storage stability of the chlorinated oxidant. Further, another oxidizing agent may be added.
一方、紙パルプ水系に添加する無機系酸化性殺菌剤は、特に制限されないが、塩素系酸化剤と硫酸アンモニウム、臭化アンモニウムなどアンモニウム塩や他の無機アミン化合物とを混合・反応させた塩素系の酸化性殺菌剤が挙げられる。 On the other hand, the inorganic oxidizing disinfectant added to the paper pulp water system is not particularly limited, but a chlorine-based oxidant mixed with and reacted with an ammonium salt such as ammonium sulfate and ammonium bromide and other inorganic amine compounds. An oxidizing disinfectant is mentioned.
無機系酸化性殺菌剤の添加場所は、特に制限されないが、塩素系酸化剤とスルファミン酸化合物またはその塩が水に存在する場所に添加されれば、紙パルプ水系に添加する無機系酸化性殺菌剤の添加量を少なくすることができ、紙パルプ水系の設備の腐食を抑制することができる一方で、有効にスライムを抑制し得る。そのため、塩素系酸化剤とスルファミン酸化合物またはその塩は、紙パルプ水系に導入される直前の水系紙パルプ水系に添加するのが好ましい。なお、紙パルプ水系に導入される直前の水系の菌数が少ないとき、塩素系酸化剤とスルファミン酸化合物またはその塩を紙パルプ水系に導入される直前の水系に添加してもよい。 There are no particular restrictions on the location where the inorganic oxidizing disinfectant is added, but if the chlorine-based oxidizing agent and sulfamic acid compound or salt thereof are added in water, the inorganic oxidizing disinfectant added to the paper pulp water system The addition amount of the agent can be reduced, and corrosion of the paper pulp water system equipment can be suppressed, while slime can be effectively suppressed. Therefore, it is preferable to add the chlorine-based oxidizing agent and the sulfamic acid compound or a salt thereof to the aqueous paper pulp water system immediately before being introduced into the paper pulp water system. When the number of bacteria in the aqueous system immediately before being introduced into the paper pulp aqueous system is small, a chlorine-based oxidizing agent and a sulfamic acid compound or a salt thereof may be added to the aqueous system immediately before being introduced into the paper pulp aqueous system.
紙パルプ水系に導入される直前の水に残留する塩素系酸化剤とスルファミン酸化合物またはその塩の濃度、紙パルプ水系の水に残留する塩素系酸化剤とスルファミン酸化合物またはその塩の濃度、および紙パルプ水系の酸化還元電位は、特に制限されないが、例えば、紙パルプ水系に給水される水、仕込み・濃調水として一度プロセス工程の再利用水と混合・貯留される再利用水タンク、またはこの水によって仕込み・濃調がなされる原料スラリー、またはこれらの水が集まる白水などで測定される。殺菌剤の添加量を制御することができるので、濃度や酸化還元電位は、連続的に測定してもよい。 The concentration of chlorine-based oxidant and sulfamic acid compound or salt thereof remaining in the water just prior to introduction into the paper pulp water system, the concentration of chlorine-based oxidant and sulfamic acid compound or salt thereof remaining in the water of the paper pulp water system, and The redox potential of the paper pulp water system is not particularly limited. For example, the water supplied to the paper pulp water system, the reused water tank once mixed / stored with the reused water of the process process as feed / concentrated water, or It is measured with raw material slurry charged and concentrated with this water, or white water where these waters are collected. Since the addition amount of the bactericide can be controlled, the concentration and the oxidation-reduction potential may be measured continuously.
紙パルプ水系に添加する無機系酸化性殺菌剤の添加量の制御は、特に制限されず、微生物によって分解される澱粉濃度やその分解物のグルコース濃度に基づきすることもできるが、簡易測定ができ、連続測定も行いやすいため、塩素濃度または酸化還元電位に基づくのが好ましい。 Control of the addition amount of the inorganic oxidizing disinfectant added to the pulp and paper water system is not particularly limited, and can be based on the starch concentration decomposed by microorganisms or the glucose concentration of the decomposition product, but simple measurement is possible. Since it is easy to perform continuous measurement, it is preferable to use the chlorine concentration or the oxidation-reduction potential.
