JP6450914B2 - Method for preventing deposition of manganese-containing material - Google Patents
Method for preventing deposition of manganese-containing material Download PDFInfo
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- JP6450914B2 JP6450914B2 JP2013147786A JP2013147786A JP6450914B2 JP 6450914 B2 JP6450914 B2 JP 6450914B2 JP 2013147786 A JP2013147786 A JP 2013147786A JP 2013147786 A JP2013147786 A JP 2013147786A JP 6450914 B2 JP6450914 B2 JP 6450914B2
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- 238000000034 method Methods 0.000 title claims description 101
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical group [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 title claims description 81
- 229910052748 manganese Inorganic materials 0.000 title claims description 81
- 239000011572 manganese Substances 0.000 title claims description 81
- 239000000463 material Substances 0.000 title claims description 50
- 230000008021 deposition Effects 0.000 title claims description 33
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 80
- WQYVRQLZKVEZGA-UHFFFAOYSA-N hypochlorite Chemical compound Cl[O-] WQYVRQLZKVEZGA-UHFFFAOYSA-N 0.000 claims description 72
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 64
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 49
- 239000000460 chlorine Substances 0.000 claims description 49
- 229910052801 chlorine Inorganic materials 0.000 claims description 49
- 150000003863 ammonium salts Chemical class 0.000 claims description 35
- 229910052757 nitrogen Inorganic materials 0.000 claims description 32
- 238000004519 manufacturing process Methods 0.000 claims description 22
- 239000000126 substance Substances 0.000 claims description 17
- 239000005708 Sodium hypochlorite Substances 0.000 description 51
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 51
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 29
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 29
- 235000011130 ammonium sulphate Nutrition 0.000 description 29
- 238000000151 deposition Methods 0.000 description 29
- SWLVFNYSXGMGBS-UHFFFAOYSA-N ammonium bromide Chemical compound [NH4+].[Br-] SWLVFNYSXGMGBS-UHFFFAOYSA-N 0.000 description 26
- 238000002360 preparation method Methods 0.000 description 21
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 18
- 238000001556 precipitation Methods 0.000 description 15
- 239000007864 aqueous solution Substances 0.000 description 13
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 11
- 235000011114 ammonium hydroxide Nutrition 0.000 description 11
- 239000000047 product Substances 0.000 description 10
- JHJLBTNAGRQEKS-UHFFFAOYSA-M sodium bromide Chemical compound [Na+].[Br-] JHJLBTNAGRQEKS-UHFFFAOYSA-M 0.000 description 10
- 235000019270 ammonium chloride Nutrition 0.000 description 9
- 239000008367 deionised water Substances 0.000 description 9
- 229910021641 deionized water Inorganic materials 0.000 description 9
- 239000000203 mixture Substances 0.000 description 8
- 239000000243 solution Substances 0.000 description 8
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 7
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 7
- 229910052794 bromium Inorganic materials 0.000 description 7
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 239000007800 oxidant agent Substances 0.000 description 5
- OSVXSBDYLRYLIG-UHFFFAOYSA-N dioxidochlorine(.) Chemical compound O=Cl=O OSVXSBDYLRYLIG-UHFFFAOYSA-N 0.000 description 4
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 4
- 244000005700 microbiome Species 0.000 description 4
- 239000011259 mixed solution Substances 0.000 description 4
- 230000002265 prevention Effects 0.000 description 4
- 230000001629 suppression Effects 0.000 description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 238000012790 confirmation Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 239000006104 solid solution Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 239000004155 Chlorine dioxide Substances 0.000 description 2
- 229920001131 Pulp (paper) Polymers 0.000 description 2
- 230000002411 adverse Effects 0.000 description 2
- 235000019398 chlorine dioxide Nutrition 0.000 description 2
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 description 2
- 239000000417 fungicide Substances 0.000 description 2
- QWPPOHNGKGFGJK-UHFFFAOYSA-N hypochlorous acid Chemical compound ClO QWPPOHNGKGFGJK-UHFFFAOYSA-N 0.000 description 2
- CNFDGXZLMLFIJV-UHFFFAOYSA-L manganese(II) chloride tetrahydrate Chemical compound O.O.O.O.[Cl-].[Cl-].[Mn+2] CNFDGXZLMLFIJV-UHFFFAOYSA-L 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 description 1
- 239000004254 Ammonium phosphate Substances 0.000 description 1
- ZKQDCIXGCQPQNV-UHFFFAOYSA-N Calcium hypochlorite Chemical compound [Ca+2].Cl[O-].Cl[O-] ZKQDCIXGCQPQNV-UHFFFAOYSA-N 0.000 description 1
- 150000000703 Cerium Chemical class 0.000 description 1
- 229920002488 Hemicellulose Polymers 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 229910021380 Manganese Chloride Inorganic materials 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 150000003868 ammonium compounds Chemical class 0.000 description 1
- 229910000148 ammonium phosphate Inorganic materials 0.000 description 1
- 235000019289 ammonium phosphates Nutrition 0.000 description 1
- 150000001720 carbohydrates Chemical class 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000000645 desinfectant Substances 0.000 description 1
- 229910000388 diammonium phosphate Inorganic materials 0.000 description 1
- 235000019838 diammonium phosphate Nutrition 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-M dihydrogenphosphate Chemical compound OP(O)([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-M 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 230000002070 germicidal effect Effects 0.000 description 1
- 230000009036 growth inhibition Effects 0.000 description 1
- 229910001410 inorganic ion Inorganic materials 0.000 description 1
- 229920005610 lignin Polymers 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000011565 manganese chloride Substances 0.000 description 1
- 229940099607 manganese chloride Drugs 0.000 description 1
- 235000002867 manganese chloride Nutrition 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- BZDIAFGKSAYYFC-UHFFFAOYSA-N manganese;hydrate Chemical compound O.[Mn] BZDIAFGKSAYYFC-UHFFFAOYSA-N 0.000 description 1
- 235000015097 nutrients Nutrition 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000010893 paper waste Substances 0.000 description 1
- SATVIFGJTRRDQU-UHFFFAOYSA-N potassium hypochlorite Chemical compound [K+].Cl[O-] SATVIFGJTRRDQU-UHFFFAOYSA-N 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000000644 propagated effect Effects 0.000 description 1
- 239000013055 pulp slurry Substances 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- XUXNAKZDHHEHPC-UHFFFAOYSA-M sodium bromate Chemical compound [Na+].[O-]Br(=O)=O XUXNAKZDHHEHPC-UHFFFAOYSA-M 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 230000001954 sterilising effect Effects 0.000 description 1
- 238000004659 sterilization and disinfection Methods 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
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- Paper (AREA)
Description
この発明は、マンガン含有物沈着防止方法に関し、さらに詳しくは、酸化剤を添加することにより不溶性のマンガン含有物が発生する紙パルプ製造工程の白水循環系において、アンモニウム化合物を添加することを含む、紙製品へのマンガン含有物の沈着を防止する方法に関する。 The present invention relates to a method for preventing manganese-containing material deposition, and more specifically, including adding an ammonium compound in a white water circulation system of a paper pulp manufacturing process in which an insoluble manganese-containing material is generated by adding an oxidizing agent. The present invention relates to a method for preventing deposition of manganese-containing materials on paper products.
紙パルプ製造工程では、原料となる木材に由来するセルロース、リグニン、ヘミセルロース、糖類などを栄養源として多くの微生物が工程水中に繁殖する。これら微生物は、製紙工程中のパイプラインやピットなどの壁面に付着して粘着性物質を分泌して、スライムを形成する。このスライムが、製紙原料に混入して紙切れによる生産効率の低下を引き起こしたり、紙製品の品質を低下させたりすることは、従来からよく知られている。このようなスライム障害を防止するため、種々の有機系殺菌剤が使用されてきたが、これら有機系殺菌剤には環境に悪影響を及ぼすもの、あるいは悪影響が懸念されるものが多い。このような環境影響性あるいは経済性の点から、その使用量は制限されてしまう。そこで、次亜塩素酸ナトリウムや二酸化塩素などの酸化剤を用いた微生物制御方法が提案されている。 In the pulp and paper manufacturing process, many microorganisms are propagated in the process water using cellulose, lignin, hemicellulose, saccharides and the like derived from wood as a raw material as nutrient sources. These microorganisms adhere to wall surfaces such as pipelines and pits during the paper making process and secrete adhesive substances to form slime. It has been well known that this slime is mixed into a papermaking raw material to cause a reduction in production efficiency due to a piece of paper or to reduce the quality of a paper product. In order to prevent such slime damage, various organic fungicides have been used, but many of these organic fungicides have an adverse effect on the environment or are concerned about adverse effects. From such environmental impact or economic point of view, the amount used is limited. Therefore, a microorganism control method using an oxidizing agent such as sodium hypochlorite or chlorine dioxide has been proposed.
他方、近年では紙製造工程のラインはクローズド化や古紙の利用、添加薬品の多様化などから、様々な汚れ物質が付着するようになっている。白水循環系でみられるマンガン含有物は、酸化数によって、茶色から黒色といった色を帯びるものだが、この異物が抄紙マシンの壁面やワイヤーに沈着して、抄造途中の紙面に付着し、湿紙にシミ状あるいは、塊状に付着したり、異物ごと紙が剥がれて粕穴を生じたりすることで、紙製品の商品価値を著しく落としてしまう。 On the other hand, in recent years, various dirt substances have come to adhere to the line of the paper manufacturing process due to closing, use of waste paper, diversification of additive chemicals, and the like. Manganese-containing substances found in the white water circulation system have a color ranging from brown to black, depending on the oxidation number, but this foreign matter is deposited on the walls and wires of the paper machine and adheres to the paper surface during the paper making process. The product value of a paper product will be significantly reduced by adhering to a stain or a lump, or when the paper is peeled off together with foreign matter to create a pit.
製紙工程のマンガン含有物を防止する技術としては、水系におけるマンガン析出を阻害するためのセリウム塩の使用（特表２００７−５０５７３８号公報：特許文献１参照）、無機組成物に関係するスケーリングの防止方法およびそのための組成物（特表２００３−５２５１０４号公報：特許文献２参照）などが提案されている。 Techniques for preventing manganese-containing substances in the papermaking process include the use of cerium salts to inhibit manganese precipitation in aqueous systems (see Japanese Patent Publication No. 2007-505738: Patent Document 1), prevention of scaling related to inorganic compositions. A method and a composition therefor have been proposed (see Japanese Patent Application Publication No. 2003-525104: Patent Document 2).
白水循環系などの製紙工程水からマンガン含有物が析出して製造される紙に沈着する原因の１つは、製紙工程のスライム汚れを防止するために添加される次亜塩素酸ナトリウムや二酸化塩素などの酸化剤であると考えられる。すなわち、酸化剤が水系のマンガンと反応して不溶性のマンガン含有物が生成すると考えられる。一方で、次亜塩素酸ナトリウムは、有機系殺菌剤と比べて環境に対する影響の少なさの点で優れるため、継続な使用が期待されるスライムコントロール剤である。 One of the causes of manganese deposits from papermaking process water, such as white water circulation systems, and deposits on paper produced is sodium hypochlorite and chlorine dioxide added to prevent slime stains in the papermaking process. It is thought that it is an oxidizing agent. That is, it is thought that an oxidizing agent reacts with aqueous manganese to produce an insoluble manganese-containing material. On the other hand, sodium hypochlorite is a slime control agent that is expected to be used continuously because it is superior to organic germicides in that it has less impact on the environment.
そこで、本発明は、次亜塩素酸ナトリウム等の次亜塩素酸塩が添加される製紙工程水においてマンガン含有物の紙への沈着を防止する方法を提供する。 Therefore, the present invention provides a method for preventing the deposition of manganese-containing materials on paper in papermaking process water to which hypochlorite such as sodium hypochlorite is added.
本発明は、一態様において、次亜塩素酸塩を添加することにより不溶性のマンガン含有物が生成する製紙工程水循環系において、水溶性無機アンモニウム塩又はアンモニア水を、次亜塩素酸塩と水溶性無機アンモニウム塩又はアンモニア水とのモル比が残留塩素量と窒素とのモル比として１：１〜１：２となるように添加することを特徴とする、紙製品へのマンガン含有物の沈着を防止する方法に関する。 In one aspect, the present invention provides a water-soluble inorganic ammonium salt or aqueous ammonia, water-soluble hypochlorite and water-soluble in a papermaking process water circulation system in which an insoluble manganese-containing product is produced by adding hypochlorite. Addition of manganese-containing material to paper products, wherein the molar ratio of inorganic ammonium salt or ammonia water is added so that the molar ratio of residual chlorine and nitrogen is 1: 1 to 1: 2. It relates to a method to prevent.
また、本発明は、一態様において、スライムコントロールのために製紙工程水に次亜塩素酸塩が添加される製紙工程においてマンガン含有物の紙への沈着を防止する方法であって、前記製紙工程水に次亜塩素酸塩と、水溶性無機アンモニウム塩又はアンモニア水とを添加することを含み、前記水溶性無機アンモニウム塩又はアンモニア水の添加が、前記製紙工程水における次亜塩素酸塩と水溶性無機アンモニウム塩又はアンモニア水とのモル比が残留塩素量と窒素とのモル比として１：１〜１：２となるように行われるマンガン含有物沈着防止方法に関する。 Further, in one aspect, the present invention is a method for preventing deposition of manganese-containing material on paper in a papermaking process in which hypochlorite is added to papermaking process water for slime control, the papermaking process Adding hypochlorite and water-soluble inorganic ammonium salt or ammonia water to the water, and the addition of the water-soluble inorganic ammonium salt or ammonia water is performed by adding hypochlorite and water in the papermaking process water. The present invention relates to a method for preventing the deposition of manganese-containing substances, which is carried out so that the molar ratio of the basic inorganic ammonium salt or aqueous ammonia is 1: 1 to 1: 2 as the molar ratio of residual chlorine and nitrogen.