紙パルプ水系に添加する無機系酸化性殺菌剤の添加量の制御は、特に制限されないが、塩素濃度や酸化還元電位の測定値に基づき、手動で制御してもよく、機械的に最適化することもできる。 Control of the amount of inorganic oxidative fungicide added to the pulp and paper water system is not particularly limited, but it may be controlled manually based on measured values of chlorine concentration and redox potential, and mechanically optimized. You can also.
第２の実施形態において、製紙パルプ製造工程の無機系酸化性殺菌剤が添加される紙パルプ水系に給水される水に、スルファミン酸化合物またはその塩を添加する。 In 2nd Embodiment, a sulfamic acid compound or its salt is added to the water supplied to the paper pulp water system to which the inorganic oxidizing disinfectant of the paper pulp production process is added.
スルファミン酸化合物またはその塩の添加濃度は、特に制限されないが、紙パルプ水系に０．０１〜２ｍｇ／Ｌ ａｓ Ｃｌ２、好ましくは０．５〜１ｍｇ／Ｌ ａｓ Ｃｌ２で残留させることで、紙パルプ水系に添加する無機系酸化性殺菌剤の量が少なくても十分な殺菌力を得られ、スライムを抑制できる一方で、紙パルプ水系の設備の腐食を抑制できる。スルファミン酸化合物またはその塩は、菌数の少ない工業用水や、紙パルプ水系においても有効である。スルファミン酸化合物は、クロロスルファミン酸であることが好ましい。なお、工業用水や再利用水は、一般的に次亜塩素酸ソーダによる簡易な処理が行われており、本実施形態において、水系に残留する次亜塩素酸ソーダを塩素系酸化剤として利用してもよい。 The addition concentration of the sulfamic acid compound or a salt thereof is not particularly limited. However, by leaving the sulfamic acid compound or its salt in the paper pulp water system at 0.01 to 2 mg / L as Cl 2 , preferably 0.5 to 1 mg / L as Cl 2 , Even if the amount of the inorganic oxidizing disinfectant added to the pulp water system is small, a sufficient bactericidal power can be obtained and slime can be suppressed, while corrosion of paper pulp water system equipment can be suppressed. The sulfamic acid compound or a salt thereof is also effective in industrial water having a small number of bacteria and paper pulp water system. The sulfamic acid compound is preferably chlorosulfamic acid. Industrial water and reused water are generally simply treated with sodium hypochlorite. In this embodiment, sodium hypochlorite remaining in the water system is used as a chlorine-based oxidizing agent. May be.
第２の実施形態において、他の要件は、第１実施形態におけるものと同様にすることができる。 In the second embodiment, other requirements can be the same as those in the first embodiment.
（スライム抑制剤Ａの調製）
水５００ｍＬにスルファミン酸１００ｇを溶解し、その水溶液に５０％ＮａＯＨ水溶液を１００ｍＬ、１１．６％次亜塩素酸ソーダ水溶液を４００ｍＬを加えてスライム抑制剤Ａを調製した。
(Preparation of slime inhibitor A)
100 g of sulfamic acid was dissolved in 500 mL of water, and 100 mL of 50% NaOH aqueous solution and 400 mL of 11.6% sodium hypochlorite aqueous solution were added to the aqueous solution to prepare slime inhibitor A.
（殺菌剤Ｂの調製）
０．７％臭化アンモニウム水溶液１００ｍＬと０．０８％次亜塩素酸ソーダ水溶液１００ｍＬとを混合して、殺菌剤Ｂをとした。
(Preparation of disinfectant B)
Disinfectant B was prepared by mixing 100 mL of 0.7% ammonium bromide aqueous solution and 100 mL of 0.08% sodium hypochlorite aqueous solution.