また、本発明は、一態様において、スライムコントロールのために次亜塩素酸塩が添加される製紙工程水を用いる紙の製造方法であって、マンガン含有物の紙への沈着を防止するために前記製紙工程水に、次亜塩素酸塩と、水溶性無機アンモニウム塩又はアンモニア水とを添加することを含み、前記水溶性無機アンモニウム塩又はアンモニア水の添加が、前記製紙工程水における次亜塩素酸塩と水溶性無機アンモニウム塩又はアンモニア水とのモル比が残留塩素量と窒素とのモル比として１：１〜１：２となるように行われる、紙の製造方法に関する。 Further, in one aspect, the present invention is a paper manufacturing method using papermaking process water to which hypochlorite is added for slime control, in order to prevent deposition of manganese-containing materials on paper. Adding hypochlorite and a water-soluble inorganic ammonium salt or ammonia water to the papermaking process water, wherein the addition of the water-soluble inorganic ammonium salt or ammonia water is a hypochlorite in the papermaking process water. The present invention relates to a method for producing paper, wherein the molar ratio of the acid salt to the water-soluble inorganic ammonium salt or aqueous ammonia is 1: 1 to 1: 2 as the molar ratio of the residual chlorine amount and nitrogen.
この発明によれば、例えば、マンガン含有物が発生しやすい環境下にある紙製造工程において、紙製品へマンガン含有物が混入することを効果的に抑制・防止する方法を提供でき、安定に紙を抄造する方法を提供できうる。 According to the present invention, for example, in a paper manufacturing process in an environment in which manganese-containing materials are likely to be generated, a method for effectively suppressing and preventing manganese-containing materials from being mixed into a paper product can be provided. A method for papermaking can be provided.
本発明は、次亜塩素酸ナトリウム等の次亜塩素酸塩を添加することにより不溶性のマンガン含有物が生成する紙パルプ製造工程の白水循環系において、硫酸アンモニウム及び臭化アンモニウム等といった水溶性無機アンモニウム塩やアンモニア水を添加することで、抄造した紙にマンガン含有物が沈着することを効果的に防止して、安定に紙製品を製造することができるという知見に基づく。 The present invention relates to a water-soluble inorganic ammonium such as ammonium sulfate and ammonium bromide in a white water circulation system of a paper pulp manufacturing process in which an insoluble manganese-containing material is produced by adding a hypochlorite such as sodium hypochlorite. It is based on the knowledge that by adding salt or aqueous ammonia, it is possible to effectively prevent the manganese-containing material from depositing on the paper made, and to stably produce paper products.
本発明は、限定されない一又は複数の実施形態において、次亜塩素酸ナトリウムを添加することにより不溶性のマンガン含有物が生成する製紙工程水循環系において、硫酸アンモニウム又は臭化アンモニウムを、次亜塩素酸ナトリウムと硫酸アンモニウム又は臭化アンモニウムとのモル比が残留塩素量と窒素又は臭素とのモル比として１：１〜１：２となるように添加することを特徴とする、紙製品へのマンガン含有物の沈着を防止する方法に関する。 In one or more non-limiting embodiments, the present invention provides ammonium sulfate or ammonium bromide for sodium hypochlorite in a papermaking process water cycle in which insoluble manganese content is produced by the addition of sodium hypochlorite. Of manganese-containing material to paper products, characterized in that the molar ratio of residual sulfate to ammonium sulfate or ammonium bromide is from 1: 1 to 1: 2 as the molar ratio of residual chlorine to nitrogen or bromine The present invention relates to a method for preventing deposition.
また、本発明は、限定されない一又は複数の実施形態において、スライムコントロールのために製紙工程水に次亜塩素酸ナトリウムが添加される製紙工程においてマンガン含有物の紙への沈着を防止する方法であって、前記製紙工程水に次亜塩素酸ナトリウムと、硫酸アンモニウム又は臭化アンモニウムとを添加することを含み、前記硫酸アンモニウム又は臭化アンモニウムの添加が、前記製紙工程水における次亜塩素酸ナトリウムと硫酸アンモニウム又は臭化アンモニウムとのモル比が残留塩素量と窒素又は臭素とのモル比として１：１〜１：２となるように行われるマンガン含有物沈着防止方法に関する。 Further, the present invention is a method for preventing deposition of manganese-containing materials on paper in a papermaking process in which sodium hypochlorite is added to papermaking process water for slime control in one or more embodiments that are not limited. And adding sodium hypochlorite and ammonium sulfate or ammonium bromide to the papermaking process water, wherein the addition of ammonium sulfate or ammonium bromide is sodium hypochlorite and ammonium sulfate in the papermaking process water. Alternatively, the present invention relates to a method for preventing the deposition of manganese-containing substances, which is carried out so that the molar ratio of ammonium bromide is 1: 1 to 1: 2 as the molar ratio of the residual chlorine amount and nitrogen or bromine.
また、本発明は、限定されない一又は複数の実施形態において、スライムコントロールのために次亜塩素酸ナトリウムが添加される製紙工程水を用いる紙の製造方法であって、マンガン含有物の紙への沈着を防止するために前記製紙工程水に次亜塩素酸ナトリウムと、硫酸アンモニウム又は臭化アンモニウムとを添加することを含み、前記硫酸アンモニウム又は臭化アンモニウムの添加が、前記製紙工程水における次亜塩素酸ナトリウムと硫酸アンモニウム又は臭化アンモニウムとのモル比が残留塩素量と窒素又は臭素とのモル比として１：１〜１：２となるように行われる、紙の製造方法に関する。 Further, the present invention is, in one or a plurality of non-limiting embodiments, a paper manufacturing method using papermaking process water to which sodium hypochlorite is added for slime control, which comprises adding manganese-containing material to paper. Adding sodium hypochlorite and ammonium sulfate or ammonium bromide to the papermaking process water to prevent deposition, wherein the addition of ammonium sulfate or ammonium bromide comprises hypochlorous acid in the papermaking process water The present invention relates to a method for producing paper, wherein the molar ratio of sodium to ammonium sulfate or ammonium bromide is 1: 1 to 1: 2 as the molar ratio of residual chlorine to nitrogen or bromine.
本明細書において「次亜塩素酸塩」は、一又は複数の実施形態において、次亜塩素酸ナトリウム、次亜塩素酸カリウム、及び次亜塩素酸カルシウム等が挙げられる。次亜塩素酸塩は、固形のもの又は水溶液の形態のものを使用できる。 As used herein, “hypochlorite” includes sodium hypochlorite, potassium hypochlorite, calcium hypochlorite and the like in one or more embodiments. Hypochlorite can be used in the form of a solid or an aqueous solution.
本明細書において「次亜塩素酸ナトリウム」は、特に限定されず、水溶液の形態のものを使用でき、市販の次亜塩素酸ナトリウム水溶液を使用できる。 In the present specification, “sodium hypochlorite” is not particularly limited, and an aqueous solution can be used, and a commercially available sodium hypochlorite aqueous solution can be used.
本明細書において「マンガン含有物」とは、マンガンの酸化物を含み、酸化数によって茶色から黒色を呈し、製紙工程において紙に沈着して汚れとなりうる物質をいう。マンガン含有物は、限定されない一又は複数の実施形態において、水に不溶である。マンガン含有物は、製紙工程水に存在するマンガン成分（イオン）が次亜塩素酸ナトリウムによって酸化され生成されると考えられるが、本発明はこのメカニズムに限定して解釈されなくてもよい。製紙工程における紙の汚れがマンガン含有物か否かは、例えば、蛍光Ｘ線分析によって確認できる。 In the present specification, the “manganese-containing material” refers to a substance that contains an oxide of manganese, has a brown to black color depending on the oxidation number, and can be deposited on paper in the papermaking process and become soiled. The manganese-containing material is insoluble in water in one or more non-limiting embodiments. Manganese-containing materials are thought to be produced by oxidizing manganese components (ions) present in papermaking process water with sodium hypochlorite, but the present invention need not be construed as limited to this mechanism. It can be confirmed, for example, by fluorescent X-ray analysis whether or not the paper stain in the paper making process is a manganese-containing material.
本明細書において「沈着」とは、マンガン含有物が付着又は固着すること含み、限定されない一又は複数の実施形態において、紙にマンガン含有物の色が付くことをいう。 In the present specification, “deposition” means that the manganese-containing material is attached or fixed, and in one or more embodiments that are not limited, the paper is colored with the manganese-containing material.
本明細書において「製紙工程水」とは、製紙白水（抄紙白水）、パルプ白水を含む。限定されない一又は複数の実施形態において、製紙工程水は、循環利用又は再利用されるものを含み、製紙工程水循環系における製紙工程水である。本明細書において「製紙工程水循環系」とは、製紙工程水の循環利用又は再利用される系をいう。 In this specification, “papermaking process water” includes papermaking white water (papermaking whitewater) and pulp whitewater. In one or more non-limiting embodiments, the papermaking process water includes paper that is recycled or reused, and is papermaking process water in a papermaking process water circulation system. In the present specification, the “papermaking process water circulation system” refers to a system in which papermaking process water is recycled or reused.
本明細書において「水溶性無機アンモニウム塩」は、アンモニウムイオンと無機イオンとの水溶性の塩をいい、一又は複数の実施形態において、塩化アンモニウム、臭化アンモニウム、リン酸アンモニウム、リン酸二水素アンモニウム、リン酸水素二アンモニウム、硫酸アンモニウム、及び硝酸アンモニウム等が挙げられる。水溶性無機アンモニウム塩は、固体のもの或いは水溶液のものを使用でき、水溶液の場合の濃度も特に限定されなくてよい。安定性及びスペースの観点からは濃度は高いことが好ましい。 As used herein, “water-soluble inorganic ammonium salt” refers to a water-soluble salt of an ammonium ion and an inorganic ion. In one or more embodiments, ammonium chloride, ammonium bromide, ammonium phosphate, dihydrogen phosphate. Examples include ammonium, diammonium hydrogen phosphate, ammonium sulfate, and ammonium nitrate. As the water-soluble inorganic ammonium salt, a solid or aqueous solution can be used, and the concentration in the case of an aqueous solution is not particularly limited. From the viewpoint of stability and space, the concentration is preferably high.
本明細書において「硫酸アンモニウム」は、特に限定されず、固体のもの或いは水溶液のものを使用でき、水溶液の場合の濃度も特に限定されなくてよい。安定性及びスペースの観点からは濃度は高いことが好ましい。 In the present specification, the “ammonium sulfate” is not particularly limited, and a solid or aqueous solution can be used, and the concentration in the case of an aqueous solution is not particularly limited. From the viewpoint of stability and space, the concentration is preferably high.
本明細書において「臭化アンモニウム」は、特に限定されず、固体のもの或いは水溶液のものを使用でき、水溶液の場合の濃度も特に限定されなくてよい。安定性及びスペースの観点からは濃度は高いことが好ましい。 In the present specification, “ammonium bromide” is not particularly limited, and a solid or aqueous solution can be used, and the concentration in the case of an aqueous solution is not particularly limited. From the viewpoint of stability and space, the concentration is preferably high.
本明細書において「沈着防止」とは、沈着の程度の抑制を含む。 In the present specification, “deposition prevention” includes suppression of the degree of deposition.
本明細書において「残留塩素量」は、結合塩素及び遊離塩素を含む。残留塩素量は、使用する次亜塩素酸塩水溶液の有効塩素濃度から算出してもよく、従来知られ又は今後開発される方法によって測定してもよい。 In the present specification, the “residual chlorine amount” includes bound chlorine and free chlorine. The amount of residual chlorine may be calculated from the effective chlorine concentration of the hypochlorite aqueous solution to be used, and may be measured by a conventionally known method or a method developed in the future.
本明細書において「紙製品」とは、限定されない一又は複数の実施形態において、製紙工程で製造される紙を含む。 As used herein, “paper product” includes, in one or more non-limiting embodiments, paper produced in a papermaking process.
本明細書において「スライムコントロール」とは、特に限定されないが、スライムの原因となる微生物の殺菌及び増殖抑制を含む。 In the present specification, “slime control” is not particularly limited, but includes sterilization and growth inhibition of microorganisms that cause slime.