（殺菌剤Ｃの調製）
０．６％硫酸アンモニウム水溶液１００ｍＬと０．０８％次亜塩素酸ソーダ水溶液１００ｍＬとを混合して、殺菌剤Ｃとした。
(Preparation of disinfectant C)
Disinfectant C was prepared by mixing 100 mL of 0.6% ammonium sulfate aqueous solution and 100 mL of 0.08% sodium hypochlorite aqueous solution.
［実施例１〜３］
紙パルプ工場における、加圧浮上、生物処理、砂ろ過の処理が施された再利用水に、スライム抑制剤Ａを添加し、１０分後にその水中（回収水中）の残留塩素濃度を測定した。次に、スライム抑制剤Ａを含む再利用水と製紙パルプ製造工程の白水とを２：８の割合で混合し、１０分後にその水中（混合水中）の残留塩素濃度と酸化還元電位とを測定した。次にこの混合液に殺菌剤Ｂを３（ｍｇ／L ａｓ Ｃｌ２）添加し、３０分３０℃で振とうした後、その水中の菌数の測定を行った。
[Examples 1 to 3]
Slime inhibitor A was added to reused water that had been subjected to pressurized flotation, biological treatment, and sand filtration in a paper pulp factory, and the residual chlorine concentration in the water (recovered water) was measured after 10 minutes. Next, the recycled water containing the slime inhibitor A and the white water of the pulp making process are mixed at a ratio of 2: 8, and after 10 minutes, the residual chlorine concentration and redox potential in the water (mixed water) are measured. did. Next, 3 (mg / L as Cl 2 ) was added to this mixed solution, and after 30 minutes of shaking at 30 ° C., the number of bacteria in the water was measured.
［比較例１〜３］
スライム抑制剤Ａに変えて、次亜塩素酸ソーダを添加したことを除いては実施例１〜３と同様にして、菌数の測定を行った。
[Comparative Examples 1-3]
The number of bacteria was measured in the same manner as in Examples 1 to 3 except that sodium hypochlorite was added instead of the slime inhibitor A.
ブランク時（対照１）、実施例１〜３、比較例１〜３の結果を表１に示す。 When blank (Control 1), the results of Examples 1 to 3 and Comparative Examples 1 to 3 are shown in Table 1.
比較例１〜３に示されるように、次亜塩素酸ソーダは、再利用水中や白水との混合水中でかなり分解し、ＯＲＰは十分に上昇しなかった。そのため、殺菌剤Ｂを加えても殺菌効率が効果的に上がらなかった。一方、スライム抑制剤Ａは、再利用水中で次亜塩素酸ソーダと比べて分解せず、白水と混合しても残留塩素濃度は高く、殺菌剤Ｂを加えたときの殺菌効果は高かった。他方で、ＯＲＰは十分に高かった。 As shown in Comparative Examples 1 to 3, sodium hypochlorite was significantly decomposed in reused water or mixed water with white water, and ORP did not rise sufficiently. Therefore, even when the bactericide B was added, the bactericidal efficiency did not increase effectively. On the other hand, the slime inhibitor A was not decomposed in reused water as compared with sodium hypochlorite, and even when mixed with white water, the residual chlorine concentration was high, and the bactericidal effect when the bactericidal agent B was added was high. On the other hand, the ORP was high enough.
［実施例４〜６］
工業用水に、スライム抑制剤Ａを添加し、１０分後にその水中（回収水中）の残留塩素濃度を測定した。次に、スライム抑制剤Ａを含む再利用水と製紙パルプ製造工程の白水とを２：８の割合で混合し、１０分後にその水中（混合水中）の残留塩素濃度と酸化還元電位とを測定した。次にこの混合液に殺菌剤Ｃを３（ｍｇ／L ａｓ Ｃｌ２）添加し、３０分３０℃で振とうした後、その水中の菌数の測定を行った。
[Examples 4 to 6]
Slime inhibitor A was added to industrial water, and the residual chlorine concentration in the water (recovered water) was measured 10 minutes later. Next, the recycled water containing the slime inhibitor A and the white water of the pulp making process are mixed at a ratio of 2: 8, and after 10 minutes, the residual chlorine concentration and redox potential in the water (mixed water) are measured. did. Next, 3 (mg / L as Cl 2 ) of fungicide C was added to this mixed solution, and after shaking at 30 ° C. for 30 minutes, the number of bacteria in the water was measured.