［マンガン含有物沈着防止方法］
本発明のマンガン含有物沈着防止方法は、一態様において、次亜塩素酸塩を添加することにより不溶性のマンガン含有物が生成する製紙工程水循環系において、水溶性無機アンモニウム塩又はアンモニア水（以下、これらをまとめて「アンモニウム塩等」ともいう）を、次亜塩素酸塩とアンモニウム塩等とのモル比が残留塩素量と窒素とのモル比として１：１〜１：２となるように添加することを特徴とする。また、本発明のマンガン含有物沈着防止方法は、一態様において、スライムコントロールのために次亜塩素酸塩が添加された製紙工程水を用いた製紙工程におけるマンガン含有物の紙への沈着を防止する方法であって、前記製紙工程水に次亜塩素酸塩と、アンモニウム塩等とを添加することを含み、前記アンモニウム塩等の添加が、前記製紙工程水における次亜塩素酸塩とアンモニウム塩等とのモル比が残留塩素量と窒素とのモル比として１：１〜１：２となるように行われる。
[Method of preventing deposition of manganese-containing material]
In one aspect, the method for preventing manganese-containing material deposition according to the present invention includes a water-soluble inorganic ammonium salt or aqueous ammonia (hereinafter, referred to as “water-soluble inorganic ammonium salt” or “aqueous ammonia”) in a papermaking process water circulation system in which an insoluble manganese-containing material is produced by adding hypochlorite. These are collectively referred to as “ammonium salts, etc.”) so that the molar ratio of hypochlorite and ammonium salt is 1: 1 to 1: 2 as the molar ratio of residual chlorine to nitrogen. It is characterized by doing. In addition, in one aspect, the method for preventing deposition of manganese-containing substances according to the present invention prevents deposition of manganese-containing substances on paper in a papermaking process using papermaking process water to which hypochlorite is added for slime control. A method comprising: adding hypochlorite and an ammonium salt to the papermaking process water, wherein the addition of the ammonium salt is a hypochlorite and an ammonium salt in the papermaking process water. Etc., so that the molar ratio of residual chlorine and nitrogen is 1: 1 to 1: 2.
次亜塩素酸ナトリウム等の次亜塩素酸塩を含む製紙工程水に、硫酸アンモニウム又は臭化アンモニウムといったアンモニウム塩等を添加することによりマンガン含有物の沈着を効果的に防止・抑制できるメカニズムの詳細は明らかではないが、水系に含まれるマンガンが次亜塩素酸ナトリウム等の次亜塩素酸塩と反応して酸化マンガンになることでマンガン含有物の沈着が促されるが、硫酸アンモニウムといったアンモニウム塩等を添加することで酸化マンガンの生成を抑制して、マンガンが水中に溶解した状態が維持されるものと考えられる。但し、本発明はこのメカニズムに限定して解釈されなくてもよい。 Details of the mechanism that can effectively prevent and control the deposition of manganese-containing materials by adding ammonium salts such as ammonium sulfate or ammonium bromide to papermaking process water containing hypochlorite such as sodium hypochlorite Although it is not clear, manganese contained in the water system reacts with hypochlorite such as sodium hypochlorite to become manganese oxide, which promotes the deposition of manganese-containing materials, but ammonium salts such as ammonium sulfate are added Thus, it is considered that the production of manganese oxide is suppressed and the state in which manganese is dissolved in water is maintained. However, the present invention is not limited to this mechanism.
本発明のマンガン含有物沈着防止方法は、限定されない一又は複数の実施形態において、製紙工程水の循環系において、酸化剤として使用されている次亜塩素酸ナトリウム等の次亜塩素酸塩を添加することにより不溶性のマンガン含有物が生成する対象系で行われる。製紙工程水の循環系の水質条件などにより異なるが、製紙工程水中に全残留塩素量として５．０ｍｇ／リットル以上残留している製紙工程水の循環系において、不溶性のマンガン含有物が生成しやすい傾向にある。また、製紙工程水には通常マンガン成分（イオン）が含有される。本発明のマンガン含有物沈着防止方法によれば、製紙工程水中のマンガン成分（イオン）濃度がたまたま上昇した場合であっても、効果的にその沈着を防止・抑制することができる。 The method for preventing manganese-containing material deposition according to the present invention includes, in one or a plurality of non-limiting embodiments, adding hypochlorite such as sodium hypochlorite used as an oxidizing agent in the circulation system of papermaking process water. This is performed in a target system in which insoluble manganese-containing materials are produced. Although it depends on the water quality conditions of the papermaking process water circulation system, insoluble manganese-containing substances are likely to be generated in the papermaking process water circulation system where the total residual chlorine content in the papermaking process water is 5.0 mg / liter or more. There is a tendency. Further, the papermaking process water usually contains a manganese component (ion). According to the method for preventing deposition of manganese-containing material according to the present invention, even when the manganese component (ion) concentration in the papermaking process water happens to rise, the deposition can be effectively prevented and suppressed.
本発明に用いられる次亜塩素酸塩とアンモニウム塩等とのモル比は、残留塩素量と窒素のモル比（残留塩素量：窒素）として１：１〜１：２、好ましくは１：１．１〜１：１．６である。遊離塩素の発生抑制の点から、窒素は１以上が好ましい。過剰なアンモニウム塩等によりｐＨが低下し生成物（次亜塩素酸塩とアンモニウム塩等の反応生成物）が不安定になるのを回避する点から窒素は２以下が好ましい。 The molar ratio of hypochlorite to ammonium salt used in the present invention is from 1: 1 to 1: 2, preferably 1: 1. As the molar ratio of residual chlorine to nitrogen (residual chlorine: nitrogen). 1-1: 1.6. From the viewpoint of suppressing the generation of free chlorine, nitrogen is preferably 1 or more. Nitrogen is preferably 2 or less from the viewpoint of preventing the pH from being lowered due to an excessive ammonium salt and the like (reaction products such as hypochlorite and ammonium salt) becoming unstable.
製紙工程水又は製紙工程水循環系に次亜塩素酸塩と、アンモニウム塩等とを添加する方法は、限定されない一又は複数の実施形態において、同時又は別々に添加される。同時添加の限定されない一又は複数の実施形態として、次亜塩素酸塩と、アンモニウム塩等とを予め混合して混合溶液を調製し、当該混合溶液を製紙工程水に添加することが挙げられる。 The method of adding hypochlorite, ammonium salt and the like to papermaking process water or a papermaking process water circulation system is added simultaneously or separately in one or a plurality of non-limiting embodiments. As one or a plurality of embodiments in which simultaneous addition is not limited, hypochlorite, ammonium salt and the like are mixed in advance to prepare a mixed solution, and the mixed solution is added to papermaking process water.
本発明のマンガン含有物沈着防止方法は、限定されない一又は複数の実施形態において、次亜塩素酸ナトリウムを添加することにより不溶性のマンガン含有物が生成する製紙工程水循環系において、硫酸アンモニウム又は臭化アンモニウムを、次亜塩素酸ナトリウムと硫酸アンモニウム又は臭化アンモニウムとのモル比が残留塩素量と窒素又は臭素とのモル比として１：１〜１：２となるように添加することを特徴とする。また、本発明のマンガン含有物沈着防止方法は、限定されない一又は複数の実施形態において、スライムコントロールのために次亜塩素酸ナトリウムが添加された製紙工程水を用いた製紙工程におけるマンガン含有物の紙への沈着を防止する方法であって、前記製紙工程水に次亜塩素酸ナトリウムと、硫酸アンモニウム又は臭化アンモニウムとを添加することを含み、前記硫酸アンモニウム又は臭化アンモニウムの添加が、前記製紙工程水における次亜塩素酸ナトリウムと硫酸アンモニウム又は臭化アンモニウムとのモル比が残留塩素量と窒素又は臭素とのモル比として１：１〜１：２となるように行われる。 In one or a plurality of non-limiting embodiments, the method for preventing manganese-containing deposits according to the present invention includes ammonium sulfate or ammonium bromide in a papermaking process water circulation system in which insoluble manganese-containing materials are produced by adding sodium hypochlorite. Is added such that the molar ratio of sodium hypochlorite to ammonium sulfate or ammonium bromide is 1: 1 to 1: 2 as the molar ratio of the amount of residual chlorine and nitrogen or bromine. Further, the method for preventing deposition of manganese-containing material according to the present invention is not limited to one or a plurality of embodiments. In one or a plurality of embodiments, the manganese-containing material in the papermaking process using the papermaking process water to which sodium hypochlorite is added for slime control. A method for preventing deposition on paper, comprising adding sodium hypochlorite and ammonium sulfate or ammonium bromide to the papermaking process water, wherein the addition of ammonium sulfate or ammonium bromide is the papermaking process. The molar ratio of sodium hypochlorite to ammonium sulfate or ammonium bromide in water is 1: 1 to 1: 2 as the molar ratio of residual chlorine content to nitrogen or bromine.
また、この発明の方法は、この発明の効果を阻害しない限りにおいて、公知の殺菌剤を併用添加することもできる。 Moreover, the method of this invention can also add a well-known disinfectant together, unless the effect of this invention is inhibited.
［紙の製造方法］
本発明は、一態様において、スライムコントロールのために次亜塩素酸塩が添加された製紙工程水を用いた紙の製造方法であって、マンガン含有物の紙への沈着を防止するために前記製紙工程水に次亜塩素酸塩と、アンモニウム塩等とを添加することを含み、前記アンモニウム塩等の添加が、前記製紙工程水における次亜塩素酸塩とアンモニウム塩等とのモル比が残留塩素量と窒素とのモル比として１：１〜１：２となるように行われる紙の製造方法に関する。本発明の紙の製造方法は、一又は複数の実施形態において、本発明のマンガン含有物沈着防止方法を行うことを含む紙の製造方法である。
[Paper manufacturing method]
In one aspect, the present invention provides a paper manufacturing method using papermaking process water to which hypochlorite has been added for slime control, in order to prevent deposition of manganese-containing materials on the paper. Including adding hypochlorite, ammonium salt, etc. to papermaking process water, the addition of said ammonium salt, etc., leaving a molar ratio of hypochlorite, ammonium salt, etc. in said papermaking process water The present invention relates to a paper manufacturing method which is carried out so that the molar ratio of chlorine content to nitrogen is 1: 1 to 1: 2. In one or a plurality of embodiments, the paper manufacturing method of the present invention is a paper manufacturing method including performing the manganese-containing material deposition prevention method of the present invention.
本発明は、限定されない一又は複数の実施形態において、スライムコントロールのために次亜塩素酸ナトリウムが添加された製紙工程水を用いた紙の製造方法であって、マンガン含有物の紙への沈着を防止するために前記製紙工程水に次亜塩素酸ナトリウムと、硫酸アンモニウム又は臭化アンモニウムとを添加することを含み、前記硫酸アンモニウム又は臭化アンモニウムの添加が、前記製紙工程水における次亜塩素酸ナトリウムと硫酸アンモニウム又は臭化アンモニウムとのモル比が残留塩素量と窒素又は臭素とのモル比として１：１〜１：２となるように行われる紙の製造方法に関する。本発明の紙の製造方法は、一又は複数の実施形態において、本発明のマンガン含有物沈着防止方法を行うことを含む紙の製造方法である。 In one or a plurality of non-limiting embodiments, the present invention is a paper manufacturing method using papermaking process water to which sodium hypochlorite is added for slime control, and depositing manganese-containing material on paper Adding sodium hypochlorite and ammonium sulfate or ammonium bromide to the papermaking process water to prevent the addition of ammonium sulfate or ammonium bromide to the sodium hypochlorite in the papermaking process water The present invention relates to a method for producing paper, which is carried out so that the molar ratio of ammonium sulfate or ammonium bromide is 1: 1 to 1: 2 as the residual chlorine amount and the molar ratio of nitrogen or bromine. In one or a plurality of embodiments, the paper manufacturing method of the present invention is a paper manufacturing method including performing the manganese-containing material deposition prevention method of the present invention.
本発明を試験例により具体的に説明するが、本発明はこれらの試験例により限定されるものではない。 The present invention will be specifically described with reference to test examples, but the present invention is not limited to these test examples.
（調製例Ａ）次亜塩素酸ナトリウムと硫酸アンモニウムとの混合液の調製
次亜塩素酸ナトリウム溶液（残留塩素量１４０ｇ／リットル）を脱イオン水で残留塩素量が５ｇ／リットルになるよう希釈した後、３０％硫酸アンモニウム溶液（硫酸アンモニウム（キシダ化学株式会社製）３０ｇを脱イオン水で溶解し、全量を１００ｇとしたもの）を残留塩素量と窒素のモル比が１：１．２になるよう混合した。
（調製例Ｂ）
残留塩素量と窒素のモル比が１：１．６になるよう混合したほかは調製例Ａと同様に次亜塩素酸ナトリウムと硫酸アンモニウムとの混合液を調製した。
（調製例Ｃ）
残留塩素量と窒素のモル比が１：０．８になるよう混合したほかは調製例Ａと同様に次亜塩素酸ナトリウムと硫酸アンモニウムとの混合液を調製した。
(Preparation Example A) Preparation of a mixture of sodium hypochlorite and ammonium sulfate After diluting a sodium hypochlorite solution (residual chlorine content 140 g / liter) with deionized water so that the residual chlorine content is 5 g / liter 30% ammonium sulfate solution (30 g of ammonium sulfate (manufactured by Kishida Chemical Co., Ltd.) dissolved in deionized water to make the total amount 100 g) was mixed so that the molar ratio of residual chlorine to nitrogen was 1: 1.2. .
(Preparation Example B)
A mixed solution of sodium hypochlorite and ammonium sulfate was prepared in the same manner as in Preparation Example A except that the molar ratio of residual chlorine to nitrogen was 1: 1.6.
(Preparation Example C)
A mixed solution of sodium hypochlorite and ammonium sulfate was prepared in the same manner as in Preparation Example A except that the molar ratio of residual chlorine and nitrogen was 1: 0.8.