［比較例４〜６］
スライム抑制剤Ａに変えて、次亜塩素酸ソーダを添加したことを除いては実施例４〜６と同様にして、菌数の測定を行った。
[Comparative Examples 4 to 6]
The number of bacteria was measured in the same manner as in Examples 4 to 6 except that sodium hypochlorite was added instead of slime inhibitor A.
ブランク時（対照２）、実施例４〜６、比較例４〜６の結果を表２に示す。 Table 2 shows the results of Examples 4 to 6 and Comparative Examples 4 to 6 when blank (Control 2).
比較例４〜６に示されるように、次亜塩素酸ソーダは、再利用水中や白水との混合水中でかなり分解した。そのため、殺菌剤Ｃを加えても殺菌効率が効果的に上がらなかった。一方、スライム抑制剤Ａは、再利用水中で次亜塩素酸ソーダと比べて分解せず、白水と混合しても残留塩素濃度は高くなった。そのため、殺菌剤Ｃを加えたときの殺菌効果は高かった。他方で、ＯＲＰは十分に高かった。
As shown in Comparative Examples 4 to 6, sodium hypochlorite was considerably decomposed in reused water or mixed water with white water. Therefore, even when the bactericidal agent C was added, the bactericidal efficiency did not increase effectively. On the other hand, the slime inhibitor A was not decomposed in reused water as compared with sodium hypochlorite, and the residual chlorine concentration was high even when mixed with white water. Therefore, the bactericidal effect when the bactericidal agent C was added was high. On the other hand, the ORP was high enough.
Claims (2)
前記無機系酸化性殺菌剤が、塩素系酸化剤とアンモニウム塩との混合物、または塩素系酸化剤とアミノ化合物との混合物を含む、紙パルプ水系におけるスライム抑制方法。 A step of adding a sulfamic acid compound or a salt thereof, or a chlorine-based oxidizing agent and a sulfamic acid compound or a salt thereof to industrial water or recycled water supplied to a paper pulp water system to which an inorganic oxidizing disinfectant is added Including
The slime suppression method in paper pulp water system in which the said inorganic type oxidizing disinfectant contains the mixture of a chlorine type oxidizing agent and ammonium salt, or the mixture of a chlorine type oxidizing agent and an amino compound.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2013015666A JP5729399B2 (en) | 2013-01-30 | 2013-01-30 | Slime control method in pulp and paper water system |
| PCT/JP2014/051919 WO2014119606A1 (en) | 2013-01-30 | 2014-01-29 | Method for controlling slime in aqueous paper pulp system |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2013015666A JP5729399B2 (en) | 2013-01-30 | 2013-01-30 | Slime control method in pulp and paper water system |
Publications (3)
| Publication Number | Publication Date |
|---|---|
| JP2014145145A JP2014145145A (en) | 2014-08-14 |
| JP2014145145A5 JP2014145145A5 (en) | 2014-10-16 |
| JP5729399B2 true JP5729399B2 (en) | 2015-06-03 |
Family
ID=51262319
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2013015666A Active JP5729399B2 (en) | 2013-01-30 | 2013-01-30 | Slime control method in pulp and paper water system |
Country Status (2)
| Country | Link |
|---|---|
| JP (1) | JP5729399B2 (en) |
| WO (1) | WO2014119606A1 (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103061206A (en) * | 2011-10-21 | 2013-04-24 | 纳尔科公司 | Application of composition of sulfamic acid or salts thereof and ammonium salt and/or amine or other biocides containing halogens in papermaking field |
| CN105613489B (en) * | 2014-10-28 | 2020-01-07 | 艺康美国股份有限公司 | Microbial control system and use method thereof |
| CN115262266B (en) * | 2021-07-20 | 2023-09-19 | 苏州赛维科环保技术服务有限公司 | Real-time microorganism detection regulation and control device and early warning and regulation and control method for paper machine papermaking system |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1550369B1 (en) * | 2002-05-22 | 2008-07-02 | Kurita Water Industries Ltd. | Composition for prevention of slime and method for preventing slime |
| JP5141163B2 (en) * | 2007-09-27 | 2013-02-13 | 栗田工業株式会社 | Bactericidal and algae killing method |
| JP2013198869A (en) * | 2012-03-26 | 2013-10-03 | Kurita Water Ind Ltd | Method for inhibiting waterborne bacteria |