（調製例Ｄ）次亜塩素酸ナトリウムと臭化アンモニウムとの混合液の調製
次亜塩素酸ナトリウム溶液（残留塩素量１４０ｇ／リットル）を脱イオン水で残留塩素量が５ｇ／リットルになるよう希釈した後、１％水酸化ナトリウム水溶液を２０ｍｌ／リットル加え、３０％臭化アンモニウム水溶液（臭化アンモニウム３０ｇを脱イオン水で溶解し、全量を１００ｇとしたもの）を残留塩素量と窒素のモル比が１：１．２となるよう混合した。
(Preparation Example D) Preparation of a mixture of sodium hypochlorite and ammonium bromide A sodium hypochlorite solution (residual chlorine content 140 g / liter) was diluted with deionized water to a residual chlorine content of 5 g / liter. After adding 1% sodium hydroxide aqueous solution at 20 ml / liter, 30% ammonium bromide aqueous solution (30 g of ammonium bromide dissolved in deionized water to make 100 g in total) was the molar ratio of residual chlorine and nitrogen. Was mixed to 1: 1.2.
（調製例Ｅ）次亜塩素酸ナトリウム水溶液の調製
次亜塩素酸ナトリウム溶液（残留塩素量１４０ｇ／リットル）を脱イオン水で残留塩素が５ｇ／リットルになるよう希釈した。
(Preparation Example E) Preparation of aqueous sodium hypochlorite solution A sodium hypochlorite solution (residual chlorine amount 140 g / liter) was diluted with deionized water so that the residual chlorine was 5 g / liter.
（調製例Ｆ）次亜塩素酸ナトリウムと臭化ナトリウムとの混合液の調製
次亜塩素酸ナトリウム溶液（残留塩素量１４０ｇ／リットル）を脱イオン水で残留塩素が５ｇ／リットルになるよう希釈した後、３０％臭化ナトリウム水溶液（臭化ナトリウム（キシダ化学株式会社製）３０ｇを脱イオン水で溶解し、全量を１００ｇとしたもの）を残留塩素量と臭素のモル比が１：１．２になるよう混合した。
(Preparation Example F) Preparation of a mixture of sodium hypochlorite and sodium bromide A sodium hypochlorite solution (residual chlorine content 140 g / liter) was diluted with deionized water to a residual chlorine content of 5 g / liter. Thereafter, a 30% aqueous solution of sodium bromide (30 g of sodium bromide (manufactured by Kishida Chemical Co., Ltd.) was dissolved in deionized water to make the total amount 100 g) had a molar ratio of residual chlorine to bromine of 1: 1.2. It mixed so that it might become.
（調製例Ｇ）次亜塩素酸ナトリウムと塩化アンモニウムとの混合液の調製
次亜塩素酸ナトリウム溶液（残留塩素量１４０ｇ／リットル）を脱イオン水で残留塩素量が５ｇ／リットルになるよう希釈した後、２０％塩化アンモニウム溶液（塩化アンモニウム（キシダ化学株式会社製）２０ｇを脱イオン水で溶解し、全量を１００ｇとしたもの）を残留塩素量と窒素のモル比が１：１．２になるよう混合した。
(Preparation Example G) Preparation of a mixture of sodium hypochlorite and ammonium chloride A sodium hypochlorite solution (residual chlorine content 140 g / liter) was diluted with deionized water so that the residual chlorine content was 5 g / liter. Thereafter, a 20% ammonium chloride solution (20 g of ammonium chloride (manufactured by Kishida Chemical Co., Ltd.) dissolved in deionized water to make the total amount 100 g) has a molar ratio of residual chlorine to nitrogen of 1: 1.2. Mixed.
（調製例Ｈ）
残留塩素量と窒素のモル比が１：１．６になるよう混合したほかは調製例Ｇと同様に次亜塩素酸ナトリウムと塩化アンモニウムとの混合液を調製した。
(Preparation Example H)
A liquid mixture of sodium hypochlorite and ammonium chloride was prepared in the same manner as in Preparation Example G except that the molar ratio of residual chlorine and nitrogen was 1: 1.6.
（調製例Ｉ）
残留塩素量と窒素のモル比が１：０．８になるよう混合したほかは調製Ｇと同様に次亜塩素酸ナトリウムと塩化アンモニウムとの混合液を調製した。
(Preparation Example I)
A mixture of sodium hypochlorite and ammonium chloride was prepared in the same manner as Preparation G except that the molar ratio of residual chlorine to nitrogen was 1: 0.8.
（試験例１）マンガンの析出抑制効果の確認
大阪市水１リットルにマンガンとして１０ｍｇ／リットルになるよう塩化マンガン・4水和物（キシダ化学株式会社製）を添加して溶解した。３００ｍｌビーカーに小分けし、調製例Ａ〜Ｉの各薬剤をそれぞれ所定濃度となるように添加した。３５℃で１時間撹拌した後、ビーカー内のマンガンの析出状態を目視にて確認した。結果の一例を表１に示す。
(Test Example 1) Confirmation of manganese precipitation suppression effect Manganese chloride tetrahydrate (manufactured by Kishida Chemical Co., Ltd.) was added to 1 liter of Osaka city water to make 10 mg / liter of manganese and dissolved. It subdivided into a 300 ml beaker, and each chemical | medical agent of preparation example A-I was added so that it might become a predetermined density | concentration, respectively. After stirring at 35 ° C. for 1 hour, the precipitation state of manganese in the beaker was visually confirmed. An example of the results is shown in Table 1.
表１の試験結果から、次亜塩素酸ナトリウムと硫酸アンモニウム又は臭化アンモニウムとの併用（実施例1及び2）により、マンガン含有物の析出は見られなかった。これに対し次亜塩素酸ナトリウム単独や臭化ナトリウムとの併用（比較例1及び2）では、マンガン含有物の析出が見られた。 From the test results shown in Table 1, precipitation of manganese-containing materials was not observed when sodium hypochlorite was used in combination with ammonium sulfate or ammonium bromide (Examples 1 and 2). In contrast, precipitation of manganese-containing materials was observed when sodium hypochlorite alone or in combination with sodium bromide (Comparative Examples 1 and 2).
また、次亜塩素酸ナトリウムと塩化アンモニウムとの併用（実施例8及び9）により、マンガン含有物の析出は見られず、残留塩素量と窒素のモル比が１：１．２（実施例8）及び１：１．６（実施例9）のいずれの場合においても同様の結果が得られた。 In addition, the combined use of sodium hypochlorite and ammonium chloride (Examples 8 and 9) showed no precipitation of manganese-containing substances, and the molar ratio of residual chlorine to nitrogen was 1: 1.2 (Example 8). ) And 1: 1.6 (Example 9), similar results were obtained.
（試験例２）マンガン含有物の析出抑制効果の確認
白水試料１リットルにマンガンとして１０ｍｇ／リットルになるよう塩化マンガン・4水和物（キシダ化学株式会社製）を添加して溶解した。１００ｍｌビーカーに小分けし、調製例Ａ〜Ｉの各薬剤をそれぞれ所定濃度となるように添加した。３５℃で1時間撹拌した後、ビーカー内のマンガン異物の析出を目視にて確認した。測定結果の一例を表２に示す。
(Test example 2) Confirmation of precipitation suppression effect of manganese-containing material Manganese chloride tetrahydrate (manufactured by Kishida Chemical Co., Ltd.) was added to 1 liter of white water sample so as to be 10 mg / liter as manganese and dissolved. It subdivided into a 100 ml beaker, and each chemical | medical agent of preparation example A-I was added so that it might become a predetermined density | concentration, respectively. After stirring at 35 ° C. for 1 hour, precipitation of manganese foreign matter in the beaker was visually confirmed. An example of the measurement result is shown in Table 2.
表２の試験結果から、次亜塩素酸ナトリウムと硫酸アンモニウム又は臭化アンモニウムとの併用（実施例3及び4）により、マンガン含有物の析出は見られなかった。これに対し次亜塩素酸ナトリウム単独や臭化ナトリウムとの併用（比較例3及び4）では、マンガン含有物の析出が見られた。 From the test results shown in Table 2, precipitation of manganese-containing material was not observed when sodium hypochlorite was used in combination with ammonium sulfate or ammonium bromide (Examples 3 and 4). On the other hand, precipitation of manganese-containing materials was observed when sodium hypochlorite alone or in combination with sodium bromide (Comparative Examples 3 and 4).
また、次亜塩素酸ナトリウムと塩化アンモニウムとの併用（実施例10及び11）により、マンガン含有物の析出は見られず、残留塩素量と窒素のモル比が１：１．２（実施例10）及び１：１．６（実施例11）のいずれの場合においても同様の結果が得られた。 Further, the combined use of sodium hypochlorite and ammonium chloride (Examples 10 and 11) did not cause precipitation of manganese-containing materials, and the molar ratio of residual chlorine to nitrogen was 1: 1.2 (Example 10). ) And 1: 1.6 (Example 11), similar results were obtained.
（試験例３）白水中のマンガン含有物の析出抑制効果の確認
現場白水ろ液１リットルにマンガンとして１０ｍｇ／リットルとなるよう塩化マンガン・4水和物（キシダ化学株式会社製）を添加して溶解した。この水にＬＢＫＰパルプシートを混合して、１％パルプスラリーを準備した。スラリーの水温を３０℃に設定して、調製例Ａ〜Ｉの各薬剤をそれぞれ所定濃度となるように添加した後、スターラーで1時間撹拌した。薬剤添加スラリーを吸引ろ過して、試験片シートを作成、目視でシート表面の付着物を確認した。測定結果を表３に示す。
(Test Example 3) Confirmation of precipitation suppression effect of manganese-containing substances in white water Manganese chloride tetrahydrate (manufactured by Kishida Chemical Co., Ltd.) was added to 1 liter of on-site white water filtrate so that the concentration of manganese was 10 mg / liter. Dissolved. An LBKP pulp sheet was mixed with this water to prepare a 1% pulp slurry. The water temperature of the slurry was set to 30 ° C., and the respective drugs of Preparation Examples A to I were added so as to have a predetermined concentration, followed by stirring with a stirrer for 1 hour. The chemical addition slurry was suction filtered to prepare a test piece sheet, and the deposit on the sheet surface was visually confirmed. Table 3 shows the measurement results.
表３の試験結果から、次亜塩素酸ナトリウムと硫酸アンモニウム又は臭化アンモニウムとを併用し、かつ残留塩素量と窒（臭）素のモル比が１：１〜１：２の場合（実施例5‐7）においては、マンガン含有物の析出は見られなかった。これに対し、残留塩素量と窒（臭）素のモル比が１：０．８の比較例６、次亜塩素酸ナトリウム単独（比較例7‐8）、及び次亜塩素酸ナトリウムと次亜臭素酸ナトリウムとの組合せ（比較例9‐10）では、マンガン含有物の析出が見られた。 From the test results of Table 3, when sodium hypochlorite and ammonium sulfate or ammonium bromide were used in combination, and the molar ratio of residual chlorine and nitrogen (odor) was 1: 1 to 1: 2 (Example 5) In -7), no manganese-containing precipitates were observed. In contrast, Comparative Example 6 in which the molar ratio of residual chlorine to nitrogen (odor) was 1: 0.8, sodium hypochlorite alone (Comparative Example 7-8), and sodium hypochlorite and hypochlorous acid. In the combination with sodium bromate (Comparative Examples 9-10), precipitation of manganese-containing material was observed.
また、次亜塩素酸ナトリウムと塩化アンモニウムとの併用において、残留塩素量と窒素のモル比が１：１．２（実施例12）及び１：１．６（実施例13）の場合は、マンガン含有物の析出が見られなかった。これに対し、残留塩素量と窒素のモル比が１：０．８の比較例１１では、マンガン含有物の析出が見られた。 Further, in the combined use of sodium hypochlorite and ammonium chloride, when the molar ratio of residual chlorine to nitrogen is 1: 1.2 (Example 12) and 1: 1.6 (Example 13), manganese No precipitation of inclusions was observed. On the other hand, in Comparative Example 11 in which the molar ratio of the residual chlorine amount and nitrogen was 1: 0.8, precipitation of manganese-containing material was observed.
Claims (3)
不溶性マンガンを含む前記製紙工程水に、次亜塩素酸塩と水溶性無機アンモニウム塩とを添加することを含み、
前記水溶性無機アンモニウム塩の添加が、前記製紙工程水における次亜塩素酸塩と水溶性無機アンモニウム塩とのモル比が残留塩素量と窒素とのモル比として１：１〜１：２となるように行われる、マンガン含有物沈着防止方法。 A method for preventing deposition of manganese-containing material on paper in a papermaking process in which hypochlorite is added to papermaking process water for slime control,
The papermaking process water containing insoluble manganese includes adding a hypochlorite and a water-soluble inorganic ammonium salts,
As a result of the addition of the water-soluble inorganic ammonium salt, the molar ratio of hypochlorite to water-soluble inorganic ammonium salt in the papermaking process water is 1: 1 to 1: 2 as the molar ratio of residual chlorine and nitrogen. A method for preventing the deposition of manganese-containing material.
マンガン含有物の紙への沈着を防止するために、不溶性マンガンを含む前記製紙工程水に、次亜塩素酸塩と、水溶性無機アンモニウム塩とを添加することを含み、
前記水溶性無機アンモニウム塩の添加が、前記製紙工程水における次亜塩素酸塩と水溶性無機アンモニウム塩とのモル比が残留塩素量と窒素とのモル比として１：１〜１：２となるように行われる、紙の製造方法。 A paper manufacturing method using papermaking process water to which hypochlorite is added for slime control,
Adding hypochlorite and a water-soluble inorganic ammonium salt to the papermaking process water containing insoluble manganese in order to prevent deposition of manganese-containing materials on the paper,
As a result of the addition of the water-soluble inorganic ammonium salt, the molar ratio of hypochlorite to water-soluble inorganic ammonium salt in the papermaking process water is 1: 1 to 1: 2 as the molar ratio of residual chlorine and nitrogen. The paper manufacturing method is performed as described above.
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