| JP5958076B2 (en) * | 2012-05-22 | 2016-07-27 | 栗田工業株式会社 | Microbial control method in water system containing reducing substances |
-
2013
- 2013-01-30 JP JP2013015666A patent/JP5729399B2/en active Active
-
2014
- 2014-01-29 WO PCT/JP2014/051919 patent/WO2014119606A1/en active Application Filing
Also Published As
| Publication number | Publication date |
|---|---|
| JP2014145145A (en) | 2014-08-14 |
| WO2014119606A1 (en) | 2014-08-07 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP5556838B2 (en) | Slime control method in pulp and paper manufacturing process | |
| RU2414432C2 (en) | Synergetic composition and method of inhibiting growth of microorganisms | |
| MX2012002388A (en) | Methods and kits for stabilizing oxidizers and sanitizing water. | |
| JP2009084163A (en) | Bactericidal/algicidal method | |
| CN110050791B (en) | Method for inhibiting microorganisms in aqueous systems | |
| JP2016120457A (en) | Filtration treatment system and filtration treatment method | |
| JP5729399B2 (en) | Slime control method in pulp and paper water system | |
| JP5941390B2 (en) | Industrial antibacterial methods | |
| KR20160078870A (en) | Paper manufacturing apparatus and wastewater treatment method | |
| JP5958076B2 (en) | Microbial control method in water system containing reducing substances | |
| JP5357440B2 (en) | Harmful microorganism eradication agent and harmful microorganism eradication method using the same | |
| JP5281465B2 (en) | Bactericidal algicide composition, water-based bactericidal algicide method, and method for producing bactericidal algicide composition | |
| WO2006103314A1 (en) | Electrochemical method for preparing microbiocidal solutions | |
| JP3992614B2 (en) | Disinfectant and water-based disinfecting method using the disinfectant | |
| KR20140088207A (en) | Treating agent for ship ballast water and method for treating ship ballast water using same | |
| KR102233760B1 (en) | A method of biofouling treatment by using aminoacids for replacing the free chlorine to combinded chlorine in reverse osmosis membrane system | |
| WO2015162440A1 (en) | Process for preparing chlorine dioxide | |
| US20110024367A1 (en) | Cyclic process for in-situ generation of chlorine dioxide in biguanide treated aquatic facilities | |
| US20150099014A1 (en) | Method for preparing biocidal and antifouling aqueous compositions comprising hydrobromic acid, urea and sodium hypochlorite | |
| WO2018085235A1 (en) | Stabilization of super-activated peroxy compounds | |
| JP6814917B2 (en) | Water-based slime suppression method | |
| JP2006206608A5 (en) | Water-based sterilization method | |
| JP4636334B2 (en) | How to kill microorganisms | |
| JP2006206608A (en) | Microbicidal and algicidal composition | |
| JP2003103266A (en) | Slime preventing method and apparatus therefor |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20140827 |
|
| A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20140827 |
|
| A871 | Explanation of circumstances concerning accelerated examination |
Free format text: JAPANESE INTERMEDIATE CODE: A871 Effective date: 20140827 |
|
| A975 | Report on accelerated examination |
Free format text: JAPANESE INTERMEDIATE CODE: A971005 Effective date: 20141024 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A132 Effective date: 20141028 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20141222 |
|
| TRDD | Decision of grant or rejection written | ||
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20150310 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20150323 |
|
| R150 | Certificate of patent or registration of utility model |
Ref document number: 5729399 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R150 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |